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Patented Sept. 24, 1946
2,408,027
UNITED STATES PATENT ’ OFFICE
2,408,027
METHOD or 'rnm'rmo srn'rnarro
mornmecaocs mans
Francis Clarke Atwood, Newton, Mass” assignor
‘
to National Dairy Products Corporation, New
York, N. Y., a corporation of Delaware
No Drawing. Application December 11, 1943,
Serial No. 513,952 >
2
(Cl. 8-127-6)
This invention relates to the treatment of syn
, thetically shaped protein-containing. materials.
resistant to hot water or dilute acids or alkalies.
Particularly is this so if the water solution ,con
tains an alkaline material such as would be pres
ent in' a hot solution of an ordinarysoap. Upon
the heating or boiling of such ?ber in such a solu
tion it becomes soft and spongy and takes on a
In particular vthe invention includes the treat
ment of ?ber synthetically made from protein
aceous material, such as casein, to impart thereto
properties simulating those of natural protein
?bers.
“slimy feel”. .The tensile strength of the ?ber
Many naturally occurring materials are com
and its elasticity in such a state is also greatly
prised of proteins, for example, silk, wool, hair
reduced so that the ?ber is readily deformed or
and skins. “Arti?cial materials also may be 10 broken. Upon drying such ?ber after it has been
manufactured from protein-containing material,
subjected to such treatment, it becomes brittle so
such as casein and other proteins and formed
that further handling results in excessive “drop
into various shapes, such as ?brous ?laments.
pings,” if in fact the ?ber is su?iciently'?exible
But such arti?cial protein materials differ in
to be subjected to any further processing. Ordi
many respects from natura1 protein materials.
Protein-containing materials have many 'de~
15 nary casein ?ber, in addition, does not have dye
ing properties enabling itto be dyed in a manner
similar to naturally occurring proteinaceous ?ber.
‘ sirable properties that render them valuable for
use in fabrics of all kinds, such as covering ma
terials and upholstery, and for use in articles of
The ordinary casein ?ber also is subject to a
change in properties due to contact with moisture
clothing including clothes, shoes and gloves. 20 in the air. In humid air it is relatively plastic,
These properties include the warmth, softness,
?exibility, tensile strength, elasticity and other
similar properties of protein-containing mate
but in dry air it is quite brittle. .
From the above it wil1 be seen that the syn
thetic protein ?ber as known heretofore in’ the '
rials, and are hereinafter referred to as physical
properties.
All proteins contain carbon, hydrogen, oxygen,
25
and nitrogen and many proteins also contain sul
fur and phosphorus. The proteins are thought to
art, such as that shaped from casein and hard
ened with formaldehyde, is entirely different
from natural proteinaceous ?ber such as wool,
' silk or fur, and is not suited for the uses to which '
such natural ?bers may be put. This difference is .
so marked as.not to be simply a matter of degree.
boxyl groups, and ‘are more or less chemically v30 Apparently the casein inherently is of such a na
reactive depending upon their individual consti
ture as not to possess satisfactory properties for
contain amino and probably hydroxy and car- » ’
tution. For example, di?erent proteins are af
fected di?erently by hot'water, alkaline or soap
?ber purposes. Attempts at modi?cations of the
casein have not produced a ?ber which has satis
solutions. Over long periods of time some pro
_ ?ed the textile industries.
'
In copending application, Serial Number
teins also oxidize or otherwise deteriorate more 35
rapidly than others so as to become somewhat
427,940, ?led January 23, 1942, of which this ap
brittle and lose their strength‘ and softness. Dif
plication is a continuation-in-part, a process is
ferent proteins also react di?erently with var
described in which the chemical properties of
ious other compounds, particularly dyes. In re
synthetic protein materials may be changed by
Ierring to the chemical properties of protein con 40 reaction with certain chemical compounds to im
taining materials, reference is made to their abil
part more desirable chemical properties without
ity to combine physically or react chemically with
detracting from their Physical properties. They
may be made more resistant to chemical activity
any other compound such as oxygen, water, acids,
alkalies, and dyes.
but at the same time remain soft and pliable and
While the physical properties of ?ber prepared 45 retain or even improve their tensile strength and
other physicaliproperties.
from the proteins such as casein, including the
‘common method of soaking the shaped casein
_In accordance with the Process-described in
?ber in formaldehyde solutions are satisfactory
the aforesaid cog-pending application, the syn
for some purposes, they are far from satisfactory
thetic proteinaceous ?ber is treated in a liquid
for most uses to which ?bers are to be put. With 50 containing an acylating anhydride, more particu
respect to their chemical properties particularly
larly, acetic anhydride in an inert solvent. .The
they leave much to be desired. For example, a
treating liquid comprises an inert organic solvent,
?ber prepared from a casein dispersion and
such as a hydrocarbon or a chlorinated hydro
‘ coagulated, in which process it is hardened by
. carbon, in which acetic anhydride and a small 7
the usual treatment with formaldehyde, is not 55 amount of acetic acid is included. The proteina
8,408,027
-
3
4
ceous ?ber to be treated is made by dispersing. . accepted by natural protein ?ber. Since one of
the more important-uses of the synthetic protein
casein or other proteinaceous material in an al
?ber is in admixture with natural protein ?ber
kaline solvent and spinning it into an acidic
and other ?bers natural or synthetic, "it is desir
coagulating bath, following which it is treated
able
that the two should have similar dyeing prop- .
with formaldehyde, washed and dried. The dried
errties. It is: possible to dye the new ?ber with
?ber so prepared is immersed in the treating
appropriate dyes and in baths of/the‘proper pH
liquid at an elevated temperature of about 150°
so that it accepts the dye at substantially the
same rate, so that at the end of the dyeing opera
10 tion, a mixture of synthetic protein /?ber and,
the liquid.
'
‘
other ?ber will be of substantially the same shade.
q The 'proteinaceous ?ber to be treated normally
In accordance with the invention, the treating
contains a small amount of water which is the
liquid comprises any organic ‘solvent inert with
normal moisture content of the ?ber when'it is
respect to the ?ber and the ingredients in the
in equilibrium with an atmosphere of ordinary
A hydrocarbon solvent, such as that
temperatures and humidities. This is reduced as 15 liquid.‘
known in the trade as “Solvasol," is inexpensive .
much as possible, in accordance with the proc
and for that reason is preferred. To this is added
ess in said co-pending application, since the mois
acetic anhydride in an amount of 7 to 8%, and
ture in the ?ber reacted with .the acetic anhy
acetic acid in an amount of 5 to 7%, preferably
dride in the treating liquid to form acetic acid.
51/2 to 6% by weight of the total treating liquid.
This used up aceticanhydride for no good pur 20 The amount of the acetic anhydride in the above
pose, and was thought to increase the acetic acid
formula may vary from 5% to 15%. Amounts
content to a point where it must be eliminated.
less than 5% will result in some acetylation but
In fact, in accordance with the process of said
generally it is not sufficient to Justify the treat
application, a portion of the treating liquid is
ing of the ?ber by the process; an amount above
withdrawn and neutralized with soda ash-to con 25 10% (unless lower temperatures are used) does
,vert the acetic acid to sodium acetate ‘which is
not result in a su?lcient improvement to war
to 225° F. for a period of a few minutes to an
hour, following which the ?ber is removed from
separated from the treating liquid.
_
_
rant using a larger amount, but no harm is done
It has been discovered, in accordance with the
by its presence. The temperature may vary from
invention described in this application, that if
about 150° F. to 225° F. At lower temperatures ‘
the amount of acetic acid in the treating liquid 30 the reaction is slower, and therefore, on a com
is increased, a vastly superior ?ber is obtained,
nrercial scale there is no advantage in using the
and furthermore, that by treating the ?ber in
lower temperatures. The temperature should not
the liquid containing the increased amount of
be so high as to cause yellowing or softening of
acetic acid, it isv unnecessary to neutralize the
?ber during treating. The maximum tem
acid in the treating liquid, since the ?ber as‘it is 35 the
perature will depend somewhat on the protein
removed from the treating liquid will carry with
from which the ?ber is made and the presence
it an amount of acetic acid absorbed therein
in the ?ber of ingredients which tend to yellow
which is equivalent to that formed by the reac
or char at lower temperatures. It is possible in
tion of the water in the ?ber to be treated with
all instances to operate at atemperature below ‘
acetic anhydride. In‘other words, it has‘ been 40 the
harmful temperature and at which the re
discovered that the moisture content of the ?ber ‘ I
can be adjusted as to produce an amount of
action rate permits the treatment to be concluded '
in.,a reasonable time. The temperature and
acetic acid during the treating process which will
treating time are also related somewhat to the
be absorbed in the ?ber during the treatment if
of anhydride. When ‘the temperature is
the amount of acid carried in the treating liquid 45 amount
lower
the
reaction can be speeded by larger
is at a su?lciently high level. Not only’ is the
amounts of the anhydride. There is no advan
neutralizing eliminated in this way, but a, superior
tage commercially in using the larger amount
acetylation of the ?ber results, apparently due
when the same result can be obtained by a. higher
.to the larger‘ amount of acid in association with
50 temperature. The selection of these variables‘
the acetic, anhydride in the treating solution.
will be made dependent on economic and other
In accordance with the invention a ?ber may
operating factors as will be apparent to one skilled
, be "produced that, has a superior resistance to
in the art, in view of the disclosure herein.
chemical activity of the undesired type, such as
The amount of acetic acid within the above
breakdown by bleaching agents and deterioration '
percentage is critical if the ?ber is to have the‘
by hot water, acids, or alkalides, while at the same 55 desired dyeing properties. While the acetic acid,
time it has superior chemical properties imparted
as such, apparentlyv is not an acetylating agent,
to it with respect to its reaction to dyestu?’s and
and
the acetylating reaction is apparently attrib
chemicals ordinarily used in the process of nat
uted to the acetic anhydride, nevertheless the
urally occurring proteinaceous ?bers. The ?ber
presence of. a critical amount of acetic acid has
also remains unusually soft and pliable and re 60 ‘a
great effect on the nature and extent of the
tains or even has its physical properties im
acetylatlon and the properties of the ?ber. If
proved. It acquires to a greater extent those too
little is present, the resulting ?lber has unde
properties desired by textile operators.
'sirable ‘dyeing properties and absorbs dyestu?s' I
The ?ber produced can better withstand boil
which ordinarily do not dye wool. On the other
ing for long periods of time in water, as well as 05 hand, id the acid concentration is too great, the
in hot dilute acid solutions such as‘ are used in
?ber‘ becomes too soft and is poorly acetylated.
dyeing. It is also enabled better to withstand
By controlling the amountgof acetic acid between
vigorous mechanical treatment combined with
the above critical limits it is possible to produce '
alkaline material, such as “fulling" and “scour- I
i'ng” operations, even after preparing it for dyeing 70 a ?ber which has dyeing properties closely simu-'
lating that of natural wool and which resists
operations.
.
dyes which do ‘not dye wool and is dyed'by dyes
.The ?ber also is not ’only not harmed by dyeing
operations, but has desirable properties in that
,it accepts dyes ordinarily accepted by natural
proteinaceous ?ber and rejects dyes which are not
which ordinarily dye wool and at about the same
rate.
In carrying out the process, a treating liquid
. 2,405,027
\
i
»,
is prepared in accordance with the above for- .
mula, and about‘ 300 gallons is used for each 275
pounds of the ?ber to be treated. The'?ber is
placed in the liquid and agitated therein while
6
matured as Patent No. 2,342,994 on February 29,
1945) but other processes may be employed in
making the fiber, and the process is not critical.
The ?ber should be treated with formaldehyde
after thespinning and before the treatment in
accordance with theinvention. Preferably the
' the liquid is maintained at a temperature of 150
to 225° F., preferably 185 to 195° F. The treat
ment is continued for about 10 minutse to 2
hours, preferably one-half hour, after. which the
excess of the treating liquid is separated from
the ?ber, such as by centrifuging. Following this,
10 formaldehyde vapor. A‘ process of treating spun
_ the ?ber may be placed under a vacuum and as
?ber with formaldehyde is described in copending
?ber after spim'ling is soaked in one or more
_ formaldehyde containing baths and then washed
and dried. Alternatively it may be treated with
much of the treating liquid vaporized as pos
sible.
application Serial Number 417,024, ?led October
29, 1941, but other processes may be used.
The protein may be any alkaline-dispersible
'
The proteinaceous ?ber at the time it is intro- -
duced into the treating ‘solution preferably should
15
have a moisture content of between 3 to 6%.
The moisture in the ?ber reacts with a portion
of the acetic anhydride to form acetic acid.
However, it is a characteristic of the ?ber that
it absorbs acetic acid, and the amount of acid 20
formed by this reaction is absorbed in the ?ber
when the acetic acid concentration is maintained
within the above de?ned critical limits. When
the ?ber 'is removed after the conclusion of the
acid-coagulable protein. The protein from milk,
termed animal casein, and the protein from soy‘- '
beans, often referred to as vegetable casein, may
be used advantageously and these materials are
included in the generic designation of casein as
used herein. Other proteins, such as those ob
tainled from peanuts, seeds, hair, etc., may be
use
.
The process of the invention is simple to "op
crate, and may be practiced in a continuous semi
process, it carries with it acetic acid equivalent 25 continuous or batch operation. It requires a
to that formed by the reaction of the water with
minimum' of materials, and temperatures that
the acetic anhydride. Before the next batch of
are readily obtainable. It has the advantage of "
?ber is treated in the treating liquid, additional
simplicity of operation as well as the production
acetic anhydrlde is added to bring the concen
of a superior ?ber.
tration up to the desired amount. ‘Thus for each 30
An important advantage of the invention‘ re
batch of ?ber it is necessary only to add acetic
sulting from the control of the acetic acid con
anhydride equal to that which combines with
the protein and is converted to acid by reaction
with the‘ water in the ?ber, together with an
amount of solvent equivalent to that absorbed by 35
tent within the above critical limits during the
acetylation is the rate of dye absorption. Not
only may the ?ber produced in accordance with
the invention absorb dyes which act on ,wool and
resist non-wool dyes, but the ?ber may absorb
When the moisture content is reduced to within
the above range, the process is adapted for con
the dye at about the same rate as does wool in
suitably controlled dye baths. This is an im
port-ant property, since it is important that a uni
the ?ber or lost evaporation.
,
"
tinuous re-use of the treating liquid as explained
above. This does not mean that fiber with a 40 form product be produced insofar as dyeing prop- _ ’
higher or lower moisture content cannot be used.
erties are concerned. In the dyeing of mixed
Since it is very di?icult to dry the ?ber to a
goods it is also important that the different ?bers
moisture content of less than 3% without harm
of the mixture should all be the same shade as
ing it, there will be few, if any, occasions to prac
the result of treatment for a given length of time
tice the process with a ?ber of a lower moisture 45 in the dye bath. If one of the ?bers, for example
content. It is possible to treat a ?ber with a
a synthetic proteinaceous ?ber, absorbs the dye
higher moisture content but the amount of acetic
at a faster or slower rate than another ?ber,
acid formed by reaction of this amount of mois
the dyed synthetic ?ber will be darker or lighter,
ture with acetic anhydride is in excess of that
respectively, than the natural wool dyed there
which is absorbed by the ?ber and removed with 50 with. It is entirely unobvious that the concen
it when the acid concentration is within the above
tration of acetic acid, which is not an acetylat
critical limits. Under the circumstances it is
ing agent itself, rather than the concentration
_ necessary to start with a treating liquid. having
of acetic anhydride, should a?ect and control the
an amount of acid, so that the acid produced in
dyeing properties of the ?bers.
the treatment, which is in excess of that ab 55
The process is subject to the variation in ma
sorbed by the ?ber, brings the acid concentra
tion of the treating liquid within the critical
terials and conditions described herein, and all
invention does not exclude the use of the same.
range of 150° to 225° F., said treating liquid com
prising an organic solvent inert with reference
of the same are included in the invention as are
range. If the treating liquid is to [be re-used for
within the following claims.
'
treating more ?ber of higher moisture content,
I claim:
it is necessary to neutralize the excess acid.
60
1. A process of treating a synthetically formed
After the ?ber is removed from the treating
protein-base ?ber produced by shaping into ?ber
solution, it is washed thoroughly with water and
form an alkali-soluble acid-coagulable protein
the acetic acid absorbed in the ?ber is washed
comprising casein and treating it with formalde
out, leaving the ?ber relatively free from acid.
It is unnecessary to use neutralizing or other 65 hyde, which process comprises treating said ?ber
while having a moisture content of about 3 to 6%
Q‘ basic ingredients in the wash water, although the
The protein ?ber to be treated in accordance
with the invention is made by dispersing the pro
in a treating liquid at a temperature within the‘ ‘
_ to the ?ber and the ingredients contained in the _
tein in water with an alkaline material, such as 70 liquid and containing about 5 to 15% acetic anhy
caustic, following which the dispersion is spun
dride and about 5 to 7% of acetic acid, the tem
perature and the amount of acetic anhydride
tain a tanning agent. A process, which may be
within the above ranges being selected with refer
used is described in co-pending application Serial
ence to each other and to the ?ber'being treated
Number 309,028, ?led August 23, 1939, (which 75 so as to impart more desirable chemical prop
' into an acidic coagulating bath which may con
9,408,087
7
.
erties to the ?ber without undue yellowing there
.
_
-
_ 8
e
_ in a treating liquid at a temperature of 150° to
225' r. for 10 minutes to 2 hours, ‘said treating
liquid comprising an organic solvent inert with ‘
amount 0! acetic acid formed by reaction of the - - reference to the ?ber and the ingredients con
tained in the liquidv and containing. about 5 to
moisture in the ?ber with the acetic anhydride in
15% acetic anhydride and about 5 to 7% of acetic
the treating liquid as a result of the speci?ed
- oi’. and removing the ?ber from the treating liq
uid having absorbed thereinl substantially the
moisture content 01' the ?ber and the acid con- _
tent of the bath.
a
2.’ A process of treating a synthetically formed '
protein base ?ber produced by shaping into ?ber
form an alkali- luble acid-coagulable protein
comprising casein and treating it with formalde
hyde, which process comprises treating said ?ber
while having a moisture content of about 3 to 6%
acid, and removing the ?ber from the treating
liquid having absorbed therein substantially the
amount or the acetic acid formed by reaction oi '
the moisture in the ?bernwith the acetic anhydride
in the treating liquid as a result or the speci?ed
moisture content of the ?ber and’ the acid con
. tent of the bath.
FRANCIS CLARKE A'I'WOOD.
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