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Патент USA US2411840

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Nov. .26, 1946.
Original Filed March 26, 1957
2,41 1,840
~~ 2,411,840’
Patented Nov. 26, 1946
. ooMeoUNmNG ‘RUBBER Hypno
:William 0. Calvert, Gary, ‘Ind, assignor to
Wingfoot Corporation, Wilmington, Del., and
Akron, Ghio, a'corporation of Delaware
Griginal application March 26, 1937, Serial No.
133,172. vDivided and this application August 2,
1946, Serial No. 587,897
4 Claims.
' '
(Cl. 260F738)
rubber hydrohalides', viz. rubber hydrochlorides,
rubber hydrobromides' and rubber hydroiodides,
and the treatment of resulting rubber hydrohalide
compositions. The invention will be described
more particularly as applied to the treatment of
rubber hydrochlorides.
at the times and temperatures indicated as “time .
1n minutes”/“degrees Fahrenheit.”
. 20/26‘0.__‘______> ____ _____,____.___; 10‘parts MgO
" '
In milling and molding and otherwise treating
rubber hydrohalides such as rubber hydrochloride
. .20/260_.____,___p__‘
. 20/260,____‘__(____
gv__ 10 vparts CaO
___ 10 parts PbO
. 29/260,____ _‘__._‘__\_________'____7_,20 parts CaO
.'60/260 _________ __,__: _______ __' 20 parts QaO
When the mechanical manipulation of the rubber
hydrochloride is carried‘out at an elevated tem
perature it has been found that in many oper
. 20/260___,T______
__ 20 parts MgO
g 20 partsMeo
-.-__ 3.0 parts CaO
- Bil/2th-.-.
- ?ll/2'15","
ations the admixture of a basic material with
the rubber'hydrochloride gives improved results.
For example, in milling and then molding vrubber
The following materials were milled into 100
parts of rubber hydrochloride and then molded
This invention relates to the compounding of
- sci/260-.
hydrochloride it has been found that the addi
.__.- 30 parts 0.69
,- 30 parts'Mgo
. 60/275 ____________________ __, 30 parts vlvlgo
was foundthat these compositions could be
milled under conditions of times and temperatures‘
tion of inorganic basic materials such as lime and
magnesia,etc. give improved products.’ Theuse
which would cause evolution of hydrogen chlo
of: bases ‘such as hex'amethylene tetramine ‘and
diphenyl guanidine has likewise beeniound ad;
ride rgfrom rubber hydrochloride containing no
basic material. Other compositions satisfactorihr
homogeneouslymilled together and then molded
vantageous. > For certain operations it'has been
found desirable to compound with the rubber
hydrochloride and basic material a .plasticizing
material such as rubber or other softener. Pig.
12. 60/220—11 parts vulcanizable rubber stock
ments may be milled into the rubber hydrochlo~~ 25 13. 60/220..—11 parts vulcanizable rubber stoc
ride where colored products are desired.
plus 25 parts gas black
- This invention relates more particularly to the
compounding ofv basic materials with rubber hy
drohalides by milling and the molding and calen
dering of compositions comprising rubber hydro 30
halides and basic materials." “But it is to’ beun
derstood that it'is not essential to incorporate
basic materials with.‘rubberihydrohalides for all
such operations. For example, rubber hydrochlo
ride may be satisfactorily milled
perature in the absence of basic
those instances where the use of
rial is desirable the amount of
14. 60/220-1'1 parts vulcanizable rubber stock
plus 2- parts diphenyl guanidine
plus 25 parts gas ‘black
. 20/220—2 parts diphenyl, guanidine
. 20/220-25 parts gas black
. ‘20/220,—l-2~parts diphenyl guanidine plus 25
parts ‘gas black
. 20/260-5-5 parts‘ hexamethylene tetramine
. 20/260—.10»parts Ivory soap
at a lowv tem
materials.‘ In
a basic'mate-y‘
basic material
. 60/260-20 parts CaO plus 10 parts cumar
. .60/260-1-20 par-ts CaO plus 10_ parts mineral
required .for'entirely satisfactory ‘results depends
upon the temperature employed, the length of‘
time during which the rubber *h'ydrochlorideis
subjected to the temperature;etc.v For example,
. -6D/26.0—:20 parts CaO ' plus '10. parts factice
. 610/260-—.20 parts ,CaO plus 10 parts coal tar
.- 60/:260-20 parts CaO plus ‘5 parts hexameth
116.116 tetramine
. 160/275-4211 narisiGaQp‘lus 5 parts hexameth
in‘v molding a mixture consisting of rubber’ hy
drochloride and an inorganic basiomaterial such
as-CaO,'MgO or PM). it has been .found rm
general that 10 parts of one of the above ‘bases
. 60/260-20 parts CaO plus 20 parts gas black
. ‘60/275—20 parts CaO plus 20 parts gas black
and 100 parts of rubber‘hydrochloride- can'be
. 60/-260+—,2.0 parts Meoxplus 5 par-ts hcxameth
satisfactorily molded or curedy'a's a thin slab for 20
minutes at 260° F.; Whereas 20 parts of the base
was preferred for 60‘minutes molding at this-11cm‘
perature’a'nd 30 parts for 69 minutes molding at‘,
275° F. Molding at such higher temperatures?
caused'blowing on uncornpounded rubber hydro-4‘.
; rlene tetra-mine
~ylene ‘tetrami-ne
. 6il/27'5-e-20 parts 1Mgo plus‘5 parts heXameth-~
;y-1ene tetramine
30. '60/26'0-—2_0 parts MgO plus '20 parts gas black
' The vulcanizable rubber stock of Examples l2,
l3 and 14 was composed of 100 parts ‘rubber;
and in certain instances caused pitting;v ' 1 part mercaptobenzothiazole, 1 part stearic acid,
55 5 partsizinc voxide and 3 parts sulfur;
gen chloride over that theoretically required by
31. Somewhat over 1.5 parts glyceryl butyl
phthalate were incorporated in 100 parts rubber
hydrochloride on a cold mill. By incorporating
10 parts of pale crepe rubber (about 400 plas
the empirical formula (C5H9C1) z. The introduc
tion of hydrogen chloride is then discontinued
and the reaction of the hydrogen chloride with
the cement is allowed to progress ,until a washed
and dried sample indicates that 29 to 30.5% of
ticity) on a cold mill a product less tough than
that containing no rubber was obtained; Four
parts of diphenyl guanidine was incorporated
into the rubber hydrochloride-glyceryl butyl .
chlorine is combined with the rubber. Generally
the time required is about 20 hours. The reac
tion mixture is then steam distilled to remove
phthalate mixture on a hot mill. Each of these
products was quite ?exible. A sheet of the last 10 the benzene and the excess hydrogen chloride.
The resulting mass is broken up on a rubber
composition was pressed into felt at 240° F. using
Washer and washed thoroughly and dried in a
4000 and 9000 pounds pressure. The rubber hy
vacuum at approximately 160° F. The rubber
drochloride was pressed almost completely into
the felt with the latter pressure.
32. A dark red sheet was obtained by com
hydrochloride is then dissolved in chloroform or
16 dichlorethylene in the ratio of about one part
rubber hydrochloride to twenty parts of the
solvent. The ageing properties of the ?lm may
pounding two parts diphenyl guanidine and 0.3
part Oil Red 3B (American Aniline Company)
on a hot mill.
be improved by adding a small amount of an
This Was pressed into felt at
Hexamethylene tetramine and
satisfactory product was obtained by pressing into 20 methylene amino aceto nitrile are effective for
240° F. using 2500 and 6000 pounds pressure. A
this purpose. Where a colorless transparent ?lm
is desired it is advantageous to use 3% of ditetra
hydro furfuryl amine or dicycle hexyl amine with
guanidine, 0.1 part Oil Red 3B and 60 parts
11/2% of hexamethylene tetramine. The anti
rubber hydrochloride on a hot mill. The best
26 oxidant is dissolved in the solvent with the washed
results are obtained by heating both plates.
felt at 240° F. with 2500 pounds pressure a com
position obtained by sheeting 1.2 parts diphenyl
reaction mass.
~ 33. A good sheet was obtained by milling 1.2
The invention will be further explained in con
nection with the drawing, in which
hydrochloride and then molding in a press at
Fig. l is a plan of apparatus showing one
240° F., heating 5 minutes before applying the
30 method of manufacturing the sheets of this in
full pressure of 2500 pounds.
34. Fifteen parts butyl stearate was milled into
Fig. 2 shows a frosted sheet with a clear win
124 parts rubber hydrochloride and a sheet formed
on the mill was then pressed into felt at 240° F.
Fig. 3 shows a method of modifying a perfectly
using 2500 pounds pressure. The rubber hydro
chloride was quite soft after pressing but hard 35 smooth sheet.
Fig. 4 shows a sheet with a protuberance there
ened on standing.
in; and
35. One part pale crepe rubber (400 plasticity)
parts diphenyl guanidine into 60 parts rubber
Fig. 5 shows apparatus for calendering or
was milled into ?ve parts rubber hydrochloride.
smoothing out a ?lm of rubber hydrochloride, as
A sheet of this was pressed into felt at 240° F.
using 2000 pounds pressure. There was prac 40 explained below.
In making a ?lm for wrapping purposes from
tically no indication of rubber hydrochloride
a rubber hydrochloride solution such as described
decomposition. A light coat of triethanol amine
the material may be run onto a continuous belt in
stearate was used on the press without detri
such an amount as to produce a ?lm about 1/1000
mental effect.
’ 36. Rubber hydrochloride was sheeted out on 45 of an inch thick after the solvent has been evap
orated. Heat is applied and the solvent is evap
the mill at such a temperature that there was
orated slowly without boiling. A clear transpar
some‘ evidence of decomposition. This was then
ent ?lm results. Irregularities in the under sur-‘
pressed to felt at 260° F. and 280° F. using 2500
face of the ?lm are produced by using a belt
I pounds pressure without evidence of further de
50 having complementary irregularities in its sur
37. On pressing rubber hydrochloride to felt at
elevated temperatures which caused darkening of
the rubber hydrochloride it was found that the
addition of ?ve parts hexamethylene tetramine
per 100 parts rubber hydrochloride reduced or 55
If a certain area of the ?lm is to be de
pressed, that portion of the belt on which this
area of the ?lm is formed will be raised or a form
of suitable shape may be fastened to the belt.
If a portion of the ?lm is to be raised to produce
an embossed e?ect, the portion of the belt on
prevented darkening.
which it is formed will be depressed. If a very
' This invention also contemplates the trans
thin ?lm is produced, the variations in vthickness
formation of perfectly ?at sheets of rubber hydro
are preferably kept at a minimum to prevent dis
chloride into sheets one or both surfaces of which
are irregular. By this transformation the thick 60 tortion of the ?lm in drying. If a thicker sheet
is to be formed somewhat greater Variations in
mess of the ?lm in certain areas may be decreased
thickness are possible without causing distor
or increased, or a limited area of the sheet may
tion of the sheet. The raised or depressed por
be stretched to a desired size and shape. The
tions may constitute a trade-mark or other de
rubber hydrochloride may be formed in the fol
65 sign which may be merely for decorative purposes
lowing way.
or they may comprise printed matter or may be
Twenty pounds of plasticized pale crepe rubber
used for any other purpose.
are dissolved in 313 pounds of benzene, giving a
In Fig. 1 the apparatus for forming a sheet is
rubber cement of approximately 6% concentra
shown as comprising two rollers, 5 and 6, ‘over
tion. The cement is cooled to about 10° C. and
hydrogen chloride gas is introduced into it while 70 which a belt ‘I is passed. A rubber hydrochloride
solution is supplied to the belt through the pipe,
it is vigorously agitated. After about six hours
8 and a perforated header 9. The belt travels
the increase in weight of the composition due
in the direction of the arrow. The rubber hy
to the introduction of hydrogen chloride gas
drochloride solution after being applied to the
should be approximately 11.6 pounds which cor
responds to a slight excess of available hydro-' 75 belt is passed under the scraper or knife I0 to
form :a .very thin ?lm, and the guides I i are pro.
vided to prevent the excess of ‘the ?lm from run.
ning over the edges of the belt. The belt and
tuberances of large area and varying depth may
be formed by stretching a limited area of a sheet
of the rubber hydrochloride. Where a consider
able amount of stretching is required, it is prefer‘
through which'air or gas is circulated and the U1 able to apply heat before or during the stretching.
solvent evaporated. After passing over the roll
Such stretching may be accomplished by the
er 6, and returning to the roller 5,. sui?cient
gradual application of pressure between plates or
solvent has been evaporated to allow the ?lm 12
rolls or in apparatus particularly designed for
to be removed from the belt. The'?lm is then
the purpose in which the stretching may be ef
passed through further drying apparatus if nec l0 fected by the movement of one or more members
essary to remove the last traces of the solvent.
after the area surrounding the part to be
Any desired design is formed by providing inden
stretched'has been tightly clamped in place. The
tations or raised areas on the ‘belt, depending upon
protuberance may be shaped in a heated mold
whether the design is to be embossed on or en
if this is, desired.
graved into the ?lm. The drawing shows diamond 15
If the sheet is to be stretched to any consider
shaped depressions l3 in the belt which produce
able extent, this may be advantageously accom
raised areas M on the ?nished ?lm.
plished by treatment of the sheet during its for—
By pebbling or cross-hatching, a frosted effect
mation, before all of the solvent has been evap
may be produced. By frosting only a portion of
orated from it. For instance, in the manufac
the surface and leaving another portion un 20 ture of the rubber hydrochloride ?lm from a solu
frosted a ?lm is formed which when used for
tion of chloroform, after evaporating mostof the
wrapping directs attention to that portion of the
solvent, for example when the solvent content has
wrapped package which isseen through the un
been reduced to about 10%, certain areasmay be
frosted portion. Fig. 2 shows a section of the ?lm
stretched vto form desired protuberances, partic
20 which is frosted over its entire surface except
ularly if the stretching is effected while the film
for the clear window 2! which may be made of
is still Warm. The balance of the solvent may
any shape desired. Various novel'eifects in Wrap
then be evaporated.
ping ?lms may be produced by forming a ?lm
If considerable stretching is required to form.
on a belt having an irregular surface.
the desired‘ protuberance, the portionof the sheet
Instead of forming films of irregular thick
which is to be stretched may be made somewhat
ness in this way a perfectly uniform sheet of the
thicker than the surrounding portion by form
rubber hydrochloride may ?rst be formed on a
ing it on a belt with depressed areas to give the
belt having a perfectly smooth surface and this
desired thickness at the required portions of the
may be after-treated to produce the effects de
sired. The rubber hydrochloride is thermoplastic
Although the invention relates more partic
and while still warm from the process of manu
ularly to the manufacture of transparent ?lms,
facture or by heating, if necessary, the surface
it includes sheets of greater thickness and sheets
rollers are preferably enclosed in a chamber
may be altered as desired and certain alterations
in the surface may be made at room temperature
by the proper application of pressure; The un
saturated hydrochloride produced in the manner
above described is slightly extensible and can be
marked by stamping without destroying its tex
ture and waterproo?ng‘ properties.
stamping at room temperature produces some
effect on a sheet or ?lm, it is preferable to stamp
in a press heated to 80—85° C. for example, or to
which are not transparent.
Colored sheets may
be formed by'the addition of dyestuffs.
The‘invention also contemplates spreading a
solution of‘ rubberhyd'rochlo'ride ‘in a volatile sol
' vent on a suitable surface and after evaporating
solvent from the exposed surface subjecting it
to a “smoothing out” operation. This smoothing
out is preferably effected while the ?lm still con
tains a small amount of solvent and then the
balance of the solvent is evaporated.
?rst heat the sheet and then stamp it. Where
The ?lm may advantageously contain between
depressed or raised areas of large dimension are
5 and 15% by Weight of solvent when subjected
to be formed, the sheet should be heated until it 50 to the smoothing out operation to remove irreg
softens somewhat. The sheet may also be marked
ularities from the surface. For example, to pro
by passing it through rolls, after ?rst passing it
duce a ?lm of high transparency from rubber
through heated rolls if necessary. Fig. 3 shows
hydrochloride a solution of 7% of a partially sat
rollers 30 and 3|. The upper roller 30 is pro
urated rubber hydrochloride (for example, rub
vided with raised lines or ridges 32 which in 55 ber hydrochloride containing 29-30.5% chlorine)
pressing against the smooth surface of the roller
dissolved in benzene is spread out as a thin ?lm
3|’ cause depressions 33 to be formed in the ?lm
on anendless smooth surfaced belt in such a Way
34. In this way lines may be pressed into one or
as to produce a continuous ?lm. The benzene
both of the surfaces or ridges may be raised on one
is allowed to evaporate, preferably with a forced
or both surfaces. Any desired portion of one or 60 draft, until its solvent content has been reduced
both surfaces may be altered to produce an en
to about 5 to 15% of the Weight of the rubber hy
graved or embossed effect.
drochloride. It is then passed between highly
It often happens that for wrapping articles of
polished pressure rolls. This removes irregulari
irregular shape or for enclosing them in a pro
ties in the surface of the ?lmfrom which the
tective layer which comprises a part of the article 65 benzene has been volatilized. The ?lm is then
itself, or for covering or protecting an inner con
subjected to ‘further drying to allow evaporation
sistuent of a fabricated article a sheet which is
of the balance of the solvent. The highly polished
not altogether flat is preferred to a perfectly ?at
rolls may if desired contain some marking or
sheet. For example, in wrapping a perfectly
design to impress or emboss a ?gure or design
square articleon which is a protruding handle, 70 upon the ?lm, but the major portion of the rolls
a sheet with a protuberance shaped to ?t the han
will be smoth and highly polished. A minimum
dle is preferable to a perfectly ?at sheet. Fig. 4
temperature of about 150° F. is advantageously
shows ?lm 4i} on which a protuberance 4| has
employed and for usual operating conditions 190"
been formed which is of predetermined shape.
or 200° F. is preferred.
Thimble-like or ?nger-like protuberances or pro 75
Various methods of smoothing out the ?lm
surface may be employed. For example, pressure
is festooned over rollers 59 and 60. Here air cir
may be applied to the ?lm before it is removed
culation means (not shown) removes the balance
from the surface on which it is formed as by ap
of the solvent through suitable vents (not shown).
The rubber hydrochloride may be made in any
plying pressure to the ?lm before it is removed
from the endless belt. If rollers are employed
for smoothing out the surface of the ?lm it may
be advantageous to use a rubber covered roll or
a hard rubber roll in combination with a steel
suitable way, such for example as that described
in my issued Patent 1,989,632. It may advanta
geously contain a stabilizer such as those there
mentioned. For example, it may contain about
one per cent of hexamethylene tetramine. Films
roll, with the steel roll contacting with the sur
face of the ?lm from which solvent has been 10 of any thickness may be prepared, which may be
.005 to .002 inch thick, or thinner or thicker as
evaporated, because of the di?iculty in obtaining
described in said patent.
two steel rolls with surfaces of the exact uni
From the above it is seen that rubber hydro
formity required to calender a ?lm with a thick
chloride can be compounded with a variety of in
ness of the order of a thousandth of an inch.
By using a roll with a resilient surface in com 15 gredients and utilized in many ways. It can be
molded to fabrics, etc. It can be molded into all
bination with a steel roll any deviations from
sorts of shapes for use in the manufacture of
uniformity in the surface of the steel roll are com
electrical instruments and a, multitude of other
pensated by the resilient roll and uniform pres
articles now made from other plastics.
sure on the ?lm is obtained.
This application is a division of application
.The invention is illustrated diagrammatically
Serial No. 133,172, ?led March 26, 1937, which is
in Fig. 5 of the accompanying drawing. The
in part a continuation of my applications 682,116,‘
coated belt is indicated by numeral 5|. The hood
?led July 25, 1933, and 102,225, ?led September
52 is provided to carry off vapors of the solvent
23, 1936, which latter is in part a continuation of
from the chamber enclosing the ?lm. The solu
my application 2,843, ?led January 22, 1935.
tion of rubber hydrochloride is fed onto the belt
I claim:
through suitable means attached to the feed pipe
1. A composition of matter comprising a rub
' 53. A spreader or scraper to regulate the thick
her hydrohalide and litharge.
ness of the film is indicated at 54. The ?lm 55
2. A plastic composition comprising as an es
after the majority of the solvent has been evap
sential ingredient a rubber hydrochloride inti
orated is passed through the pressure rolls 56 and
mately admixed with a minor proportion of a
51. The roll 58 is a steel roll. The roll 51 is pref solid lead compound.
erably covered with rubber or other resilient ma
3. A plastic composition comprising as an es
terial. The upper surface of the ?lm from which
sential ingredient a rubber hydrochloride inti
solvent has evaporated contacts with the pres
sure roll 56. It is somewhat irregular as the film 35 mately admixed with a minor proportion of lead
enters between the rolls 56 and 51, but the highly
4. A plastic composition comprising as an es
polished surface of the roll 56 smooths out ir
sential ingredient a rubber hydrochloride inti
regularities present in the surface of the partially
mately admixed with a minor proportion of
formed ?lm, From these rolls the ?lm passes
through further drying means of suitable design 40 litharge.
here indicated by the drier 58 in which the ?lm
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