Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
- 10~4463
~ his invention relates to antistatic coating compositions
and to photographic films and materials comprising them.
It is known that in photographic materials the usual
synthetic film supports have the property of being charged
electrostatically, so that the charged films strongly attra~t
the surrounding dust and thereby become soiled at their
surface. Moreover, when such film sùpports are provided
with a silver halide emulsion layer, discharge images may
become visible in the light-sensitive layer upon development.
- 10 ~uch an electrostatic charging results from the friction
. .
of the film support or light-se~sitive photographic material
during winding or unwinding in the coating, cutting or
: . .
packing machines and by rl~nning the photographic material
- through the camera and the projector.
Although it is known tha-t in practice the appearance
of electrostatic charges on synthetic resin supports can
be avoided by the application thereto of an electroconductive
` layer, it is also known that in the case of a polyester
. ............................................. .
film support it is very difficult -to establish and maintain
a satisfactory bond between the surface of the polyester
~ film support and the antistatic layer applied thereto In
- most cases more than one layer is needed, e.g. first a
- special adhesive layer followed by the proper antistatic
layer, whereto sometimes a protective layer is applied.
~- In order to give a sufficient dimensional stability to
the polyester film support it is necessary to orient the
., ~ .
- GV.821 P~
`.: ., . .':, . ' ~: ~ ' ': .' .:
; . ` . . . - : , ~ ~ ', .: ' . ,
... . .. . . . .
1054463
film biaxially and to heat-set it at a relatively high
temperature. ~his biaxial orienting can be performed by
subjecting the film simultaneously to a longitudinal and
a transversal stretching, usually, however, by stretching
the film first in one direction and afterwords in a
direction perpendicular to the first. ~his stretching
of the film up to 3 to 5 times the original dimensions is
performed at a temperature comprises between the glass
..
transition temperature and the softening temperature of the
polyester. In the case of films of polyethylene terephthalate
the stretching is performed usually between ~0 and 90C.
After the biaxial stretching the film is conducted
^ through a heat-setting zone wherein the film is heated until
a temperature between 1~0 and 220C is reached, the filmi':`
being kept under tension in both directions. In this way a
~` dimensionally stable fully clear polyester film is obtained.
~he present invention provides a process for adhering
an antistatic layer to a dimensionally stable polyest,:,
film support, which process comprises applying to an un-
` 20 stretched or only monoaxially stretched polyester film
.
support an antistatic layer from an aqueous coating composition,drying said antistatic layer and stretching it biaxially or
in a direction perpendicular to the first stretching operation
together with the polyester film support and heat-se-tting
the polyester film, said aqueous coating composition
comprising 30 to ~0 % by weight of an electro-conducti~e
"`:
product, 10 to 40 % by weight of a stretch-improving agent
GV.821 PC~ - 2 -
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` .
- ~054463
and 10 to 40 % by weight of an inert filter material.
~ he coating composition for the antistatic layer com-
prises 30 to 80 % by weight of an electroconductive product,
which may be a polymeric material chosen from a ver~
large number of known polymers or copolymers such as :
- polyethylene oxide
- alkali metal salts of copolymers of acr~lic, methacrylic
or maleic acids,
" .
- the free acids and the amine of ammonium salts of polymeric
sulphonic acids such as :
- partially or completely sulphonated polystyrene
- sulphoalkyl esters of polymers or copolymers of acrylic,
methacrylic or maleic acids,
- polyvinylsulphonic acid,
- polyvinylsulphobutyral,
- polyvinylsulphobenzal,
- polyethylenimine hydrochloride,
- guaternized polyethylenimine,
- quaternized polymers of vinylpyridine and derivatives,
. 20 - pol~mers and copolymers of :
- N-vinyl-4-methyl-2-oxazolidinone,
- ~-vinyltrimethylammonium chloride,
- N-(3-acrylamido-propyl)-trimethylammonium chloride,
- acryloyloxyethyldimethylsulphonium chloride
-
~ -(methacryloyloxyethyl)-trimethylammonium chloride,
.:. GV.821 P~
. .
.-. .,
,::
;..
- ~. - . . ... ,. . . . .. ~ . , . . - - , - ..
lOS4463
.... .
~ - ~-(methacryloyloxyethyl)-trimethylammonium methyl sulphate,
,' -N-(2-hydroxy-3-methacryloyloxypropyl)-trimethylammonium
- chloride,
- N-methyl-4-vinylpyridinium chloride,
- vinylbenzyltrimethylammonium chloride,
: -.
; - polymers obtained when polyepichlorohydrin is used as
- quaternizing agent for a tertiar~ amine, a tertiary
~- phosphine or a secondary sulphide,
- polymers obtained by the reaction of polyepichlorohydrin with
.'r' ~ 10 a secondary amine, e.g. morpholine or with a mercaptan such
; as 2-mercapto-ethanol, followed by the ~uaternization with
r ~ :
. an alkylating agent such as an ester of an alcohol and a
strong acid such as the methyl or ethyl ester of sulphuric
,, .
-- acid, phosphoric acid, hydrochloric acid, hydrobromic acid
or hydroiodic acid, e.g. dimethyl sulphate or bromoethanol.
In these polymers or copolymers the recurring units
- carrying anionic or cationic groups are responsible for the
electroconductivity of the antistatic layer. In order to
obtain a sufficient electroconductivity the polymers and
copolymers have to be formed of at least 50 % of recurring
~ .
units comprising these anionic or cationic groups.
In principle it is possible to replace the electro-
conductive polymer in the coating composition for the anti-
`~ static layer partially by a compatible non-electroconductive
.,
~ polymeric or monomeric ingredient. Such an addition can be
,
~ GV.821 PC~ - 4 -
.; .
,f ',
:
.
., .
.: :~ . . , : . . .
.. : - ~ :~ . ,
~'; ' '~ :
- 1~54~3
made to improve certain physical characteristics of the
coating solution. ~or instance polymeric or other
thickening agents, spreading agents etc.
Instead of the polymeric electroconductive products as
exemplified above also low molecular weight antistatic
compounds can be used such as cationic, anionic or amphoteric
compounds that are dispersible or soluble in a~ueous solutions.
In the first place may be used the acid forms and the alkali
metal salts of benzenesulphonic acids, e.g. the sodium salt
of p-nitro-benzene sulphonic acid, p-toluene sulphonic acid
the sodium salt of 4-chloro-m-toluene sulphonic acid~ the
sodium salt of p-bromo-benzene-sulphonic acid, 2,5-dichloro-
benzene-sulphonic acid, the sodium salt of p-hydroxy-benzene
sulphonic acid, and sulphosalicylic acid. Salts of poly-
basic carboxylic acids, e.g. of mellitic acid, citric acid,
salicylic acid, succinic acid, oxalic acid, and maleic acid
can be used also. Moreover, alkyl phosphates having alkyl
.::
; chains of 1 to 5 carbon atoms are also suitable, e.g.
ethyl dihydrogen phosphate, butyl dihydrogen phosphate and
dibutyl hydrogen phosphate. Very interesting are also
~uaternary ammonium compounds such as dimethyl stearamido-
propyl-2-hydroxyethyl ammonium nitrate and the long alkyl
chain-substituted imidazolium derivatives as described in
- the published German patent application 2,128,~03 filed
. .
;. June 9, 1971 by ~uji Shashin ~ilm ~abushiki Kaisha.
;,
. . .
If the low molecular weight antistatic compound is film-
,
... .
GV.821 PC~ - 5 -
, . .
... .. . . ..
, . . . , I , . , . ~:
. ., '' . .'.-: ". ,,; ,'~ ,'
; . - .. - :, ~ . - i , .
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-~ lOS4~63
forming, it can be used as such in the antistatic layer. In
the other case, i-t is mixed with a film-forming inert binder.
A crystalline film of polyethylene terephthalate is
obtained by extruding polyethylene terephthalate in the
-~ melt and to quench it immediately on a cooling cylinder to
form an amorphous film. ~his amorphous film is then
; stretchedlongitudinally and transversally, i.e. ~irst
- longitudinally and then transversally, or first transversally
and then longitudinally, or in but a single operation, i.e.
biaxially, the stretching being performed at 80 to 90C to
form a crystalline film having its dimensions increased by
3 to 5 times. A layer applied before a stretching operation
must meet two special requirements :
1. in unstretched condition and consequently being 3 to 5 times
thicker than after having been stretched, the layer should
possess sufficient adheSion to the polyester film and
sufficient hardness so that it is not easily damaged during
the stretching operation.
. .
2. ~he layer should have a softening temperature which is lower
than the stretching temperature used, which is generally
; from ~0 to 90C so that it can be stretched to a homogeneous
~,~ layer without the appearance of microscopic cracks.
In the case of polymeric antistatic agents this
stretchability often presents problems because the glass
transition temperature (~g) of such polymers usually exceeds
100C. ~hus, polyacrylic acid with a glass transition temper-
ature of 106C (see O.Griffin ~ewis : Physical constants of
; GV.821 PC~ - 6 -
,~.,',
.:.;.
- . . . .
. . .
~. . -..... .
. . . . . . .
- ~54463
: linear homopolymers, Springer Verlag 1963) in anhydrous form is
not stretchable at ~0 to 90C.
Since the glass transition temperature of ionic (co)
.~ polymers cannot be found in the Scientific literature, a
softening temperature, which can be determined on a Koffler-
hot bench, provides a suitable criterion. Examples of such
`;;i~ values are as follows : Softening temperature
`- co(ethylene-maleic acid) 130C
- co(styrene-maleic acid sodium salt) 200C
polystyrene sulphonic acid 220C
polyvinylbenzyl trimethylammonium
chloride >220C
~` An addition of stretch-improving agents according to the
invention has the effect of lowering the softeningtemperature
` of the layer to below ~0 - 90C, which is the usual stretching
temperature.
Most suitable are aliphatic polyhydroxy compounds, which
lower the softening temperature of the layer, e.g. glycerol,
tri (~-hydroxyethyl)glycerol, 1,1,1-tri(hydroxymethyl)propane,
2-nitro-2-ethyl-1,3-propanediol, 1,3-dichloro-2-propanol,
- 1,2,4-butanetriol, 3-hydroxymethyl-2,4-dihydroxypentane,
1,2,6-hexanetriol, 2-hydroxymethyl-4-hydroxy-amyl alcohol,
glycerol-aldehyde and mannitol.
`. .:
Equally suitable compounds are caprolactam and ~ di-
methylurea.
r
Other suitable stretch-improving agents are aliphatic
.~
or sulphonic acids, even though they do not lower the softening
GV.$21 PC~ 7
, . . .
,'' . . ' : : . ` '
; . ' ` ~ . : ~ , ' ' . ';
4~;3
temperature of the layer, e.g. malonic acid, glutaric acid,
adipic acid, azelaic acid, sebacic acid, mono- and dichloro-
acetic acid, 1,2,3-propene tricarboxylic acid, acrylic acid,
methacrylic acid, maleic acid, fumaric acid, itaconic acid,
and 2-sulpho-ethyl methacrylate; further aromatic acids
such as phthalic acid, o-sulphobenzoic acid, o-nitrobenzoic
acid, o-aminobenzoic acid, p-hydroxybenzoic acid, and sali-
cyclic acid.
~ inally 10 to 40 % by weight of an inert filler material
is added to the coating composition of the antistatic layer
as well. ~he purpose of the addition of the filler material
is to improve the mechanical properties of the layer, mainly
with respect to the scratchability, the surface-vulnerability,
wet finger prints, etc. ~he best results are obtained by the
addition to the layer of heterodisperse particles having a
,,:
softening temperature above 50C. In this respect the
primary and secondary polymeric dispersions of i.a. poly-
styrene, polyalkyl methacrylate, polyethylene and poly-
propylene can be mentioned. Very good results can also be
obtained with inorganic pigments such as amorphous or
crystalline silicon dioxide, titanium dioxide and calclum
` carbonate, although some of these pigments give the layer t
a somewhat mat aspect as a result of their high refractive
. ~
index. Amorphous silicon dioxide, i.a. obtained by
hydrolysis in situ of silane compounds, however, gives a
clear layer with optimal mechanical and antistatical charac-
teristics.
.,
~ GV.821 PC~ - 8 -
,~ .
`:~
`` ~05~463
. Appropriate silane compounds correspond to the following
general formula :
R ~ ,R"
R'~ R"'
wherein :
. each of R and R' represents hydrogen, alkyl, chloroalkyl,
:~ aminoalkyl, alkoxy, hydroxyalkoxy, aminoalkoxy, epoxy-
~ alkoxy, alkoxyalkoxy, acetyloxy, vinyl or phenyl, the
; different alkyl and alkoxy groups containing 1 to 4 carbon
atoms, and
each of R" and R"' represents cyanoalkyl, aminoalkyl, amino-
alkoxyalkyl, epoxyalkoxyalkyl, alkoxycarbonylalkyl,
.;` (meth)acryloyloxyalkyl, (meth)acrylamidoalkyl, chloro-
f.~ acetamidoalkyl~ ~(aminoalkyl)-aminoalkyl, bis(~-hydroxy-
:: .
`: alkyl)-aminoalkyl, alkoxy, hydroxyalkoxy, aminoalkoxy,
epoxyalkoxy, alkoxyalkoxy, phenoxy, acetyloxy, and
. ~-r7-oxabicyclo-(4,1,0)-heptylJ-alkyl, the different alkyl
;~-. or alkoxy groups containing 1 to 4 carbon atoms.
. Suitable silane compounds according to the invention
; 20 are e.g. :
`i. dimethyl-diphenoxy-silane
- -
~ dimethyl-bis(2,3-epoxypropoxy)-silane
'?.; diphenoxy-diphenyl-silane
;~ diethoxy-dimethyl-silane
diethoxy-methyl-(4-aminobutyl)-silane
~-;` diethoxy-diphenyl-silane
.. ;;
.- GV.821 PC~ ~ 9 ~
.
s
~L~54463
2-(ethoxycarbonyl)-propyl-diethoxy-silane
dimethoxy-methyl-~N(2-aminoethyl)-3-amino-2-methyl-propyl3-
silane
dimethoxy-bis¦N-(2-hydroxyethyl)~-3-aminopropyl-silane
3-chloropropyl-trimethoxy-silane
trimethoxy-3-(methacryloyloxy)propyl-silane
trimethoxy-~N-(2-aminoethyl)-3-aminopropyl3-silane
trimethoxy-t3-(2,3-epoxypropoxy)-propylJ-silane
bis(2-aminoethoxy)-methyl-~3-(2-aminoethoxy)-propyl~-silane
trimethoxy-2-~3-r7-oxabicyclo-(4,1,0-heptyl)J-ethyl~-silane
triethoxy-silane
methyl-triethoxy-silane
triethox~-vinyl-silane
phenyl-triethoxy-silane
2-cyanoethyl-triethoxy-silane
3-aminopropyl-triethoxy-silane
(2-ethoxycàrbonyl-ethyl)-triethoxy-silane
(3-chloroacetamido-propyl)-triethoxy-silane
(3-acrylamidopropyl)-triethoxy-silane
:
20 tripropoxysilane
. tributoxysilane
tris(2-methoxyethoxy)-vinyl-silane
.; tris(2,3-epoxypropoxy)-ethyl-silane
., .
~~~ tetraethoxysilane
`~. tetrapropoxysilane
.`-; tetrabutoxysilane
.~-. tetrakis(2,3-dihydroxypropoxy)-silane
- GV.~21 PC~ - 10 -
.j:
!: :
- . ~ ` `~
`` 10544~3
vinyl-triacetox~-silane.
Aqueous solutions of polymeric compoundS with a glas~
transition temperature above 50C such as gelatin and poly-
vinyl alcohol can also be used as filler material.
In order to form the antistatic layer on the polyester
film support the electroconductive product and the other
ingredients are dissolved or dispersed in water or in mixtures
of water and solvents such as in lower alcohols, which are
not swelling agents for the amorphous polyethylene tereph-thala-te
and thus will not bring about crystallization of the polyester.
The antistatic coating composition is applied in such
concentration and manner known in the art as to yield on the
polyester film support after stretching an antistatic layer
having a thickness of preferably between 0.1 and 1.0 ~um.
To give the layer a sufficlent electroconductivity and
for the use thereof as an antistatic coating on a polyester
film, the surface resistance should not exceed well defined
..;
` limits, which themselves are influenced by the degree of
relative humidity. ~or example, the surface resistance at
.
30% relative humidity should be lower than 1.1011 ohm/sq. 9
whereas at 60% relative humidity it should be lower than
5.~,i 1.101 Ohm/Sq-
~hus the electroconductivity of the antistatic layer
.~ is determined by measuring its surface resistance. ~herefore,
~?~ after conditioning at a specific relative humidity of a
.-- . .
~ . ,
~ material composed of a polyester film support, to which an
,. . i
GV.821 PCT - 11 -
` -
1~54~63
antistatic coating according to the invention has been
applied, the surface resistance of the material is measured
by means of a cell, both poles of which have a width of
0.5 cm and are at a distance of 1 cm from each other.
Ir, the examples various layers and their electro-
conductivity are described.
In addition to the electroconductive product, the
stretch-improving agent and the filler material, the
composition of the antistatic layer may include small amoun-ts,
e.g. between 10 and 20 % by weight with respect to the dry
weight of the wole coating composition, of a waxy material,
such as unbranched saturated fatty acids, e.g. stearic acid
and palmitic acid, esters derived from fatty acids and fatty
alcohols, e.g. stearyl stearate and n-hexadecyl palmitate,
pentaerythritol esters of fatty acids such as stearic acid,
, :~
~ palmitic acid and lauric acid, sucrose diesters of fatty
:;
; acids such as sucrose distearate, ~,N-alkylene-bis-fatty
acid amides, e.g. ~,N-ethylene-bis-oleylamide and montan
wax derivatives, which are generally glycerol, glycol or
polymerised ethylene glycol esters of acids from montan wax.
- ~hese waxy materials are added to the coating composition of
. the antistatic layer to further improve its resistance
. . .
~ to friction and scratching.
;- ~he layer according to this invention may be applied by
, .
spray, brush, roller, doctor blade, air brush, or wiping
techniques.
.,
` GV.821 PC~ - 12 -
~.
:- - 105~463
. ` ,
The adhesion of the antistatic layer to the polyester
film support is excellent. ~his adhesion can be tested by
cross-wise scratching the antistatic layer by means of a
; sharp knife. Upon these scratches a pressure-sensitive
adhesive tape is pressed and thereafter torn off at once.
~he adhesion is considered to be good if but very small
- pieces of the antistatic layer are torn off.
~he advantage of the process according to the invention
' is manifest. If, as described hereinbefore~ the coating
composition for the antistatic layer is applied to the
polyester film support before the transversal stretching of
the film, the film then has a width 3 to 5 times less than
after -the stretching operation. Consequently a 3 to 5
,- times narrower coating machine suffices, which is a very
~f'
` interesting advantage from an economic viewpoint. ~he drying
cabinets can also be made smaller 3 to 5 times.
~he invention offers an other advantage. Indeed after
~ the stretching a heat-setting of the polyester support at
`, 180 to 220C is necessary i.a. to complete the crystallizatlon
of the polymer and to secure the dimensional stability of
-~ the polyester film. ~his heating at 1~0 to 220C gives
,~. .
, rise to a superficial interdiffusion between the antistatic
,~ layer and the polyester support, thus resulting in an
improved adhesion of the antistatic layer to the support
without the need of the addition of adhesion-improving agents.
~; Another advantage of the antistatic layer according to
the invention is the permanent antistatic effect obtained
GV.821 PC~ - 13 -
'~: , .. ' . ' . . , .. , ., ': , . , - - . . . -
- 1054463
with this layer even after rinsing of the film with water
- or photographic baths. ~his is a consequence of the partial
interdiffusion of the layer in the suppor~ during heat-
setting. Moreover, the heat-setting sometimes causes partial
thermic cross-linking when an electro-conductive polymer
i is used, which makes these antistatic agents less readily
soluble.
According to the invention also a photographic fil~
material is provided comprising a polyester support, at
least one light-sensitive silver halide emulsion layer on
one side of the polyester support, and on the other side
~ of that support an antistatic layer comprising an electro-
-- conductive product, a stretch-improving agent and an
,
inert filler ~aterial as hereinbefore defined.
~ilms having an antistatic layer according to the
- present invention may serve for the manufacture f photo-
graphic black-and-white as well as colour films.
According to the invention also the monolayer antistatic
i coating can be applied to both sides of a polyester film
`; 20 support. In this way a material is obtained that does not
. attract the surrounding dust, that has excellent optical
properties and can be used as a mounting foil, a drafting
foil, or as a support for copying processes.
.
he examples hereinafter are especially directed to the
use of polyethylene terephthalate film as support for the
antistatic layer and the other layers applied thereto. The `~
. .
GV.821 PC~ - 14 - `
. .
`- 1~544~;3
,
- antistatic layer can, however, be applied also to other
` polyester films, e.g. films of polyesters resulting from
the polycondensation of glycol, or mixtures of glycols with
terephthalic acid, or mixtures of terephthalic acid with
minor amounts of other dicarboxylic acids such as isophthalic
acid, diphenic acid, and sebacic acid.
~ he invention is illustra-ted by the following examples.
Example 1
A substantially amorphous polyethylene terephthalate
;. 10 film having a thickness of approximatively 2.2 mm was formed
- by extrusion of molten polyethylene terephthalate at
~ about 280C on a quench drum and was chilled to about 75C
and then stretched in the longitudinal direction over a
differential speed roll stretching device to 3.5 times its
,, .
. initial dimension a-t a temperature of 84C.
An antistatic layer was applied to the thus stretched
;
film at a ratio of 70 sq.m/liter from the following coating
composition :
polystyrene sulphonic acid as a 10 %
; aqueous solution adjusted to pH 8.5 with
ammonium hydroxide 600 ml
. glycerol ~0 ml
methylcellulose (low viscosity) as a 10%
aqueous solution 100 ml
.~. ,.
- UL~RAVON W (10 % aqueous solution)5 ml
water to make 1000 ml.
., .
~` GV.821 PC~ - 15 -
, .
' .
. .,, ~ .
'
"
,. :, . . . .
~054463
~ UL~RAVON W is the trade mark of CIBA A.G., Switzerlancl,
-; for a dispersing agent consisting of the disodium salt o~
heptadecylbenzimidazole disulphonic acid.
~he layer was dried in a hot airstream whereafter the
film was stretched transversal]y to 3.5 times its original t
r. width at a temperature of abou1; $7G in a tenter frame.
~he final thickness of the film was about 0.180 mm.
The film was then conducted into an extension of the
tenter frame, where it was heat-set while kept under tension
~- 10 at a temperature of 200C for about 10 seconds. After heat-
- setting the coated film was cooled and wound up in the
normal manner.
~he antistatic layer adhered very well to the polyester
support, which was proved according to the method of the
;~ pressure-sensitive adhesive tape described hereinbefore.
~ .
The surface resistance of the antistatic layer measured
at a relative humidity of 30 % was 1.5 x 108 Ohms/s~.
Example 2
. ~ ,
~- ~he method described in Example 1 was repeated, with the
difference, however, that the following coating composition
- was used :
polystyrene sulphonic acid as a 10%
a~ueous solution adjusted to pH 8.5
with ammonium hydroxide 900 ml
methylsulphonic acid adjusted to pH 8.5
with ammonium hydroxide 15 ml
. ,
GV.821 PC~ - 16 -
,.
` 10~4463
; 30% aqueous polyethylene dispersion 75 mL
UL~RAVON W (10 % aqueous solution) 5 ml
` water until 1000 ml.
- ~he antistatic layer adhered very well to the suppor-t
-~ and i-ts surface resistance at 30 ~ of relative humidity
was 5.107 Ohms/sq.
Example ~
r~ ~he method described ir! ~xample 1 was repeated, with
,...
the difference, however, that -the following coating compo-
sition was used :
~ co(ethylene/maleic acid) sodium salt as
.~ 10 % aqueous solution 500 m~
.,.3~ .
'~'r glycerol 50 ml
SILANE A-186 50 ml
saponine (a 12.5 % solution in a mixture ;
of water and ethanol (80:20) ~ ml
r~ water to make 1000 ml.
Silane A-186 is the trade mark of Union Carbide, U.S.A.
for a silane compound of the formula :
.,;" ~
CH2~ IOCH3
o~ccH22 I C 2 CH2 li OC~3
.-, ~CH2
~he antistatic layer adhered very well to the support
~! and its surface resistance at a relative humidity of ~0 %
was 2.109 Ohms/sq.
.,
. --
GV.821 PCT ~ 17 -
jr ' . : . ~ ~;
' :'''~ '. ' .
:,., . . '
,:........... . : ' , :
. : ~
.. : - . ' , , . '' '
` 105~463
xample 4 t
r, The method described in Example 1 was repeated, with
the difference, however, that the following coating compo-
sition was used :
co(styrene/maleic acid) sodium salt as a
:~ 20 % aqueous solution 500 ml
.` ~RIOL H 50 ml
30 % aqueous dispersion of colloidal
: silicon dioxide 150 ml
10% aqueous solution of UL~RAVON W 5 ml
.-: water to make 1000 ml.
RIOL H is the trade mark of Rheinpreussen A.G., Germany,
- for hexanetriol of the formula :
' ~ CH20H
H C-CHOH-CH -~H
CH20X
~ he antistatic layer adhered very well to the support
and its surface resistance at a relative humidity of 30 %
-~ was 2.109 Ohms/sq.
Example 5
The method described in Example 1 was repeated, with
the difference, however, that the following coating composi-
tion was used :
. polystyrene sulphonic acid as a 10%
; aqueous solution adjusted to pH 8.5 with
~ ammonium hydroxide 500 ml
GV.821 PC~ - 18 -
:
.
. . .
~' ' , .
54~63
diethylene glycol monoe-thyl ether 15 ml
- SILANE Y-4087 25 ml
-; 10 % aqueous solution of ULTRAVON W 5 ml
water to make 1000 ml.
ANE Y 4087 is the trade mark of Union Carbide, U.S.A.
for a silane compound of the formula :
., H2 ~ CH-CH2-0-(CH2)3-liOCH
OCH3
- 10 The antistatic layer adhered very well to the support
;
and its surface resistance at a relative humidity of 30 %
was 8.109 Ohms/sq.
Example 6
The method described in Example 1 was repeated, with
the difference, however, that the following coating compo-
:
~` sition was used :
,;, .
10 % aqueous solution of CA~ANAC SN500 ml
30 % aqueous dispersion of polystyrene100 ml
` maleic acid 40 g
r`,: 20 10 % aqueous solution of ULTRAVON W 5 ml
water to make 1000 ml.
CATANAC SN is the trade mark of American Cyanamid for a
65 % paste in a mixture of water and isopropanol of
-~ stearamidopropyl dimethyl ~-hydroxyethyl ammonlumnitrate.
he antistatic layer adhered very well to the support
.;~ ......................................................................... .
...... :
!"~, GV.821 PCT - 19 -
.: ~
, ,:
:
......
'',.. ' ' , ' . .' :, ' , . ' ' ' ` :, . ' ' .
"`~` ' ' ` : ~ ~' ' ' . . '
;' ' ' , ' ' ' ' - ' .
. ' .
105~4~3
and its ~urface resistance at a relative humidity of 3V %
was 7.5 . 108 Ohms/sq.
Example 7
The method described in Example 1 was repeated9 with
the difference, however, that the following coating compo-
sition was used :
-: 10 % aqueous solution of CALGON
`; CONDUC~IVE POLYMER 261 700 ml
glycerol 20 ml
10 % aqueous solution of gelatin 100 ml
12.5 % solution of saponine in a
mixture of water and ethanol (~0:20)10 ml
water to make 1000 ml.
` CALGON CONDUC~IVE POLYMER 261 is the trade mark of
Calgon Corporation, U.S.A., for an electroconductive polymer
containing 39.1 % by weight of active conductive solids, and
having recurring units of the following type :
. .
` 3 ~N~ 3
- EC CH2CH Cl _
H2
- ~he antistatic Iayer adhered very well to the support
and its surface resistance at a reLative humidity of 30 %
was 6.107 Ohms/sq.
.~ GV . 821 PC~ - 20 -
.;,~
.
1~4463
Example 8
~he method described in ~xample 1 was repeated, with
the difference, however, that the following coating compo-
- sition was used :
10% aqueous solution of CALGON CO~DUC~IVE
POLYMER 261 300 ml
. 10 % aqueous solution of adipic acid
adjusted to pH 8.5 with ammonium hydroxide 400 ml
20 % aqueous solution of polyvinyl alcohol 150 ml
: 10 10 % aqueous solution of UL~RAVO~ W 5 ml
water to make 1000 ml.
. ~he antistatic layer adhered very well to the support
and its surface resistance at a relative humidity of 30 %
:- was 1.5 . 10 Ohms/sq.
- Example 9
~ A substantially amorphous polyethylene terephthalate ~-
film having a thickness of approximatively 1.2 mm was formed
by extrusion of molten polyethylene terephthalate at a
temperature of about 280C on a quench drum and was chilled
to a temperature of about 75C and then stretched in the
longitudinal direction over a differential speed roll
. stretching device to 3.5 times its initial dimenslon at
a temperature of 84C.
~ One side of this support was coated with an antistatic
.. layer as described in example 4. ~he other side of the support
was coated with a subbing layer of a co(vinyl chloride,
~ GV.821 PC~ - 21 -
.. :
-. ~054~L63
vinylidene chloride, butyl acrylate7 i-taconic acid)
(63/30/5/2) as described in the U.K.Patent Specification
1,234,755-
~he layer was dried in a hot airstream, whereafter
,.~.,
;- the film was stretched transversa:lly in a tenter frame to
3.5 times its original width at a temperature of about
87C. ~he final thickness of the film was about 0.1 mm.
~ he film was then conducted into an extension of the
tenter frame, where it was heat-set while kept u~der
tension at a temperature of 180C for about 20 seconds.
~ he subbing layer comprising vinyl chloride copolymer
is then coated with the following composition at a ratio
of 30 sq.m per liter :
gelatin 8 g
; colloidal silicon dioxide 12 g
caprolactam 4 g
hexanetriol 2 g
: glyoxal 1 g
surface-active coating aids 0.6 g
water 600 ml
,
- methanol 400 ml~
After drying, a light-sensitive gelatin silver halide
emulsion of the positive fine grain type was coated thereon.
:
he antistatic properties of this photographic material
;~ were very good. Dust was not attracted by this film. It
appeared that after storage in roll form, the emulsion, which r
;; had been in contact with this rear side, had not been influenced
adversely.
` GV.821 PC~ - 22 -
' ',:
. . . . .
.. , - , ":
., . . ,.~ ~ .
