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Патент USA US2411878

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Patented Dec.
a ' umrspjrsraras PATENT; OFFICE;
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2,411,818‘
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A,
I Albert Hershberg'er, Kenmore,N. .Y., aaignor to
E. I. du Pont de Nemours &1Company,_Wil- '
mington, Del,‘ a corporation of
I
a I
. N. Drawing.’ Application September 21,1942,
Serial'No. 459,187
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a
' ‘10 em. (01. 154-139)
Tl invention ‘relates to. the lamination of ' non-?brous, synthetic film and rubber-like vuldense,“ non-?brous, non-vulcanizable, ‘relatively i canlzable butadiene copolymer, which bond is not
‘aifectedyby gasoline. v'I'hese and other objects
non-porous, self-sustaining, synthetic ?lm,
sheets, pellicles ‘and-the like-to ,copolymers‘ of "will more clearly appear hereinafter.
The above. objectsare accomplished by this
butadiene. More particularlythis invention re
lates to the bonding of self-sustaining, non-vul
:
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' invention which, brie?y stated, comprises apply
‘canizable,.synthetic ?lms-oi nylon, regenerated
ing to either the self-sustaining, non-vulcaniz
cellulose, cellulose esters, as cellulose acetate,
able, non-?brous, synthetic ?lm or to the buta
diene, and of isobutylene and butadiene. ~
polymerization catalyst, dissolved together in a
diene‘copolymer, or to both, aliquid composition
polyvinyl alcohol, polyvinyl acetal, as polyvinyl
butyral, etc. to rubber-like vulcaniz'able copoly '10 comprising essentially polyvinyl butyral and
thermo-setting, resin-forming ingredients com
mers of butadiene, such as the copolymers of
prising polyhydric phenol, aldehyde and a basic,
acrylonitrile and butadiene', of styrene and buta
Because of their exceptional resistance to the I, volatile organic solvent, causing the resin-form
deteriorating in?uence of gasoline and relatively 15 ing ingredients to react whereby to form an ad
hesive coating, and thereafter pressing together
low penetrability of vgasoline vapors, compounded
stocks of rubber-like vulcanizable butadiene
_ the ?lm and copolymer with the adhesive coating
therebetween, at an elevated temperature.
It is essential that the polyvinyl butryal used
with acrylonitrile, have‘ been widely employed in
the construction of'self-sealing fueltanlgs for 20 in the adhesive composition be one in which at
least.30%, but no, more than 90%, of the hy
military planes andilike motorized equipment.
copolymers, such as the copolymers of- butadiene ‘
However, with the advent of gasoline-of‘ very
. droxyl groups of polyvinyl alcohol are substi
high octane rating dueito the presence therein
tuted by reacting the polyvinyl alcohol with
. of aromatichydrocarbons, the impenetrability of
butyraldehyde. , This corresponds to the range
’ these copolymers is no longer entirely satisfac-~ 25 of from 20.7% to 47.4% combined butyraldehyde.
The polyvinyl butyrals in which the degree of
' , tory. and the need arises for materials exhibiting
'.'_'still higher resistance’ to the penetration of‘ these
vapors.
,1} It has now been found that self-sustaining,
‘l'non-vulcanizable, ‘non-?brous, synthetic ?lm of
jfmaterials such as nylon, regenerated cellulose,
ff cellulose acetate, polyvinyl ‘alcohol, polyvinyl
' acetals, etc., when laminated to rubber-like vul
substitution is in the range of from 50% to 85%‘
431.3% to 45.7% combinedybutyraldehyde) are
preferred.
The polyvinyl ‘butyrals produced by. butyrali
zation of polyvinyl alcohol substantially free of
, any ester groups are preferred.
However, poly
vinyl butyrals containing a minor proportion of
ester. groups may be used with good results.
canizable copolymers of butadiene possess the
desired impenetrability. In addition, the fuel 35 ‘As ‘the thermo-setting, resin-forming ingredi
ents of the adhesive, the polyhydric phenols and
barrier so formed has the lightness, compactness,
~ toughness and freedom‘ from shattering which is
‘,aldehydes‘which are soluble to the extent of 1%
. essential in virtually all materials entering into
to 10% ‘or more in the organic solvent employed,
airplane construction.
~
are preferred. The resin should‘ be capable of
, An object of this invention, therefore, is to 40 polymerizing rapidly and completely to a sub
provide for the bonding of self-sustaining, non
vulcanizable, non-?brous, synthetic ?lm to co
. polymers of butadiene. Another object is to pro
, vide a novel laminated structure of self-sustain
;ing, non-vulcanizable, non-?brous, synthetic ?lm
joined to rubber-like vulcanizable butadiene co
, polymer. A further object is to provide a light,
_"compact,
tough, non-shatterable, laminated
[structure of self-sustaining, non-vulcanizable,
stantially insoluble, 'infusible stage at tempera
The polyhydric
L tures of about 125° C.'or less.
phenols having the hydroxyl groups in vthe benz
45 ene nucleus meta with respect to one another,
such as resorcinol, phloroglucinol and orcinol are
- preferred. vAlso suitable vare the naturally occur
ring polyhydric phenols, e. g. the tannins ex
tracted from the bark of the quebracho tree,
known asvquebracho extract. As the aldehyde
" norh?brous, synthetic ?lm and rubber-like vul 50 member
of the resin-forming ingredients, form
'canizable butadiene copolymer which} is more
aldehyde, paraeformaldehyde, acetaldehyde, fur- .
impenetrable to gasoline vapors than isthe' same
fural and aldol are especially satisfactory. Pref
' thickness of the'butadiene copolymer alone. A’
erably, the aldehyde is used in some excess of that '
"s'till‘further object is to provide a tenacious
‘I‘Zbond' ‘between self-sustaining, non-‘vulcanizable,
55 theoretically required to react with all the phenol
2,411,878
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present in order to insure polymerization of all
the phenol.
A basic catalyst, to promote polymerization of
the resin-forming ingredients, such as NaOH,
KOH, etc., in concentrations of 0.5% to 1.5% by
weight. on the basis of the resin-forming mate
rials, is preferred.
The ratio of the partial polyvinyl butyral to
the polyhydric phenol-aldehyde resin-forming in
100 pounds per square inch, to obtain the best
bond, but reasonably satisfactory results can be
obtained by setting up the structure at substan
tially lower pressures, e. g. 5 to 10 pounds per
square inch. Also, the temperatures of curing will
vary, depending on the speci?c butadiene co
polymer and various compounding ‘ingredients
in the compounded stock. In general, this tem
perature may range ‘from 80° C. to 160° C. Also,
gredients is important. Best results are obtained 10 the time‘may be varied. At the lower tempera
when the partial polyvinyl butyral is used in con
tures, it’ is generally advisable to prolong the
centrations between 30% and 45% of the total
period for setting up the structure and curing
weight of tlie solvent-free adhesive layer, al
the butadiene copolymer, while at the higher
though good results are obtainable when the con
temperatures the time can be somewhat shorter.
centration of the polyvinyl butyral resin is within 15 While the time may be varied from a few minutes
the range of from 25% to 60% of the total weight
to several hours,. in general the time range from
of the solvent-free adhesive layer.
20 minutes to 80 minutes is preferred.
The composition ' consisting of a polyvinyl
The following examples further illustrate the
butyral and the resin-forming ingredients dis
solved in a suitable organic solvent may be ap
plied to the ?lm, sheet or pellicle by spraying, by
brushing, by doctoring or by any other suitable
means, and the solvent evaporated at room tem
perature or at an elevated temperature. At some
invention. Parts are by weight.
20
Example I
An adhesive for bonding polyvinyl alcohol ?lm
to “Ameripol” (a compounded acrylonitrile-bu
tadiene copolymer) is prepared as follows: 15
stage in the drying process or subsequent'to dry 25 parts of polyvinyl butyral prepared by combining
ing, it is preferred that the temperature be raised
. about 85% of the hydroxyl groups of polyvinyl al
to a point above 65° C.,' but not in excess of 125° C..
cohol with butyraldehyde are dissolved in 85 parts
for a short time to insure polymerization of the
of ethyl alcohol denatured with methyl alcohol.
resin-forming materials to a substantially in
To this solution is added a solution comprised of
soluble, infusible form. However, ?nal heating 30 15 parts of resorcinol, 31 parts of formalin (37%
of the polyhydric phenol-aldehyde resin to the
formaldehyde in water), 3 parts of 10% solution
infusible, insoluble state need not take place until
of NaOH in water and 104 parts of ethyl alcohol
the laminated structure issubjected to an ele
vated temperature to cure the compounded buta
denatured with methyl alcohol. After thoroughly
mixing the two solutions together, the composi
diene copolymer.
tion is applied to a polyvinyl alcohol ?lm to form
The butadiene copolymers, such as the copoly
a coating thereon when dry that is not greater
mer of acrylonitrile and butadiene, the copolymer
than 0.0001 inch in thickness. The coated ?lm
of styrene and butadiene, and the copolymer of
is allowed to air-dry for a few minutes to evap
isobutylene and butadiene, may be mixed or com
orate the bulk of the solvent therefrom and then
pounded with any of the usual compounding ma 40 a sheet of “Ameripol” is pressed on by hand with
terials, such as pigments, ?llers, softeners or plas
the aid of a squeezing roller and the laminated
structure is subjected to heat for 30 minutes at
ticizers, accelerators, stabilizers, dispersing
90° C. It was found that the “Ameripol” adhered
agents, aging resistors, sulfur, etc. It is essen
tial, however, that the butadiene copolymer bc
very well to the polyvinyl alcohol ?lm and could
be separated only with great di?iculty.
uncured at the time it is joined to the adhesive
layer and cured in place.
‘
When the laminated structure was prepared
» The ?lm, sheet or pellicle to which the buta
similar to the process described above but cured in
diene copolymer may be adhered includes any of
a press at 135° C. for 40 minutes while held under
the dense, non-?brous, relatively non-porous,
pressure of 250 pounds per square inch, the
self-sustaining, synthetic ?lms available, such as 50 “Ameripol” was so tenaciously bonded to the
films of nylon, regenerated cellulose, cellulose
esters, such as cellulose acetate, cellulose pro
polyvinyl alcohol ?lm that the two could not be
separated without tearing the “Ameripol” or the
pionate, cellulose aceto-propionate, cellulose
aceto-butyrate, polyvinyl alcohol, polyvinyl
?lm.
Example II
acetal, or mixed acetals such as polyvinyl formal,
polyvinyl propional, polyvinyl benzyl formal, and
especially certain partial polyvinyl butyrals' The
polyvinyl butyrals in which at least 40% (26.3%
combined butyraldehyde), but no more than
A similar adhesive as in Example I for bond
ing polyvinyl butyral prepared by reacting 55%
(about 33.7% combined butyraldehyde) of the
hydroxyl groups of polyvinyl alcohol with bu
65% (38.1% of combined butyraldehyde), of the 60 tyraldehyde to “Hycar” (a compounded acrylo
nitrile-butadiene copolymer) is prepared as fol
hydroxyl groups of polyvinyl alcohol are sub
lows: 15 parts of polyvinyl butyral prepared by
stituted by reacting the polyvinyl alcohol with
combining about 73% of. the‘ hydroxyl groups of
butyraldehyde, are exceptionally useful as fuel
polyvinyl alcohol with butyraldehyde are dis
barriers in view of their low permeability factor
solved in 85 parts of ethyl alcohol denatured with
and relatively high resistance to shattering. The
methyl alcohol. To this solution is added a solu
partial polyvinyl butyrals in which the degree of
tion comprised of 15 parts of resorcinol, 30 parts
hydroxyl substitution is in the range of from
of formalin (37% formaldehyde in water), 3 parts
50% to 60% (31.3% to 35.8% combined butyr
aldehyde) are preferred.
of 10% solution of NaOI-I in water and 100 parts
The pressure, temperature and time under 70 of ethyl alcohol denatured with methyl alcohol.
which the laminated structure is finally set up
After thoroughly mixing the two solutions to
‘ and the butadiene copolymer cured, may of course
gether, this composition is applied to a sheet of
be varied within reasonable limits. It is gener
“Hycar” and after air-drying for some minutes,
ally desirable to maintain the structure under
the polyvinyl butyral ?lm is applied against the
reasonably high pressure, for example, at least 75 resin-coated surface and the laminae pressed to
annoys
gether under a pressure of 250 pounds per square
inch and heated to a temperature of 135° C. for
40 minutes while maintaining the pressure. The
polyvinyl butyral could not be separated ‘from
the "Hycar" without tearing one or the other.
Example III
pressing said materials together with the adhe
sive composition therebetween and maintaining
said pressed materials at an elevated temperature
for a su?lcient length of time to ?rmly unite said
materials and to cure said butadiene copolymer
material.
j
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3. A method for laminating self-sustaining, non
vulcanizable, non-?brous, synthetic ?lm material
The adhesive prepared as in Example 11 is ap
with butadiene copolymer material which com
plied to a ?lm of nylon and after the solvent is
substantially eliminated by air-drying, a sheet of 10 prises forming on the surface of at ‘least one of
said materials an adhesive composition consisting
“Hycar” is applied against the resin-‘coated sur- _
essentially of a polyvinyl butyral containing 31.3%
face and the laminae pressed together under a
to 45.7% combined butyraldehyde, and a poly
pressure of 250 pounds per square inch and
hydric phenol-aldehyde resin, and thereafter
heated to a temperature of 135°C. for 40 minutes
while maintaining the pressure. It was found 15 pressing said materials together with the ad
hesive composition therebetween and maintain-'
that the "Hycar” adhered to the nylon ?lm ten
ing said pressed ‘materials at an elevated tem- aciously and could not be separated without tear
perature for a sufllcient length of time to ?rmly
ing the "Hycar” or the ?lm.
unite said materials and to cure said butadiene
While it is generally preferred to coat the hu
tadiene copolymer with the adhesion composition 20 copolymer material.
4. A method for laminating self-sustaining,
herein described, substantially as good results are
non-vulcanizable, non-?brous, synthetic ?lm ma
I obtained by applying the adhesive to the film or
terial with rubber-like vulcanizable butadiene co
by applying‘ the adhesive coating to both the film
polymer material which comprises applying to a
and the butadiene copolymer.
surface of at leastone of said materials a liquid
The laminated structures comprised of syn
composition consisting essentially of a polyvinyl
thetic ?lms and butadiene copolymers and pre
butyral containing 20.7% to 47.4% combined
pared in accordance withthis invention are
' butyraldehyde, and resin-forming ingredients
especially useful as fuel barriers .in self-seal
consisting of a polyhydric phenol, an aldehyde
ing fuel tanks for military and naval air
planes. Not only is the ?lm, which is bonded 30 and a basic polymerization catalyst, dissolved to
gether in a volatile organic solvent, heating to
to the butadiene copolymer exceptional in its
convert the resin-forming ingredients to a resin
low permeability but the adhesive layer itself,
whereby to form an adhesive coating, and there
which is extremely thin, being of the order
after bringing said materials into association and
of 0.0001 inch in thickness, contributes sub-v
with said adhesive composition therebetween, and
stantially to the impermeability of the lami
nated structure forming the fuel tanks. The‘ maintaining said associated materials at an ele-,
'vated temperature for a su?icient length of time
satisfactory joining of butadiene copolymers and
to ?rmly unite said materials and to cure said
compounded stock containing the same to vari-_
butadiene copolymer material.
ous synthetic ?lms, sheets, pellicles, and the like
provides laminated structures that are eminently 40 ' 5. A method for laminating self-sustaining,
non-vulcanizable, non-?brous, synthetic ?lm ma
suited for various uses, not only in connection
terial with rubber-like vulcanizable butadiene co
with airplanes and other armaments, but also in
polymer material which comprises applying to a
various ?elds of civilian use. Furthermore, the
surface of at least one of said materials a liquid
preparation of laminated structures in accord
ance with this invention is simple and no very 45 composition consisting essentially of a polyvinyl
butyral containing 20.7% to 47.4% combined
hightemperature nor long period of baking is re
butyraldehyde, and resin-forming ingredients
quired to set up the resin in the adhesive.
consisting of a polyhydric phenol, an aldehyde
Since it is obvious that various changes and
and a basic polymerization catalyst, dissolved to
modi?cations may be made without departing
from the nature and spirit of the invention, it, is 50 gether in a, volatile organic solvent, heating to 7
convert the resin-forming ingredients to a resin
to be understood that the invention is not to be
whereby to form anadhesive coating, and'there
limited except as set forth in the following claims.
after pressing said materials together with the
I claim:
adhesive composition therebetween and main
1. A method for laminating self-sustaining,
taining
said pressed materials at an elevated tem
non-vulcanizable, non-?brous, synthetic ?lm ma 55
perature for a. su?icient length of time to ?rmly
terial with butadiene copolymer material which
unite said materials and to cure said butadiene
comprises forming on the surface of at least one
copolymer material,
of said materials an adhesive composition con
sisting essentially of a polyvinyl butyral contain
aing 20.7 % to 47.4% combined butyraldehyde, and .60
a polyhydric phenol-aldehyde resin, and there
after bringing said materials into association and
with said adhesive composition therebetween, and
' 6. A method for laminating self-sustaining,
non-vulcanizable, non-?brous, synthetic ?lm ma
terial with rubber-like vulcanizable butadiene co
polymer material which comprises applying to a
surface of at least one of said materials a liquid
composition consisting essentially of a polyvinyl
maintaining said associated materials at an ele;
vated temperature for a sufficient length of time 65 butyral containing 31.3% to 45.7% combined
butyraldehyde, and resin-forming ingredients
to ?rmly unite said materials and to cure said
consisting of a, polyhydric phenol, an aldehyde
butadiene copolymer material.
'
and a basic polymerization catalyst, dissolved to
2. A method for vlaminating self-sustaining,
gether in a volatile organic solvent, heating to
non-vulcanizable, non-?brous; synthetic ?lm ma
terial with butadiene copolymer material which 70 convert the resin-forming ingredients to a‘ resin
comprises forming on the surface of at least one
whereby to form an adhesive coating, and there
of said materials an adhesive composition consist
after. pressing said materials together with the ’
adhesive composition therebetween and main
taining said pressed materials at an elevated tem
polyhydric phenol-aldehyde resin, and thereafter 75 perature for a su?icient length of time to ?rmly
ing essentially ofa polyvinyl butyral containing
20.7% to 47.4% combined butyraldehyde, and a
2,411,878
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unite said materials and to cure said butadiene
copolymer materials.
'
7. A method for laminating self-sustaining,
non-vulcanizable, non-?brous, synthetic ?lm ma
terial with rubber-like vulcanizable butadiene co
polymer material which comprises applying to a
surface of at least one of said materials a, liquid
composition consisting essentially of a polyvinyl
butyral containing 31.3% to 45.7% combined
8
sustaining, non-vulcanizable, non-?brous, syn
thetic ?lm bonded to a butadiene copolymer by
a composition consisting essentially of a polyvinyl
butyral containing 20.7% to 47.4% combined
butyraldehyde, and a, substantially insoluble, in
fusible polyhydric phenol-aldehyde resin.
9. An article of manufacture comprising a self
sustaining, non-vulcanizable, non-?brous, syn
thetic ?lm bonded to a butadiene copolymer by
butyraldehyde, and resin-forming ingredients 10 a composition consisting essentially of a poly
consisting of a polyhydric phenol, an aldehyde
and a basic polymerization catalyst, dissolved to
gether in a volatile organic solvent, heating to
convert the resin-forming ingredients to a resin
whereby to form an adhesive coating and there 15
after joining said materials together with the
adhesive therebetween and maintaining a pres
sure of at least 100 pounds per square inch and
a temperature of from 80° C, to 160° C. for a s‘uf
vinyl butyral containing 31.3% to 45.7% com
bined butyraldehyde, and a substantially‘ insol
uble, infusible polyhydric phenol-aldehyde resin.
10. .A composite self-sustaining ?lm compris
ing a self-sustaining, non-vulcanizable, non
?brous, synthetic ?lm laminated to a ?lm of a
rubber-like vulcanizable butadiene copolymer by
a composition consisting essentially of a polyvinyl
~butyral containing 31.3% to 45.7% combined
?cient length of time to ?rmly adhere said ma 20 butyraldehyde, and asubstantially insoluble, in
terials.
fusible polyhydric phenol-aldehyde resin.
8. An article of manufacture comprising a, self
_
ALBERT HERSHBERGER.
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