U.S. patent number 3,884,699 [Application Number 05/380,410] was granted by the patent office on 1975-05-20 for photographic materials having reduced static chargeability and method for their production.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Elio Cavallo, Fulvio Furlan.
United States Patent |
3,884,699 |
Cavallo , et al. |
May 20, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Photographic materials having reduced static chargeability and
method for their production
Abstract
The inclusion of both a substantially fluorinated surfactant and
a non-fluorinated betaine and/or N-oxide surfactant into
photographic layers and materials reduces the static chargeability
of such materials.
Inventors: |
Cavallo; Elio (Carcare,
IT), Furlan; Fulvio (Savona, IT) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
11275635 |
Appl.
No.: |
05/380,410 |
Filed: |
July 18, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Jul 24, 1972 [IT] |
|
|
51726/72 |
|
Current U.S.
Class: |
430/502;
430/527 |
Current CPC
Class: |
G03C
1/85 (20130101) |
Current International
Class: |
G03C
1/85 (20060101); G03c 001/06 () |
Field of
Search: |
;96/87A,114.2,114.7,114.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Suro Pico; Alfonso T.
Attorney, Agent or Firm: Alexander, Sell, Steldt &
DeLaHunt
Claims
What we claim is:
1. A method for reducing the chargeability of photographic layers,
upon a support, which essentially consist of a hydrophylic
colloidal binder comprising gelatin, said method consisting of
introducing at least one surfactant having a substantially
fluorinated cation or anion bonded to a hydrophilic group and at
least one of a nonfluorinated betaine or N-oxide surfactant into
said layers by mixing the hydrophilic colloidal binder and
surfactants prior to formation of the photographic layer containing
the surfactants.
2. The method of claim 1, characterized in that said fluorinated
surfactant is a surfactant having a substantially fluorinated
cation.
3. The method for reducing the chargeability of photographic layers
of claim 1, said photographic layers containing a non-fluorinated
anionic surfactant, characterized in that at least one fluorinated
cationic surfactant comprising a substantially fluorinated
aliphatic hydrocarbon residue linked, by means of a chemical bond
or a divalent organic residue comprising a carbonylamino or a
sulphonylamino group, with a chemical residue comprising an
ammonium group, and at least a non-fluorinated betaine surfactant
comprising a non-fluorinated aliphatic hydrocarbon residue linked
with a betaine residue by means of a divalent organic residue
comprising a carbonylamino group, are introduced into said layers
by mixing the hydrophilic colloidal binder and surfactants prior to
formation of the photographic layer containing the surfactants.
4. Method for reducing the chargeability of a photographic material
comprising:
a. a base;
b. at least one layer of a silver halide emulsion dispersed in a
hydrophylic colloidal binder;
which consists of introducing at least one surfactant having a
substantially fluorinated anion or cation and at least a
non-fluorinated betaine and/or N-oxide surfactant into the said at
least one emulsion layer by mixing the surfactants and binder prior
to formation of the layer containing the surfactants.
5. A photographic layer, on a support, essentially consisting of a
hydrophilic colloidal binder comprising gelatin characterized in
that it contains at least one surfactant having a substantially
fluorinated cation or anion and at least a non-fluorinated betaine
and/or N-oxide surfactant.
6. A photographic layer on a support, the layer essentially
consisting of a hydrophylic colloidal binder comprising gelatin,
characterized in that it contains at least one surfactant having a
substantially fluorinated anion or cation, at least one selected
from the group of non-fluorinated betaine and N-oxide surfactants,
and at least one non-fluorinated anionic surfactant.
7. The photographic layer of claim 5 wherein said fluorinated
surfactant is fluorinated cationic surfactant.
8. The photographic layer of claim 7, characterized in that it
contains a non-fluorinated anionic surfactant; at least a
fluorinated cationic surfactant comprising a partially or wholly
fluorinated aliphatic hydrocarbon residue linked, by means of a
chemical bond or a divalent organic residue comprising a
carbonylamino or a sulphonylamino group, with a chemical residue
comprising an ammonium group; and at least a non fluorinated
betaine residue comprising a non-fluorinated aliphatic hydrocarbon
residue linked with a betaine residue by means of a divalent
organic residue comprising a carbonylamino or sulphonylamino
group.
9. The photographic layer of claim 5, characterized in that the
fluorinated surfactant corresponds to the formula:
R.sub.F -- A -- Y
wherein:
R.sub.f represents a substantially fluorinated hydrocarbon
residue;
A is a chemical bond or a divalent organic residue; and
Y represents an anionic, non-ionic, or cationic betaine or N-oxide
hydrophylic group.
10. The photographic layer of claim 9, characterized in that
R.sub.F is a fluorinated alkyl group having from two to eight
carbon atoms, A is a chemical bond or a divalent organic residue
comprising at least a carbonyl, sulphonylamino, alkylene residue
having from one to three carbon atoms, oxygen, carbonylamino,
sulphonylamino, aminocarbonyl, aminosulphonyl, ester,
polyoxyalkylene having from two to 40 oxyalkylene unities and/or R
is an alkyl group having from four to 18 carbon atoms and Z is a
betaine hydrophylic group comprising an ammonium group and an
anionic group or a group comprising an N-oxide bond.
11. A photographic element comprising at least a base and a
photographic layer according to any of claim 5.
12. In a photographic element including:
a. a base;
b. two layers of silver halide emulsion, dispersed in a hydrophylic
colloidal binder comprising gelatin, each emulsion layer being
coated on separate faces of said base;
c. two protective layers, essentially consisting of a hydrophylic
colloidal binder comprising gelatin, each protective layer coated
on one of said emulsion layers, said protective layer containing at
least a non-fluorinated anionic surfactant,
the improvement, which lies in that said protective layers contain
at least one surfactant having a substantially fluorinated anion or
cation and at least a non-fluorinated betaine and/or N-oxide
surfactant.
13. The photographic element of claim 12, characterized in that
said fluorinated surfactant is a fluorinated cationic
surfactant.
14. The photographic element of claim 13, characterized in that it
contains said fluorinated cationic surfactant comprising a
partially or wholly fluorinated aliphatic hydrocarbon residue
linked, by means of a chemical bond or a divalent organic residue
comprising a carbonylamino or sulphonylamino group, with a chemical
residue comprising an ammonium group; and at least a
non-fluorinated betaine surfactant comprising a non-fluorinated
aliphatic hydrocarbon residue linked with a betaine residue by
means of a divalent organic residue comprising a carbonylamino or a
sulphonylamino group.
15. The improved photographic element according to claims 12,
characterized in that the fluorinated surfactant corresponds to the
formula:
R.sub.F -- A -- Y
wherein:
R.sub.f represents a partially or wholly fluorinated hydrocarbon
residue;
A represents a chemical bond or a divalent organic residue; and
Y represents a hydrophylic anionic, non-ionic, cationic, betaine or
N-oxide group; and/or
the non-fluorinated betaine and/or N-oxide surfactant corresponds
to the formula:
R -- a -- z
wherein:
R represents a non-fluorinated hydrocarbon residue;
A has the same meaning as said above;
Z represents a hydrophylic betaine or N-oxide group.
16. The photographic element of claim 15, characterized in that
R.sub.F is an alkyl group having from two to eight carbon atoms, A
is a chemical bond or a divalent residue at least comprising a
carbonyl, sulphonyl, amino, alkylene residue having from one to
three carbon atoms, oxygen, carbonylamino, sulphonylamino,
aminocarbonyl, ester, polyoxyalkylene having from two to 40
oxyalkylene unities and/or R is an alkyl group having from four to
18 carbon atoms and Z is a hydrophylic betaine group comprising an
ammonium and an anionic group or a group comprising an N-oxide
bond.
17. The method of claim 4 wherein the photographic material further
comprises at least one protective layer comprising gelatin for said
emulsion layer, and where said surfactants are present in at least
one of said emulsion and protective layers.
18. The process of claim 4 wherein the emulsion layer further
contains at least one non-fluorinated anionic surfactant.
19. The process of claim 17 wherein the at least one of said
emulsion or protective layers containing the surfactants further
contains at least one non-fluorinated anionic surfactant.
20. The photographic layer of claim 6 wherein said fluorinated
surfactant is a fluorinated cationic surfactant.
21. The photographic layer of claim 6, characterized in that it
contains a non-fluorinated anionic surfactant; at least a
fluorinated cationic surfactant comprising a partially or wholly
fluorinated aliphatic hydrocarbon residue linked, by means of a
chemical bond or a divalent organic residue comprising a
carbonylamino or a sulphonylamino group, with a chemical residue
comprising an ammonium group; and at least a non-fluorinated
betaine residue comprising a non-fluorinated aliphatic hydrocarbon
residue linked with a betaine residue by means of a divalent
organic residue comprising a carbonylamino or a sulphonylamino
group.
22. The photographic layer of claim 6, characterized in that the
fluorinated surfactant corresponds to the formula:
R.sub.F -- A -- Y
wherein:
R.sub.f represents a substantially fluorinated hydrocarbon
residue;
A is a chemical bond or a divalent organic residue; and
Y represents an anionic, non-ionic, or cationic betaine or N-oxide
hydrophylic group.
23. The photographic layer of claim 9 wherein at least one of the
non-fluorinated betaine and N-oxide surfactants correspond to the
formula:
R -- A -- Z
wherein:
R is a non-fluorinated hydrocarbon residue,
A is a chemical bond or a divalent organic residue, and
Z represents a betaine or N-oxide hydrophilic group.
24. The photographic layer of claim 6 wherein at least one of the
non-fluorinated betaine and N-oxide surfactants correspond to the
formula:
R -- A -- Z
wherein:
R is a non-fluorinated hydrocarbon residue,
A is a chemical bond or a divalent organic residue, and
Z represents a betaine or N-oxide hydrophilic group.
25. The photographic layer of claim 22, characterized in that
R.sub.F is a fluorinated alkyl group having from two to eight
carbon atoms, A is a chemical bond or a divalent organic residue
comprising at least a carbonyl, sulphonylamino, alkylene residue
having from one to three carbon atoms, oxygen, carbonylamino,
sulphonylamino, aminocarbonyl, aminosulphonyl, ester,
polyoxyalkylene having from two to 40 oxyalkylene unities and/or R
is an alkyl group having from four to 18 carbon atoms and Z is a
betaine hydrophylic group comprising an ammonium group and/or an
anionic group or a group comprising an N-oxide bond.
26. A photographic element comprising at least a base and a
photographic layer according to claim 6.
27. The improved photographic element according to claim 14
characterized in that the fluorinated surfactant corresponds to the
formula:
wherein:
R.sub.f represents a partially or wholly fluorinated hydrocarbon
residue;
A represents a chemical bond or a divalent organic residue; and
Y represents a hydrophylic anionic, non-ionic, or cationic betaine
or N-oxide group; and/or
the non-fluorinated betaine and/or N-oxide surfactant corresponds
to the formula:
R -- A -- Z
wherein:
R represents a non-fluorinated hydrocarbon residue;
A has the same meaning as said above;
Z represents a hydrophylic betaine or N-oxide group.
28. The photographic element of claim 27, characterized in that
R.sub.F is an alkyl group having from two to eight carbon atoms, A
is a chemical bond or a divalent residue at least comprising a
carbonyl, sulphonyl, amino, alkylene residue having from one to
three carbon atoms, oxygen, carbonylamino, sulphonylamino,
aminocarbonyl, ester, polyoxyalkylene having from two to 40
oxyalkylene unities and/or R is an alkyl group having from four to
18 carbon atoms and Z is a hydrophylic betaine group comprising an
ammonium and an anionic group or a group comprising an N-oxide
bond.
Description
The present invention relates to a method for reducing the
chargeability of photographic layers and photographic elements, to
photographic layers and photographic elements obtained with such a
method.
A photographic material generally consists of a base, at least one
layer of a silver halide emulsion dispersed in a hydrophilic
colloidal binder and, possibly, of at least one protective layer
for such an emulsion, essentially consisting of a hydrophilic
colloidal binder. Such a protective layer can be found either
outside or inside such a photographic material (in this last case,
for instance in color photographic materials, it is called
"interlayer"). It is also known that a photographic material may
include sub-layers, anti-halo layers and other auxiliary layers
adjacent or not the emulsion layers. A photographic material
suitable for radiography particularly consists of a base, at least
two emulsion layers each coated on one surface of said base and at
least two protective layers for said emulsion layers. Such a
material may also contain two sub-layers coated between the
emulsion layers and the base.
It is further known that it is desirable to produce photographic
layers, i.e., emulsion layers and auxiliary layers (such as for
instance protective layers, interlayers, sublayers and anti-halo
layers) exhibiting a reduced static chargeability. During
preparation, packaging or use, such layers are prone to stresses
which may cause electrostatic charges to be formed, which by
discharging produce undesired sensitizations in light-sensitive
emulsions. Particularly, a radiographic material should be usable
in angiographic tables (AOT) and in rapid machines wherein the film
is conveyed at a high speed by means of rollers which exert thereon
a strong pressure and friction action.
In such use, strong electrostatic charges are formed at the surface
of contact between the protective layer and the rollers, thus
giving rise to undesired sensitizations. Such sensitizations are
equivalent to undesired exposures and after the processing sequence
the photographic element will have variedly shaped specks which can
be found above all along the film sides where the contact
rollers/protective layers occurs.
In addition to a reduced chargeability, radiographic materials
suitable for AOT must exhibit a rather high slipperiness index
which reduces the dangers of the apparatus jamming. In some cases,
indeed, the slipperiness index can be related to the static
chargeability itself.
The chargeability of the layers is generally due to the fact that
the layers essentially consist of gelatin or of another hydrophilic
colloidal binder equivalent to gelatin which exhibits a low work
function, i.e., a positive type chargeability. Such a chargeability
is generally modified by the presence of surfactants which induce a
positive or a negative type chargeability into the layers according
to their nature. "Non-fluorinated" anionic surfactants of the type
known to those skilled in the art generally induce a positive type
chargeability into the layers. Fluorinated anionic, non-ionic
N-oxide or betaine surfactants induce a negative type chargeability
into the same layers. Betaine and/or N-oxide non-fluorinated
surfactants in combination with non-fluorinated anionic surfactants
do not substantially improve the static characteristics of the
photographic layers, while on the contrary they improve
slipperiness characteristics. Fluorinated surfactants in
combination with anionic non-fluorinated surfactants improve the
static characteristics of the photographic layers only at a certain
range of relative humidity and leave slipperiness characteristics
unaltered.
The main scope of the present invention is that of providing a
method for removing or at least reducing the electrostatic
chargeability of the photographic layers and above all of the
protective layers, the photographic material consists of.
A further scope of the present invention is that of providing
photographic and radiographic materials having improved
characteristics of electrostatic chargeability.
Another scope of the present invention is that of providing
photographic and radiophotographic materials having improved
characteristics of static chargeability ahd slipperiness.
According to the present invention, we have found that the use of
fluorinated surfactants in combination with non-fluorinated betaine
and/or N-oxide surfactants allows the chargeability of photographic
layers to be reduced at all relative humidities for all of those
photographic layers having a positive chargeability including
chargeability due to the presence of non-fluorinated anionic
surfactants.
Non-fluorinated anionic surfactants, normally used in photography,
for instance as coating, coagulant or dispersing agents, are
surfactants of the type including hydrophobe group linked to an
anionic hydrophilic group directly or by means of a bridge
consisting of a divalent organic residue, as expressed by the
following formula:
R -- A -- X
wherein
R is a non-fluorinated aliphatic, aromatic or a mixed hydrocarbon
residue substituted or not substituted and preferably a linear or
ramified alkyl group having from four to 18 carbon atoms or an aryl
group substituted with one or more alkyl groups altogether having
from four to 18 carbon atoms;
A is a chemical bond or a divalent organic residue, preferably a
carbonyl, a sulphonyl, an amino or an alkylene group preferably
having from one to three carbon atoms, an oxygen atom or groups
consisting of two or more of the above-mentioned groups, such as
for instance carbonylamino, sulphonylamino, aminocarbonyl,
aminosulphonyl, ester or polyoxyalkylene groups preferably
containing from two to forty oxyalkylene unities; and
X is an anionic group of the sulphonate, carboxylate, phosphate and
sulphate type.
Anionic surfactants of this type are described for instance in
Schwarz et al. "Surface Active Agents and Detergents," Vol. I and
II, Interscience Publ., in the U.S. Pat. Nos. 2,992,108; 3,068,101;
3,201,152; 3,165,409; in the French Pat. Nos. 1,556,240; and
1,497,930 and in the British Pat. Specification Nos. 580,504 and
985,483. They will be hereinafter called "non-fluorinated" anionic
surfactants.
With fluorinated surfactants according to the present invention we
mean herewith any type of fluorinated surfactants capable of
inducing a negative charge into the photographic layers containing
them. They include preferably a hydrophobic portion R.sub.F linked
to a hydrophilic portion Y of every kind, may it be anionic,
non-ionic, cationic betaine or N-oxide, by means of a bridge A
which represents a chemical bond or a divalent organic residue, as
expressed by the formula:
R.sub.F -- A -- Y
wherein:
R.sub.f is a substantially fluorinated hydrocarbon residue,
preferably a fluorinated alkyl group having at least two carbon
atoms and more preferably from two to 18 carbon atoms;
A is a chemical bond or a divalent organic residue, preferably of
the above-defined type; and
Y is a hydrophilic group of any type, may it be non-ionic, anionic,
cationic, betaine or N-oxide, and preferably a cationic group.
A substantially fluorinated hydrocarbon residue is by definition a
fluorinated saturated monovalent non-aromatic radical of at least
two carbon atoms. The aliphatic chain may be straight, branched,
or, if sufficiently large, cyclic and may include oxygen or
trivalent nitrogen atoms bonded only to carbon atoms. A fully
fluorinated radical is preferred, but hydrogen or chlorine atoms
may be present as substituents provided that not more than one atom
of either is present for every two carbon atoms, and preferably,
the radical contains at least a terminal perfluoromethyl group.
While radicals containing a larger number of carbon atoms will
function adequately, compounds containing not more than about 20
carbon atoms are preferred since larger radicals usually represent
a less efficient utilization of fluorine than is possible with
shorter chains. Fluoroaliphatic radicals containing about two to
eight carbon atoms are most preferred.
Groups of this type are for instance a polyoxyalkylene group
including from two to 40 oxyalkylene unities, wherein the alkylene
group preferably has from one to three carbon atoms, a group of the
sulphonate, carboxylate, sulphate or phosphate type, or an ammonium
or phosphonium group, or a betaine group including a cation of the
ammonium type and an anion of the carboxylate or sulphonate type,
or a N-oxide group. Groups of this type are, for instance:
##SPC1##
wherein:
R.sub.1, r.sub.2 and R.sub.3 are hydrogen or alkyl group having
from one to 10, preferably from one to six carbon atoms, wherein
said alkyl group possibly can be substituted for instance with an
aryl group, preferably phenyl;
R.sub.1 and R.sub.2 or R.sub.1, R.sub.2 and R.sub.3 altogether also
represent the non-metallic atoms necessary to form a heterocyclic
quaternized nitrogen nucleus, such as for instance piridinium and
imidazolinium;
D.sup.- represents an anion such as for instance halide,
sulphate;
B is an alkylene group possibly comprising a heterous bond,
preferably having from one to six carbon atoms; and
X.sup.- is a carboxylate or sulphonate anion.
Fluorinated surfactants useful to the scope of the present
invention are for instance described in U.S. Pat. Nos. 2,759,019;
2,764,602; 3,589,906; in the Belgian Pat. No. 739,245; and in the
French Pat. No. 2,025,688.
With betaine or N-oxide non-fluorinated surfactants, all those
surfactants which present betaine or N-oxide hydrophilic groups are
hereby intended. This group is preferably linked to a hydrophobic
group R by means of a bridge A, as expressed in the following
formula:
R -- A -- Z
wherein:
R and A preferably represent groups of the above-defined type;
and
Z preferably represents a betaine group, such as for instance of
the type comprising a cation of the ammonium type and an anion of
the carboxylate and sulphonate type, such as for instance of the
above-described type or a group of the N-oxide type, as described
above.
Betaine compounds of this type are for instance described in the
U.S. Pat. No. 3,573,049 and N-oxide compounds of this type are for
instance described in McCutcheon's Detergents and Emulsifiers 1963
Annual (page 8).
Briefly, the present invention concerns a method for reducing or
removing the electrostatic chargeability of a photographic layer
which consists of introducing at least a fluorinated surfactant, as
defined above and at least a non-fluorinated betaine and/or N-oxide
surfactant, as defined above, said layer preferably containing at
least a non-fluorinated anionic surfactant.
The present invention particularly relates to a method for reducing
or removing the electrostatic chargeability of a photographic layer
which consists of introducing into said layer a cationic
fluorinated surfactant, preferably comprising a partially or wholly
fluorinated aliphatic hydrocarbon residue linked, by means of a
chemical bond or a divalent organic residue comprising a
carbonylamino or sulphonylamino group, with a chemical residue
comprising an ammonium group, and at least a betaine or N-oxide
non-fluorinated surfactant preferably a betaine comprising a
non-fluorinated aliphatic hydrocarbon residue linked, by means of a
divalent organic residue comprising a carbonylamino or
sulphonylamino group, with a betaine residue, said layer containing
an anionic non-fluorinated surfactant.
The present invention relates to a photographic layer obtained with
the above-described method and to a photographic element containing
said layer.
The present invention further refers to an improved photographic
material including:
a. a base;
b. at least one layer of a silver halide emulsion;
c. at least one protective layer for said emulsion layer, said
emulsion layer and/or said protective layer containing at least one
non-fluorinated anionic surfactant, as defined above,
the improvement lying in that said emulsion and/or said protective
layer contains at least a fluorinated and a non-fluorinated betaine
and/or N-oxide surfactant, as defined above.
The present invention particularly relates to a material of the
above-described type containing the fluorinated and the
non-fluorinated betaine and/or N-oxide surfactant at least in said
protective layer for said emulsion layer.
More particularly, the present invention relates to an improved
radiographic material including:
a. a base;
b. two emulsion layers each coated on one surface of said base;
c. two protective layers of said emulsion layers, said protective
layers containing at least a non-fluorinated anionic surfactant, as
defined above, the improvement lying in that said protective layers
contain at least one fluorinated and one non-fluorinated betaine
and/or N-oxide surfactant, as described above.
The present invention particularly relates to a material of the
above defined type containing at least a fluorinated cationic
surfactant, at least a non-fluorinated betaine or N-oxide
surfactant and at least a non-fluorinated anionic surfactant, said
fluorinated cationic surfactant preferably comprising a partially
or wholly fluorinated aliphatic hydrocarbon residue linked, by
means of a chemical bond or a divalent organic residue comprising a
carbonylamino or sulphonylamino group, with a chemical residue
comprising an ammonium group; and said non-fluorinated betaine
surfactant preferably comprising a non-fluorinated aliphatic
hydrocarbon residue linked with a betaine residue by means of a
divalent organic residue comprising a carbonyl-amino or
sulphonylamino group.
Compounds of the non-fluorinated anionic surfactant type, as
defined above, are for instance: ##SPC2##
Compounds of this type are sold under registered trade makr, such
as for instance Teepol, Tergitol 4, Nekal BX, Alrowet D 65,
Maprofix LK and Manoxol N.
Compounds of the fluorinated surfactant type, as defined above, are
for instance:
10. C.sub.7 F.sub.15 CO.sub.2 NH.sub.4
11. c.sub.8 f.sub.17 so.sub.2 n (c.sub.2 h.sub.5)ch.sub.2 cook
12. c.sub.8 f.sub.17 so.sub.2 nhc.sub.3 h.sub.6 n.sup.+
(ch.sub.3).sub.3 cl .sup.-
13. C.sub.8 F.sub.17 SO.sub.2 N (C.sub.2 H.sub.5)C.sub.2 H.sub.4
(OC.sub.3 H.sub.6).sub.5 OH
14. c.sub.7 f.sub.15 conhc.sub.3 h.sub.6 n.sup.+ (ch.sub.3).sub.2
ch.sub.2 ch.sub.2 coo .sup.- ##SPC3##
16. c.sub.7 f.sub.15 co.sub.2 h ##SPC4##
18. c.sub.8 f.sub.17 so.sub.2 nhc.sub.3 h.sub.6 n.sup.+
(ch.sub.3).sub.2 c.sub.2 h.sub.5 os.sup.- o.sub.2 oc.sub.2
h.sub.5
19. c.sub.8 f.sub.17 so.sub.2 nhc.sub.3 h.sub.6 n.sup.+
(ch.sub.3).sub.3 i .sup.-
20. c.sub.7 f.sub.15 conhc.sub.3 h.sub.6 n .sup.+ (ch.sub.3).sub.3
c.sup.- ##SPC5## 22. c.sub.4 f.sub.9 so.sub.2 nh c.sub.3 h.sub.6
n.sup.+ (ch.sub.3).sub.3 cl .sup.-
23. C.sub.8 F.sub.17 SO.sub.2 NH C.sub.3 H.sub.6 N .sup.+
(CH.sub.3).sub.2 C.sub.6 H.sub.13 Br .sup.-
24. C.sub.8 F.sub.17 SO.sub.2 N (CH.sub.3) C.sub.3 H.sub.6 N .sup.+
(CH.sub.3).sub.3 T .sup.-
25. c.sub.2 f.sub.5 conhc.sub.3 h.sub.6 n .sup.+ (ch.sub.3).sub.3 i
.sup.- ##SPC6##
compounds of the non-fluorinated betaine and N-oxide surfactant
type, as defined above, are for instance:
26. *cocco -- CONH (CH.sub.2).sub.3 N.sup.+ (CH.sub.3).sub.2
CH.sub.2 COO .sup.-
27. stearyl -- N.sup.+ (CH.sub.3).sub.2 CH.sub.2 COO .sup.+
28. lauryl -- N.sup.+ (CH.sub.3).sub.2 (CH.sub.2).sub.3 COO
.sup.-
29. stearyl -- N.sup.+ (CH.sub.3).sub.2 (CH.sub.2).sub.3
SO.sub.3.sup.- ##SPC7##
The above-listed compounds can be found on the market or prepared
in a conventional way.
Particularly, compound no. 17 has been prepared in the following
way:
To a solution of 127 g. of C.sub.6 F.sub.13 SO.sub.2
NH(CH.sub.2).sub.3 N.sup.+ (CH.sub.3).sub.3 Cl.sup.- in 200 g. of
isopropyl alcohol was added 0.2 mole of 25% methanolic Na O
CH.sub.3. The mixture was digested at 60.degree.-70.degree.C for
1.5 h., then cooled and filtered. The precipitate was washed with
water to give a fine granular powder of the formula:
C.sub.6 F.sub.13 SO.sub.2 N.sup.- (CH.sub.2).sub.3 N.sup.+
(CH.sub.3).sub.3
To a solution of 3.8 g. of ClCH.sub.2 COOH in 80 g. of isopropyl
alcohol and 32 g. of methanol was added 8.6 g. of 25% Na O CH.sub.3
in methanol and then 20 g. of the above:
C.sub.6 F.sub.13 SO.sub.2 N.sup.- (CH.sub.2).sub.3 N.sup.+
(CH.sub.3).sub.3
The mixture was heated at 74.degree.C for 14.5 h., then cooled and
filtered. The precipitate was washed with 80/20 isopropyl
alcohol/methanol. The filtrate and washings were combined and
evaporated to dryness on a hot plate to give a residue of formula:
##SPC9##
Infrared spectroscopy showed a strong carbonyl bond at 6.2.mu..
Calculated: 30.2% C, 3.1% H, 5.0% N. Found: 28.3% C, 3.0% H, 5.0%
N.
The photographic layers of the present invention comprise or
essentially consist of hydrophilic colloidal binder. Such a
hydrophilic colloidal binder preferably is gelatin or any other
film-forming binder permeable to the conventional processing baths
for photographic materials alone or mixed with gelatin.
Such a hydrophilic binder can obtain, dispersed, hydrophobe polymer
particles in order to improve the physical characteristics of the
layers, thus obtained. Particles of this type consist for instance
of polyethylacrylate obtained for instance under the form of a
latex.
Such layers can be hardened with hardeners known to those skilled
in the art, such as for instance formaldehyde, glyoxale,
succinaldehyde, glutaraldehyde, resorcinaldehyde, mucochloric acid,
epoxides used alone or in association and can contain any other
coating materials known to those skilled in the art.
In the case of photographic emulsion layers, the layers will
contain, dispersed, silver halides, such as for instance bromide,
iodide and chloride or mixtures thereof and antifog compounds and
stabilizers in association therewith. In the case of color
emulsions, such as layers can also contain couplers which upon
color development with p-phenylene diamines give rise to yellow,
magenta and cyan dyes.
The above is described for instance in C. E. Kenneth Mees and T. H.
James, "The Theory of the Photographic Process," third edition.
Photographic layers of the above-mentioned type can contain anionic
non-fluorinated surfactants preferably in a quantity ranging from
0.1 to 25, preferably from 1.5 to 5 g. per 100 g. of gelatin or of
another equivalent hydrophilic colloid. The fluorinated and the
non-fluorinated betaine or N-oxide surfactants are for instance
added preferably in a quantity which respectively ranges from 0.1
to 25 and from 0.5 to 30 g. per 100 g. of gelatin or equivalent
colloid, and more preferably in a quantity which respectively
ranges from 0.1 to 5 and from 5 to 15 g. per 100 g. of gelatin.
The above-described surfactants can be both introduced into the
photographic layers before being coated under the form of
solutions, as known to those skilled in the art. The solvents
preferably used are water, alcohol and acetone or mixtures thereof
or any other solvent, provided that it causes no damage to the
photgraphic emulsion.
The chargeabilitiy of the photographic layers according to the
present invention and of the photographic materials they consist of
has been estimated with the following method.
A ring of the material is stretched by several steel rollers and
conveyed upon friction by a steel and gum roller. By means of a
magnetic clutch, the ring is started to move from a speed 0 till to
reach a given speed and the discharged immediately before the
steel/gum roller couple by means of a 3M Type 210 electrostatic
discharger. The charge generated on the film by the passage between
these two rollers is then measured. The characteristics of the
device and the measurement conditions are the following:
film speed = 60 m/minute;
film tension = 0.55 kg/cm.;
pressure between the steel and the gum roller = 1 kg/cm.;
diameters of the gum and the steel roller = 8.2 cm. and 2.5 cm.,
respectively.
The charge density has been measured at a distance of 10 cm. from
the roller axis.
In particular, the slipperiness of the radiographic material in
sheets has been measured by means of an ElemaSchonander device,
wherein the sheet is placed between two intensifying screens, of
the type known in radiography, on which a constant pressure is
exerted. The force necessary to pull out the film from the screens
gives a slipperiness measure. Obviously, the higher the
slipperiness, the lower is such a force.
EXAMPLE 1
A silver bromo-iodide (98% bromide and 2% iodide) radiographic
emulsion has been digested and added with the normal coating finals
known in the photographic field (antifog agents, stabilizers,
harderners, etc.). The emulsion, thus obtained, has been coated on
both surfaces of a polyester base with the aid of anionic
surfactants. Two protective layers have then been coated on both
emulsion layers: They consisted of gelatin and contained silica, as
a matting agent, and the above-described Compound No. 8 and No. 2,
as a coating surfactant, respectively in a quantity of 0.72 and 1.6
g. per 100 g. of gelatin. The same protective layers have been
added or not with the surfactants of the present invention.
The electrostatic chargeability values for the materials with the
additions of the various surfactants, measured as described above,
are shown in Table 1. The quantity in grams of such compounds must
be referred to 100 g. of gelatin.
TABLE 1 ______________________________________ Compound Charge
.mu.c/m.sup.2 ______________________________________ 11 26 25% R.H.
50% R.H. 70% R.H. ______________________________________ 0 g. 0 g.
9 9 2.1 0.25 g. 0 g. -5.5 -4 -4.8 1.0 g. 0 g. -9 -8 -4.5 4.0 g. 0
g. -6 -7 -2.5 0 g. 5 g. 9.2 6 0 0 g. 10 g. 9 5 0 0.15 g. 10 g. -0.8
-1.5 0 0.25 g. 10 g. -5 -7 -0.3 1.0 g. 10 g. -10 -9 -0.3 4.0 g. 10
g. -9 -10 0 13 26 25% R.H. 50% R.H. 70% R.H.
______________________________________ 0 g. 0 g. 9 9 2.7 0.25 g. 0
g. 7 6 0.8 1.0 g. 0 g. -4.6 -1 0.5 4.0 g. 0 g. -10 -4 -0.7 0.25 g.
10 g. 8.4 5 0 1.0 g. 10 g. 7.2 1 0 4.0 g. 10 g. -6.4 -3 0 14 29 25%
R.H. 50% R.H. 70% R.H. ______________________________________ 0 0 9
9 2.7 4.0 0 -5.4 -4.5 -0.5 4.0 10 3 2 0 12 28 25% R.H. 50% R.H. 70%
R.H. ______________________________________ 0 0 9 9 2.7 0.1 0 -9.5
-3 -1.6 0.25 0 -10 -9 -1.6 0.50 0 -9.5 -10 -1 0 5 6 4 0.4 0 10 7
5.5 0 0.1 10 6 4 0 0.25 10 2 -1 0 0.50 10 -4 -3.5 0
______________________________________
EXAMPLE 2
A material like that described in example 1 was produced. Such a
meterial contained or did not contain compounds nos. 16 and 26 of
the present invention. The hereinafter enclosed table 2 gives the
electrostatic chargeability values measured as described above. The
quantities in grams of the compounds added to the emulsion must be
referred to 100 g. of gelatin.
TABLE 2 ______________________________________ Compound Charge
.mu.c/m.sup.2 12 26 25% R.H. 50% R.H. 70% R.H.
______________________________________ 0 0 10 10 0.3 0.15 0 -1.2 -2
-3.5 0.25 0 -4.2 -5.2 -6.5 0 10 8 2.5 0.3 0.15 5 0.7 -0.5 -0.1 0.15
10 5 0.5 0 0.25 5 -0.7 -1.4 0 0.25 10 1.5 -0.4 0
______________________________________
EXAMPLE 3
The same material, as described above, added or not with Compounds
No. 12 and No. 26, according to the present invention, has been
tested from the point of view of the antistatic characteristics in
an angiographic table. The material, cut into sheets and passed
through the table, has been developed with a conventional
photographic developer suitable to radiography, fixed and washed.
We have then examined the sheets to see if they contained specks
caused by electrostatic sensitizations. The results are shown in
Table 3. The quantities of the additions are referred to 100 g. of
gelatin.
TABLE 3 ______________________________________ Compound
Electrostatic charges 12 26 25% R.H. 50% R.H. 70% R.H.
______________________________________ 0 0 YES YES YES 0.15 0 NO NO
YES 0.25 0 NO NO YES 0 5 YES YES NO 0 10 YES YES NO 0.15 10 NO NO
NO 0.25 10 NO NO NO ______________________________________
EXAMPLE 4
The same material, as described above, added or not with Compounds
No. 12 and No. 26 according to the present invention, has been
tested from the point of view of its slipperiness characteristics
with the above-described method. The results are shown in Table
4.
The quantities must be referred to 100 g. of gelatin in the
protective layer.
TABLE 4 ______________________________________ Compound
Slipperiness 12 26 ______________________________________ 0 0 890
g. 0.15 0 900 g. 0.25 0 870 g. 0 5 710 g. 0 10 560 g. 0.25 10 550
g. ______________________________________
EXAMPLE 5
The same material, as described above, added or not with Compounds
No. 12 and 30 according to the present invention has been tested
from the point of view of its antistatic characteristics with the
above-described method. The results are shown in Table 5.
The quantities must be referred to 100 g. of gelatin in the
protective layer.
TABLE 5 ______________________________________ Compound Charge
.mu.c/m.sup.2 12 30 25% R.H. 50% R.H. 70% R.H.
______________________________________ 0 0 10 8 2.1 0.15 0 -3.0
-2.7 -2.8 0.25 0 -6.8 -5.7 -5.1 0 10 9.1 6.8 0.2 0.15 10 -0.5 -1.5
0.2 0.25 10 -1.8 -2.0 0.1
______________________________________
* * * * *