Note: Descriptions are shown in the official language in which they were submitted.
~057554
The invention relates to a process for the hardening of
photographic layers which contain protein, preferably gelatine
Numerous substancés have already been described as
hardeners for protein and particularly for gelatine, for
example metal salts such as chromium, aluminium or zirconium
salts, aldehydes and halogen-containing aldehyde compounds,
in particular formaldehyde, dialdehydes and mucochloric acid,
1,2- and 1,4-diketones such as cyclohexane-1,2-dione and
quinones, chlorides of dibasic organic acids, the anhydrides
of tetracarboxylic acid, compounds which contain several
reactive vinyl groups, such as vinyl sulphones, acrylamides,
compounds containing at least two heterocyclic 3-membered
rings which can easily be split, such as ethylene oxide and
ethylene imine, polyfunctional methane sulphonic acid esters
and bis-~-chloroacyl amido compounds.
High-molecular weight hardeners have recently become
known, for example polyacrolein and its derivatives or copolymers
as well as alginic acid derivatives. These are used especially
as hardeners which are con~ined to the layer into which they
are introduced.
Many of the known compounds, however, are unsultable
for photographic purposes. Some of them are photographically
active and therefore unsuitable for hardening photographic
materials while others cannot be used because they have a
harmful effect on certain of the physical properties of
gelatine layers such as their brittleness. Other may cause
discoloration or a change in pH during the hardening reaction.
Furthermore, it is particularly important for hardening
photographic layers that maximum hardening should be reached as
soon as possible after drying so that the material which is
A-G 1198 - 2 - ~
1057554
being hardened does not continuously change its permeability
to the developer solution as is the case, for example, with
mucochloric acid or formaldehyde.
Some cross-linking agents for gelatine, for example the
ethylene imine compounds, also have a deleterious effect on the
skin so that for physiological reasons they are unsuitable.
It has long been known to use trichlorotriazine and
dichloroaminotriazines as hardeners. Their disadvantages are
their relatively high vapour pressure and their physiological
action. Water-soluble derivatives which contain carboxyl and
sulphonic acid groups and which have been obtained by the
reaction of cyanuric chloride with one mol of dimainoalkyl or
diaminoacryl sulphonic acid or carboxylic acid do not have these
disadvantages and have therefore recently been proposed as
hardeners. Their practical utility is, however, limited by
the fact that, owing to their high solubility, they decompose
when left to stand in aqueous solution and therefore rapidly
lose their activity. Hydroxy dichlorotriazine has also been
proposed as hardener. Lastly, in a hardener used for photo-
graphic layers which contain gelatine it is of the utmostimportance both for reason~ of preparation of the photographic
material and its processing that the onset of the cross-linking
reaction should be controllable within certain limits, for
example by suitable choice of the drying t~mperature or the
pH.
Compounds which contain two or more acrylic acid amido
or vinyl sulphone groups in the molecule are also known as
hardeners for photographic gelatine layers, e,g. divinyl
sulphone, arylene-bis-vinyl sulphones, N,N~,N~-tris-acryloyl-
hydrotriazine or methylene-bis-vinyl sulphonamide.
Although hardening of the compounds is quite satisfactory
after some time, the compounds are only sparingly soluble in
A-G 1198 - 3 -
10575S4
water, With the result that the layer may be unevenly hardened.
The consequences of the undesirable properties o the known hard-
eners described above are extremely important or photographic purposes
because important photographic properties such as the gradation and sensitivity
and, in many cases, also the silver covering power depend on the degree of
cross-linking of the layer-forming colloid and alter during storage. Although
this disadvantage can be attenuated by brie treatment of the solidified layer
with ammonia or an amine~ it cannot be completely overcome by this method
and there is the added disadvantage that aliphatic disulphones have pro-
perties which are damaging to the skin.
Carbamoyl pyridinium salts are also known as hardeners with a very
good cross-linking action for gelatine and high molecular weight compounds or
mixtures of compounds which contain carboxyl groups and amino groups. The
disadvantage of these hardeners is that they are liable to split off pyridine
or pyridine derivatives during their reaction with the binder and their com-
mercial applications are therefore limited.
It is an object of this invention to develop quick-acting hardeners
for layers which contain protein, in particular gelatine layers for photo-
graphic purposes, which hardeners will not have the technical disadvantages
of the known compounds.
According to the present invention, there is provided a process
for the hardening of a photographic layer which contains protein, in whicha
l-carbamoyloxpyridinium salt of the formula
1 / N - C - O ~ RR5 X~
in which Rl represents an alkyl or aryl group; R2 represents an alkyl or
aryl group or one of the groups
R6 ~
N-C-, or R --6
o o
~0575S4
in which R6 represents hydrogen or an alkyl or aryl group; R7 represents an
alkyl group and R8 represents an alkyl group or Rl and R2 may together re-
present the atoms required to complete a heterocyclic ring system or a
piperazine ring in which the second nitrogen atom establishes the connection
to a second, similar, molecular residue of the general formula; R3 represents
hydrogen or halogen or an alkyl, oxyalkyl, cyanol -CONH2 or -NH-COO alkyl
group; R4 represents hydrogen or an alkyl group; R5 represents hydrogen or a
methyl group or X represents an anion, is used as hardener.
More particularly, this invention relates to a process for harden-
ing p~otographic layers which contain protein, ~preferably gelatine), which
is characterised by the use of a carbamoyl oxypyridinium salt as hardener,
wherein the hardeners correspond to the general formula
N - C - O - N ~ X
-4a-
,
~ :J
~057559~
in Which
Rl ~epresents an alkyl group with~preferably 1 to 3 carbon
atoms or an aryl group such as a phenyl group,
R2 represents an alkyl group with preferably 1 to 3 carbon
atoms or an aryl group such as a phenyl group or the groups
\ N - C - R8-0-C-,
in which
R6 represents hydrogen, an alkyl group such as a methyl or
ethyl group or an aryl group,
R7 represents an alkyl group such as a methyl or ethyl group
and
R8 represents an alkyl group with preferably 1 to 4 carbon atoms; or
Rl and R2 may together represent the atoms required to
complete a heterocyclic ring system such as a pyrrolidine-,
morpholine-, piperidine-, perhydroazepine-, 1,2,3,4-tetra-
hydroquinoline- or imidazolidine-2-one-ring or
Rl and R2 may together represent the atoms required to complete
a piperazine ring in which the second nitrogen atom establishcs
the connection to a second, similar, molecular residue of the
general formula,
R3 represents hydrogen, a halogen atom such as chlorine or
bromine, an alkyl group such as a methyl or ethyl group, an
oxalkyl group with preferably 1 to 3 carbon atoms, a cyano
group or a -CONH2 or -NH-C-0 alkyl group (such as a methyl
or ethyl group)
R4 represents hydrogen or an alkyl group such as a methyl or
ethyl group and
R5 represents hydrogen or a methyl group;
10575S4
X represents an anion such as a Cl-, B~4- or-C104- ion.
The follo~ing compounds have been found to be particularly
adrantageous. The list is giren purely by ~ay of example and is not intended
to restrict the scope of the inrention.
1057554
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A- G 1198
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A-G 1198 - 8 -
1057554
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A G 1198 - 10 -
1057554
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A-G 1198 - 12 -
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A_G 1198 - 14 -
1057554
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A-G 1198 - - 15 -
- 1057554
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A-G 1198 - 16 -
1057554
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A-G 1198 - 18 -
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A_G 1198 . - 19 -
lOS7SS4
l-carbamoyloxy- and l-allophanyloxy pyridinium salts are
new compounds~ the preparation of which has not previously
been described, but they can be obtained by a surprisingly
simple method, namely by reacting carbamide chlorides or
allophanic acid chlorides with pyridine-N-oxides in aprotic
media, sometimes also in alcoholic solution or even in aqueous
systems. They are stable for a considerable time at room
temperature in the pure state and, even in aqueous solution at
pH-values between 5 and 7, they undergo degradation surprisingly
slowly. The stability of the new compounds can be even further
improved by suitable choice of so-called hard anions, e.g.
fluoborate or perchlorate. Whereas the chlorides are in
many cases hygroscopic,j;the fluoborates or perchlorates which
are easily obtainable by salt conversion with sodium fluoborate
or sodium perchlorate do ~ot show this characteristic.
The N-~x~des used as starting materials are known. They
are usually prepared from the free bases by oxidation with
organic peracids or mixtures o~ hydrogen peroxides and organic
acids. Special representatives of these compounds, e.g.
alkoxy pyridine-N-oxides, however, can generally be prepared
more satisfactorily by nucleophilic exchange reactions from the
corresponding nitropyridine- or halopyridina-N-oxides.
Reference may be made in this connection to "Aromatic Amine
Oxides" by E. Ochiai, Elsevier 1967 and the
references given therein as well as to the publication "Die
Einf~hrung von Substituenten in den Pyridin-Ring" by K. Thomas
and D. Jerchel in the journal "Angewandte Chemie" vol. 70,
pages 719-746 (1958).
N,N-disu~stituted carbamide chlorides can be obtained
from the corresponding secondary amines by reaction with phosgene.
Generally speaking, di- or tri-substituted allophanic acid
chlorides are prepared by reacting the corresponding alkyl ureas
A-G 1198 - 20
~0575S4
with phosgene (see H. Ulrich, J.N. Tilley, A.A.R. Sayigh;
J. Org. Chem. 2g, 2401 (1964) and German Offenlegungsschrift
2 008 116).
Several methods are available for the preparation of
the new hardeners according to the invention. These methods
will now be illustrated with the aid of six examples.
Method of preparation A
22 g of dimethylcarbamide chloride are added dropwise
to 19 g (0.2 mol) of pyridine-N-oxide in 100 ml of anhydrous
acetone at O to 15C over a period of 15 minutes. The
temperature is kept at 10 to 15C for a further 45 minutes
until the product crystallises. The reaction mixture is then
suction-filtered.
The yield was 36 g, which was 89 ~ (of the theoretical yield)
and the melting point was 163 to 167C with decomposition.
Compound 15:
30 g of morpholine carbamide chloride in 50 ml of
methylene chloride are added dropwise with stirring to 19 g
(0.2 mol) of pyridine-N-oxide in 100 ml of methylene chloride at
O - 15C. The product is suction-filtered after 60 minutes.
The yield was 45 g which was 92~ of the theory with a melting
point of 132 C (decomposition). According to the analytical
results obtained after crystallisation from ethanol/ether,
compound 15 corresponds to the monohydrate CloH13N203Cl.H20.
Found: C: 45.8 H: 5.7 N: 10.8 Cl: 13.7
Calculated: 45.7 5.7 10.7 13.5
AJG 1198 - 21 -
1057554
Method of preparation B
Compound 11:
27g (0.2 mol) of diethylcarbamide chloride in 50 ml of
ether are added dropwise with stirring to a solution of 22 g
(0.2 mol) of 2-methylpyridine-N-oxide in 100 ml of ether at
0-10C. Stirring is continued for a further two hours at 5C
and the reaction mixture is then cooled to 0C, the supernatant
ether is decanted from the oil and 36 g of sodium perchlorate
in ethanol are added. After the reaction mixture ha~ been
left to stand overnight, it is suction-filtered to remove the
precipitated sodium chloride, concentrated by evaporation
under vacuum at a temperature below 30C and left to stand for
crystallisation.
The yield was 40 g which was 65 ~ of the theory the melting
point was 130 to 132C, with decomposition.
Method of preparation C
Compound 17:
20 g of sodium perchlorate is added with as little water
as possible to a solution of 24 5 g (0 1 mol) of compound 15 in
60 ml of water The reaction mixture is left to stand for 30
minutes and then suction-filtered.
The yield was 27 g, and the melting point was 150 to 152C,
with decomposition.
Compound 16
A solution of 24.5 g (0.1 mol) of compound 15 is added to
a solution of 14 g of sodium fluoborate in 25 ml of water. The
r0action mixture is suction-filtered after 60 minutes.
The yield was 25 g, and the melting point was 138 to 140C
with decomposition.
A-G 1198 - 22 -
1057S54
Method of preparation D
Compound 3~:
30 g (0.2 mol) of morpholine carbamide chloride are added
dropwise at room temperature to 36.4 g (0.2 mol) of 3-ethoxy-
carbonyl aminopyridine-N-oxide in 150 ml of isopropanol. After
10 hours, 30 g of sodium perchlorate in 150 ml of ethanol are
added and reaction mixture is left to stand overnight. The
precipitated crystals are suction-filtered.
The yield was 50 g, with a melting point of 162 to 163C
with decomposition.
The compounds according to the invention may be added
as aqueous or alcoholic solutions to the protein layers before
they are cast. Hardening may set in extremely rapidly or
moderately soon, depending on the structure of the compound and
the concentration employed, but even with the slowest compounds
it is completed within one to two days so that no after-
hardening effects need be expected. The most rapid hardeners
are the allophanyl oxypyridinium salts derived from allophanic
acid chlorides, somewhat slower are those carbamoyl oxypyridinium
salt~ which are derived from electro-negatlvely substituted
pyridine-N-oxides while the slowe~t are those repre~éntatives
of the new class of compounds which are derived from alectro-
postively substituted pyridine-N-oxides. These, and
particularly the carbamoyl oxypyridinium salts derived from alkyl
pyridine-N-oxides, are so stable that they can be kept in aqueous
solution for many days without any loss of their hardening
action and they do not increase the visco~ity of a gelatine
solution at 38C over several hours.
One particularly advantageous method of applying the
hardeners consists of casting the protein solutions before they
have been treated with hardener and then coating the resulting
layers, optionally when they are already dry, with a solution
A-G 1198 - 23 -
1057554
of the hardening compounds. If desired, however, the compounds
may also be added as aqueous solutions while the photographic
material is being processed, for example it may be added to a
bath of the unhardened or only slightly hardened photographic
layers before development.
The compounds described here may be used either singly
or as mixtures. They may advantageously be used for hardening
photographic layers which, in addition to containing gelatine,
also contain other homopolymers and copolymers with carboxyl
groups as binders It is assumed that the compounds according
to the invention are capable of effecting cross-linking of
gelatine and polymers which contain carboxyl groups.
The term ~photographic layers~ is used here in a quite
general sense to mean layers which are used in photographic
materials, for example light-sensitive silver halide emulsion
layers, protective layers, filter layers, antihalation layers,
backing layers or photographic auxiliary layers in general.
Light-sensitive emulsion layers for which the hardening
process according to the invention is particularly suitable
include, for e~ample, those layers which are based on unsensitised
emulsions, X-ray emulsions and other spectrally sensitised
emulsions. The hardening process according to the invention has
also been found satisfactory for hardening the various gelatine
layers used for black-and-white and colour photographic
processes. The process according to the invention has been
found to be particularly suitable for hardening photographic
layer combination~ which are used for carrying out colour
photographic processes, e.g. combinations which contain emulsion
layers with colour couplers or emulsion layers which are intended
to be treated with ~olutions which contain colour couplers.
The action of the compounds used according to the invention
is not deleteriously affected by the usual photographic
A-G 1198 - 24 -
10575S4
additives ~he hardeners are also inert towards photographically
active substances such as water-soluble and emulsified water
insoluble dye components, stabilisers, sensitisers and the like.
Moreover, they have no influence on the light-sensitive silver
halide emulsions. Furthermore, the compounds can be combined
with any compounds from the classes of hardeners previously
known, for example formalin, mucochloric acid, triacrylo~ormal,
bisvinyl sulphones, bisvinyl sulphonamides, dialdehydes, bis-
chloroacetamides or inorganic salts, e.g. tervalent chromium,
tervalent aluminium or zirconium salts.
The layers may contain water-soluble high-polymer compounds
in addition to gelatine, in particular polyvinyl alcohol,
polyacrylic acid sodium and other copolymers which contain
carboxyl groups, polyvinyl pyrrolidone, polyacrylamide or
high-molecular weight natural substances such as dextranes,
dextrines, starch ether, alginic acid or alginic acid
derivatives.
The concentrations at which the hardeners according to the
invention ale used may vary within wide limits and depend
mainly on the particular compound used as hardener.
Satisfactory results are obtained with quantities of 0.5
to 10 ~ by weight and particularly 1 to 5 ~ by weight, based
on the dry weight of binder.
The activity of the hardening compounds is assessed by
means of the melti~g point of the layers, which can be
determined as follows:
A layer cast on a support is half dipped into water which is
continuously heated to a temperature of 100C. The temperature
at which the layer begins to run off the support (formation of
streaks) is taken as the melting point or melting-off point.
According to this method of measurement, pure protein or gelatine
layers which are free from hardener in no case show an increase
A-G 1198 - 25 -
105755~
in melting point. The melting-off point under these conditions
is 30 to 35C.
Swelling of the layer is determined gravimetrically in
distilled water at 22C after 10 minutes~ treatment. It i9
characterised by the swelling factor:
wet weight of layer = swelling factor.
dry weight of layer
To determine the wet scratch resistance, a metal tip
of a specified size is passed over the wet layer and loaded wi~h
with an increasing weight. The wet scratch resistance is
indicated by that weight at which the tip leaves a visible
scratching trace on the layer. A high weight corresponds to
a high wet scratch resistance.
The compounds accord~g to the invention react surprisingly
quickly with proteins after the drying process and thereby
enable materials which contain protein to be hardened to an
optimum degree within a very short time. This unexpected
effect of the compounds is particularly important for
hardening photographlc materials which contain proteins and
polymers with carboxyl groups as binders, The desired degree
of hardening can easily be adjusted quite accurately at the
stage of preparation of the materials without prolonged storage
times and the attendant uncertainties of uncontrollable
subsequent hardening.
The hardening compounds used according to the invention
are thus distinguished by a hardening reaction which is
surprisingly rapid and without after-effects. This property of
the compounds makes them eminently suitable for the preparation
of very hard photographic layers with a clearly defined and low
degree of swelling. This result can be obtained simply by
treating the dry or slightly swelled photographic layer with
A-G 1198 - 26 -
1057554
a solution of the hardening compound for a short time and then
rapidly drying the layer, Any degree of hardening can easily
be achieved in this way.
The following examples serve to explain the invention
more fully.
Example 1
5 ~ aqueous solutions are prepared from compounds 1, 2,
3, 4, 5, 6, 7, 9, l o, 11, 13, 14, 15, 16, 17, 18, 19, 20, 21,
22, 23, 25, 26, 27, 29, 30, 34, 36, 39, 43, 44, 45, 50, 51, 52,
53, 54, 55, 56, 57, 58. Strips of a gelatine layer 10 ,u in
thickness which has been cast on a prepared cellulose triacetate
substrate and which contains 18 % by weight of a cyan coupler of
the formula OH
CO - NH-- (CH2)17- CH3
S03Na
are half dipped into these solutions for 10 seconds and dried in
a blast of hot air. The sample strips are then washed with
water at 80C. In all the sample strips, the layer adheres to
the half which has been dipped into solution but is washed off
the unhardened half.
Example 2
Strips of gelatine layers similar to those described in
example 1 are treated with aqueous solutions of the compounds
according to the invention indicated in the following table
and dried as described in example 1. The layer melting points,
swelling factor and wet strength are then determined. The
results are shown in the table.
For comparison, 2 samples in each case of the same
unhardened gelatine layer were dipped into a 2.5 % solution of
tris-acryloyl-hexahydro-s-triazine (A) and mucochloric acid (B)
for 1 minute or 3 minutes and the melting point of the layer was
A-G 1198 - 27 -
1~57554
determined as already described:
Comparison Layer melting Swelling factor Wet strength
sample point
after after after
drying 1 day 1 day 3 days 1 day 3 days
A ~5 C
B 35C
The results show that the compounds according to the
invention will harden unhardened gelatine layers to an extent
which is ~ast to boiling either immediately a~ter drying or,
at the latest, after one day's storage and that no subsequent
hardening takes place.
A-G 1198 - 28 -
10575S4
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1057554
Example 3
Aqueous solutions of the compounds according to the invention
are used as described in example 2 in the freshly dissolved
state and after 3 hours~ storage and 24 hours~ storage Or the
solutions at room temperature Yor bathing strips of an unhardened
gelatine layer imilar to that described in example l, The
layers are dried and their properties are determined after 1
day~s storage at room temperature. The results are shown in
the following table, in which SF = swelling factor and WS =
wet strength.
A-G 1198 - 31 -
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o o c`~
O ~ C~ D 0 0 C~ ~ 0
o
A-G 1198 - ~2 -
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The results of example 3 show the excellent stability of
the aqueous solutions of the compounds according to the invention
even after one day's storage. There is therefore no doubt that
the compounds are sufficiently stable for large-scale industrial
use.
Example 4
Compounds 1, 2, 3, 5, 15, 18, 20, 21, 22, 249 25, 26, 27,
34, 39, 43, 45, 46, 47, 48, 49, 50 are added to samples of a
10% gelatine solution in quantities of 2 ~, based on the
gelatine. 30 minutes after addition of the compounds, the
gelatine is cast on a transparent cellulose triacetate substrate
covered with a bonding layer to form gelatine layers 10 ~ in
thickness which are then dried. 24 hours after casting, the
layer melting point, swelling factors and wet strength values
were determined. The results are shown in the following
table:
Compound Layer melting Swelling Wet strength
(2 % based point factor (in pond)
on gelatine)
l . . _ __
1 10'100 3.4 550 p
2 10~100 3.4 450 p
3 10'100 4.0 35 P
10~100 4.4 200 p
10~100 3.8 550 p
18 10~100 ~I.O 750 p
10l100 4.8 600 p
21 ~0'100 4.4 500 p
22 10l100 3.3 450 p
24 10l100 3.8 350 p
10'100 5.0 250 p
26 10'100 3.4 400 p
27 10'100 4.2 300 p
34 10'100 4.3
39 10'100 3.5 55 P
43 10'100 4.1 450 p
10l100 3.5 450 p
46 10'100 3.1 450 p
47 10l100 4.1 450 p
48 10'100 4.4 250 p
49 10'100 4.2 250 p
5o 10l100 3.5 450 p
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One part of the casting solution is left to stand at 40C
for 2 hours or 5 hours after their preparation. The viscosities
of the solutions are determined in an outflow viscosimeter and
the results are compared with those oî fresh solutions (outflow
time in seconds = ")
Compound 107~ gelatine (+ 2% hardener)
viscosit~ fresh after 2 hour after 5 hours
. . _ . ~
33" 33.5" 34"
2 26" 26" 26"
3 27" 27" 28"
28~' 28" 28"
45" 54" 75"
1& 41" 45" 45"
42" 48" 59"
21 27" 31" 36"
24 26" 26" 27"
31" 40" 41
26 28" 31" 35
27 28~ 29" 29
34 25~ 26" 27
39 32" 32" 34
43 35" 36" 41
46 27" 29" 29
47 29" 34" 37
48 30" 38" 46"
49 32" 41" 41
A_G 1198
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For comparison, the following results are obtained with
samples which, instead of containing a compound according to
the invention, contain one of the following conventional
hardeners:
5 Compound 10% gelatina (+ 2% hardener)
viscosity
freshafter 2 hours after 5 hours
~ . _
C 80~' 80" cross-linked
D 178" 222" 268n
E 149" 156" 189"
C: l-methyl-3(3l-dimethylaminopropyl)-carbodiimide hydro-
chloride
D: 2,4-dichloro-6-(2~-methoxy)-ethoxy-1,3,5-triazine
E: 2,4-dichloro-6-isopropoxy-1,3,5-triazine.
As the results show, the hardening action of the compounds
according to the invention sets in only slowly when they are
in a state of solution and lt only comes ~ully into effect
after the materials have dried. This means that the hardeners
according to the invention can be added to casting solutions
even at higher gelatine concentrations without the gelatine
being cross-linked within 5 hours or undergoing too much
increase in its voscosity. The hardeners according to the
invention therefore do not require the use of dosing devices
or other technical apparatus designed to add the hardener
immediately before casting.
A-G 1198 _ 35
1057554
Example 5
An unsensitised silver bromide emulsion layer is applied
to a paper substrate which has been laminated with polyethylene
and covered with a bonding layer, and the emulsion layer is
dried Hardening is carried out by application of a 3~ aqueous
solution of compounds 1, 2, 13, 15, 16, 18, 20, 22, 25, 44 and
55 according to the invention, followed by drying. For
comparison, another emulsion layer is hardened with 0.5 ~
formaldehyde as casting additive and another with 0.5~ of
6-methoxyethoxy-2,4-dichlorotriazine.
The samples are stored for 1, 3 and 5 days and then
exposed under a step wedge and processed at 25C as follows:
Developer: 3 g of hydroquinone,
1 g of p-methylaminophenol,
13 g of anhydrous sodium sulphite,
23 g of anhydrous sodium carbonate,
1 g of potassium bromide
made up with water to 1000 ml.
Processing: 2 minutes at 25C.
Short stop bath: 2~ acetic aoid solution, 1 minute at 25~
Fixing bath: 200 g of sodium thiosulphate,
20 g o~ potassium metabisulphite,
water up to 1000 ml
Processing: 5 minutes at 25C
Washing: 15 minutes at 20C.
The following results are obtained:
The speed is constant after 1 day when compounds 1, 2, 13,
15, 16, 20~ 22, 25 and 44 are used and after 3 days and when
compounds 18 and 55 are used. Swelling factor and speed
undergo no further changes.
A-G 1198 - 36 -
lOS75S4
In samples hardened with formaldehyde or alkoxy
dichlorotriazine hardeners, some loss in speed could still be
observed after 8 days. The final speed was practically
the same in all of the samples.
It follows that the compounds according to the invention
enable the final hardness to be rapidly obtained and give rise
to photographic products with constant speed over a
prolonged storage time.
Example 6
A colour reversal film is prepared by applying the
following layers in succession on a cellulose acetate substrate:
]. A red-sensitive silver iodobromide emulsion (70 g of
gelatine, 32 g of silver (96~ silver bromide, 4~ silver iodide)
per kg, 6 g of a cyan coupler of the
formulaOH 3 ~--C18H37
~CO-NH-~3
~03H
24 g of cyan coupler o~ the formula
OH 3~ ~C18ff37
CO - NH ~
S03H
silver application 0.9 g/m2;
A-G 1198- 37 -
~057554
2. An interlayer containing 3 g of polymeric white coupler
of the formula _ 1
-CH2-CIH - C!H I ~ n
~/ \ NH O
N CH-CH3
N ~
~H3
per kg of casting solution;
3. A green-sensitised silver iodobromide emulsion (96% AgBr,
4% AgI) containing, per kg of emulsion, 70 g of gelatine, 32 g
of silver, 25 g of a magenta coupler of the formula
C14H29
,~O-CH~CH2-0-C-NH-~ C~
CH3 - N
silver application 0.9 g/m2;
4 A silver filter layer containing colloidal silver obtained
from 1.8 g of silver nitrate in 12 g of gelatine per 1000 ml.
Colour density o.6 (measured behind blue filter);
5. A non-sensitised silver iodobromide emulsion with an
iodide content of 2~, containing, per kg, 110 g of gelatine,
70 g of silver and 45 g of a yellow coupler of the formula
C - CH2-C-NH~ / ~ S03H
~18H37
A-G 1198 - 38 -
1057554
silver application 1.3 g/m2.
The ~aterial i9 hardened by bathing it in a 2%-solution
of compound 15.
A second reversal material is built up in a similar
manner, with the difference that the red-sensitised and the
green-sensitised emulsion layer and the interlayers contain 0,4%
of 1,3,5-tris-acryloyl-hexahydro-5-triazine, based on gelatine,
and the non-sensitised layer contains o.6~ of tris-acryloyl-
hexahydro-5-triazine as hardener.
Two lengths of film are obtained, from esch of which a
sample is exposed behind a graduated wedge after 1 day, 8 days
and 28 days' storage at room temperature and then subjected to
reversal processing as described below.
One further sample from each film length is stored moist
at 35C and 80% relative humidity for 3 days.
Processing: 20C.
Black-and-white developer: (7 minutes)
300 ml of distilled water,
2 g of sodium hexametaphosphate,
2.3 ~ of p-methylamirlophenol,
g of sodium sulphite anhydrous,
6.6 g of hydroquinone,
g of sodium carbonate anhydrous,
3.5 g of potassium thiocyanate,
1.8 g of potassium bromide,
0.008 g of potassium iodide,
made up with water to 1000 ml: pH 10.
A-G 1198 - 39 -
lOS7554
Short stop bath: (5minutes)
300 -ml of distilled water,
30 g of sodium acetate crysrallised,
5 ml of acetic acid
made up to 100 ml with water: pH 5.
Washing: 10 minutes
Reversal exposure: 2minutes
Colour development: 18 minutes
300 ml of distilled water,
2 g of nitrilotriacetic acid,
3.5 g of N,N-diethyl-p-phenylenediamine,
g of trisodium phosphate,
0.7 g of potassium bromide,
0.8 g of hydroxylamine hydrochloride,
made up to 1000 ml with water: pH 11.7.
Washing: 5 minutes,
Bleaching bath: 5 minutes
8 g of potassium ferricyanide,
20 g of potassium bromide,
12 g of disodium phosphate
m&de up to 1000 ml with water, adjusted to pH 5.2
with acetic acid.
Washing: 5 minutes
Fixing bath: 5 minutes
150 g of ammonium thiosulphate,
A-G 1198 - 40 -
lQ57554
10 g of sodium sulphite anhydrous,
2 g of sodium hexametaphosphate
made up to 1000 ml with water: pH 7.
Final washing: 5 minutes.
The photographic assessment shows that the sample which
has been hardened with compound 15 according to the invention
reaches it final speed after only 1 day and has been
hardened fast to boiling. No loss of speed by subsequent
further hardening is observed.
The sample which has been hardened with conventional
hardener has a layer melting point of 40C after 1 day and 8
days, and the sample which has been hardened for 28 days shows
a distinct loss in speed compared with that of the fresh
sample. The general speed of the sample when fresh is
higher than that of the material which has been hardened with
the compound according to the invention.
Both film samples have the same final speed
after 3 days' storage in a moist atmosphere. Reversal fog,
maximum density loss and gradation changes do not occur.
A-G 1198 - 41 -
