Патент USA US2521330

2,521,328
Patented Sept. 5, 1950
UNITED STATES PATENT OFFICE
2,521,328
STABILIZING CELLULOSIC TEXTILE MATE
RIALS AGAINST SHRINKAGE EMPLOYING
GLYOXAL AND A METAL SILICOFLUORIDE
AS A CATALYST
Leo Beer, Providence, R. I.,.assignor to Alrose
Chemical Company, Cranston, R. I., a corpora
tion of Rhode Island
No Drawing. Application October 14, 1948,
Serial No. 54,581
9 Claims. (Cl. 8—116.4)
2
This invention relates to the treatment of
textile materials of naturalvor regenerated cellu
lose or mixtures thereof for the purpose of elim
inating their tendency to shrink upon washing
in aqueous soap solutions at elevated tempera
tures.
It also relates to the treatment of such desig
nated textile materials to secure excellent sta
Number 750,159, ?led May 23, 1947, the use of an
alkali metal sulfate to modify the catalytic action
of the oxalic acid is described.
Broadly, it is an object of .the present invention
The normal fabrics made from these ?bers and
mixtures containing the same, i. e. without treat
ment, have a marked yet normal tendency after
It is the object of the present invention to treat
textile materials that are formed predominantly
to secure the advantage of employing a solution
of glyoxal to render textile materials, composed
of natural cellulosic material or regenerated
cellulose, stable against shrinkage yet r?itigating
the attendant disadvantages in loss of tensile
bility against laundry shrinkage without incur
ring any appreciable loss in tensile strength or 10 strength and abrasion resistance in most pres
ently employed commercial processes.
abrasion resistance.
successive washing and cleaning to shrink to
different degrees; this affects the wearability of
the fabric.
'
Many attempts have been made to develop
and perfect processes which control the shrink
age of fabrics with and without the use of resins.
Fabrics have been treated :by conventionally em
ployed processes in the industry with formalde
hyde or compounds which split off formaldehyde,
of natural cellulosic materials or regenerated
cellulose with dilute aqueous solutions of glyoxal
in the presence of a soluble inorganic salt of
silico?uoric acid to stabilize them against shrink
age, but with no appreciable loss in tensile
strength or abrasion resistance.
It is a more speci?c object of the present inven
tion to secure stabilization of the aforesaid types
of textile materials against shrinkage but with
out signi?cantly impairing their tensile strength,
wherein the ?bers are wetted by a dilute solution
but always in the presence of strong acids, or in
the presence of a salt which is acid-reacting per 25 of glyoxal and subsequently baked at 100° C. or
higher until the desired shrinkage control has
se or becomes acidic during processing, such as
been secured i. e. a substantial reaction between
baking at elevated temperatures. This results
the cellulose and glyoxal has taken place.
in deterioration in tensile strength and abrasion
Other objects and features of the invention will
which is especially serious in the case of cotton.
By a more recent development, cellulosic ?bers 30 be apparent from the following description:
Broadly speaking, my invention consists in em
and fabrics have been treated by a process char
ploying certain inorganic salts of silico?uoric
acterized by the employment of glyoxal, and
acid in catalyzing the glyoxal-cellulose reaction
which must take place within the fibers of nat
as rayon fabrics are made shrinkproof to a great 35 ural or regenerated cellulose if shrinkage resist
ance is to be attained when using glyoxal. In
degree and the shrinkage tendency signi?cantly
my invention the acidity of the impregnated
curbed in the case of cotton fabrics, the former
goods decreases during baking of the goods at
displays a loss in the range of 20% in tensile
temperatures of 100° C. and above. In terms of
strength, and the latter the range of 50%.
In the inventor’s copending U. S. patent appli 40 pH values this means an increase of the pH, con
trary to known methods where the pH decreases
cation Serial Number 722,955, ?led January 18,
during concentration and baking. Also whereas
1947, which has become Patent 2,484,545, with
the presence of oxalic acid increases the acidity
issue date of October 11, 1949, this disadvantage
of the aqueous impregnating glyoxal solution, the
is overcome by employing a substantially neutral
water-soluble alkali metal salt of an acid whose 45 presence of magnesium silico?uoride decreases
the acidity of the aqueous glyoxal impregnating
oxidation potential in solution of unit activity
solution, because an aqueous solution of this salt
referred to the normal'hydrogen electrode at 25°
is not as acidic as the glyoxal solution. Further
C. is greater than -0.9 volt, such as the chlorate,
more as explained below,'magnesium silico?uo
nitrate of perchlorate, instead of oxalic acid.
In his copending U. S. patent application, Serial 60 ride decomposes during the baking step to yield
wherein oxalic acid is the catalyst to’ confer
stability against laundry shrinkage. But where
2,621,328
3
4
a more basic reacting component and a volatile
compounds on curing, which is the stage of the
acid component. The basic component which is
process when the glyoxal-cellulose reaction takes '
formed on the cloth protects it, which would not
be true in the case of a ?xed acid component.
as follows:
By the present invention, any form of textile
material of the types described infra is thor
oughly wetted with the aqueous solution of gly
oxal in the presence of the silico?uoride, the
excess liquid removed mechanically, the textile
material then dried, and “curedn or baked at an
elevated temperature until a substantial shrink
age reduction has been achieved. This shrink
.
place,‘ is the decomposition of the silico?uoride
The volatile silicon ?uoride acts as the reaction
catalyst while the somewhat alkaline magnesium
?uoride, which is formed directly on the cloth,
acts as a buffer or protective agent for the cloth.
It is thought that this is what transpires that
makes it possible to carry out the reaction with
age reduction may be explained as due to a. reac
out loss in tensile strength or abrasion resistance.
tion which is believed to have taken place in
In the aqueous wetting solution the suggested
the ?bers of the textile material, 1. e. the glyoxal 15 range for concentration of glyoxal is 1% to 10%
cellulose reaction The goods are then scoured,
inclusive of 100% glyoxal, preferably 1% to 5%
rinsed, hydroextracted and dried without ten
inclusive, based upon the weight of the treating
sion. Finally the fabrics are steamed and framed
solution, When the quantity is less the goods
to predetermined ?nished dimensions (as indi
treated by this process lacks signi?cant shrink
cated by a laundering test). It will be under 20 age resistance. When the quantity exceeds 10%
stood, however, that these steps subsequent to the
there is the risk of damage to the fabric, depend
baking do not form part of the present invention.
ing somewhat von the baking temperature and
As has been pointed out supra cellulosic textile
time. Technical glyoxal is sold as 30% by weight
materials treated by the present invention are
glyoxal, so the amount on the 100% basis will
characterized by permanent stability against 25 have to be computed. As to the catalyst, the
shrinkage. Glyoxal (also known as oxaldehyde
amount of about 0.3% to 3.0% by weight or‘ the
or ethandial, and whose structural formula is
aqueous impregnating solution, but preferably
CHO.CHO) is the agent which reacts with the
0.5% to 2.0% inclusive, in terms of MgSlFaGHzO,
cellulose and is responsible for conferring these
is the suggested range. The above percentages
properties. The inorganic salts of silico?uoric 30 of concentration of glyoxal and the silico?uoride
acid act as the catalyst to promote the reaction.
catalyst are each based upon a 100% pick up of
Under the condition described herein glyoxal
liquid in reference to the weight of the goods.
without-the caltalyst will not confer these prop
Fabrics or ?bers of regenerated and/or natural
erties.
cellulose display little or no tendency to shrink
While it appears that all metal salts of silico- ., upon washing after treatment according to the
?uoric acid are suitable for use as catalysts, the
present invention. The method herein disclosed
water-solubility and hydrolysis rate impose some
can moreover be successfully applied to mixtures
limitations on the selection of the salts of this
of natural and regenerated cellulose as well as
group from an operating standpoint. Since it is
to either alone, or to mixtures containing either
generally desired that the color of the treated 40 regenerated cellulose or natural cellulose with
material should remain unchanged this makes
cellulose acetate, provided the fabric does not
certain of these salts undesirable.
contain more than 50% cellulose acetate. The
The sodium-, and potassium-, and ammonium
last may be replaced by other cellulose esters or
silico?uorides have each proven satisfactory but
organic acids, such as the propionate. By the
are dimcult to handle because of their low solu
term “regenerated cellulose” I mean viscose or
bility in water and aqueous solutions. The arm
cuprammonium rayon or saponi?ed cellulose ace
monium salts furthermore tend to yellow the fab
tate, By the term “natural cellulose” I means
ric on curing.
such fibers as cotton, linen, hemp and jute, more
Zinc-, magnesium-. ‘and cadmium salts are
particularly cotton. The textile materials com
suitable, and because they are highly water-sole 50 ing within the preview of this invention are those
uble and do not have the secondary character
composed of or predominantly of cellulose ?bers
istic of discolorlng the cellulosic fabrics, either
of natural vegetative origin or of regenerated
natural or regenerated, they are the choice. In
cellulose.
'
'
general, I prefer to use magnesium silico?uoride,
The treatment by this invention, and which is
commercially avialable as MgSiF'aGHzO, because
described in more detail below, may be employed
of its ready solubility and its stability at mod
on fabrics containing any percentage of cotton
erate temperatures. That last expression will be
since the treatment has no deleterious e?ect on
understood to embrace the ranges up through
natural cellulose ?ber. This process is thus an
150° C. and somewhat above under the conditions
extremely important improvement over the
of operation herein.
60 known aldehyde processes for shrinkproo?ng
Moreover, I should like to point out that other
?bers of vegetable origin.
metal salts of silico?uoric acid, such as nickel-,
The regenerated and/or natural cellulose may
cobalt-, iron-, manganese-, or mercury are
be treated in any form, by which is meant ?la
highly water-soluble and could be used if dis
ments, ?bers, staple or yarn; woven, knitted,
coloration caused by the metallic ion is not ob 65 braided or pretreated fabrics as well as clothing
jectionable for the ultimate purpose. In fact,
or other ?nished goods. And the term “textile
it is possible by the use of these latter compounds
material” unless otherwise quali?ed includes
to obtain simultaneously shrinkage control and
these.
mildew-resistance or rotproo?ng, and in some
The step of impregnating the ?bers or ?la
cases even water repellencey, or flameproo?ng; 70 ments with the aqueous solution of glyoxal and
this can be e?ected by precipitating the metallic
silico?uoride may take place at any time subse
salt by a suitable after-treatment, i. e. after bak
quent to any desizing of the fabric which is to
ing, using alkali, soap, alkali phosphates or other
be treated. But all traces of starch, gums, glue
basic chemical agents.
or natural resin and other sizing agents should
A possible explantation of the action of these 76 be removed for optimum results in order to per
2,621,828
5
6
mit the aqueous solution to penetrate the fibrous
regenerated type treated by my invention here
in are stabilized against shrinkage upon wash
ing in aqueous solutions at elevated temperatures
as vpointed out supra. The superior nature of
The impregnation or wetting of the textile ma
this process can be appreciated when, more
terial with the aqueous liquid or solution can be
over, it is realized that this obtained effect
accomplished in any desired manner, such as by
is a permanent one, and even successive wash
immersion. spraying or coating'by other modes.
ings at the boil do not affect the results. Fab
Usually this is done in a continuous manner, the
rics of viscose or cuprammonium yarns so proc
amount applied being governed by the rate of
travel of the textile material. The excess liquid 10 essed are further improved as borne out by the
fact that they show less tendency to fuzz during
should be removed before the drying step. . This
or ?lament material and enter the heart of the
?bers.
‘
washing, as compared to an untreated material
may be achieved by various mechanical means
similarly washed. The loss in tensile strength
such as squeeze rolls, centrifugal devices or vac
after this treatment is negligible, and no diminu
uum extractors. This allows a pick-up of a pre~
determined percentage, such as 100% liquid re 15. tlon of abrasion resistance occurs. Provided
that the dyes used on the fabrics are fast to re
tention on the dry basis of the goods.
The drying and curing can, alternatively, be
peated boiling in aqueous soap solutions, the
treated materials can be considered boil-fast with
respect to shrinkage control and. wearing prop
ferred to make two steps of this, and the de
'
scription will be explained more fully as to that 20 erties.
This invention will be more clearly understood
mode. The drying is carried out at low temper—
by reference to the following examples. It is to
atures such as ‘IO-100° C. and preferably at 100°
be understood, however, that these examples are
C. although it could be at even lower tempera
merely illustrative of the process, and that the
tures, and until the moisture contact has been
reduced to about 10%; this moisture limit is not 25 invention is not limited thereto but rather is‘ de
?ned in the appended claims. In the examples
exactly critical but the fabric should not be over
the term “check” has the meaning of untreated
dry. For woven fabrics, this step is accomplished
or original. The term “total shrinkage” signi?es
on a tenter frame.
'
the entire shrinkage occurring to the material (in
The cellulosic textile material thus treated is
then baked or ‘cured”—usually in a loop dryer 80 either warp or ?lling direction) due to complete
sequence of processing and wash testing, or wash
without tension. While temperatures of 100° C.
carried out as a single operation.
But it is pre- .
testing alone in the case of untreated or check
or just slightly above can be used, because of the
sample. The term “compression shrinkage" signi
element of time, a range of 130° C. to 150° C. with
?es the total shrinkage of an untreated or unproc
an inverse time interval of 6 to 2 minutes is pre
ferred. It is of course essential that the time 35 essed materialafter the securing and wash test
ing. The term “gain over compression shrink
interval in this baking step be of sufficient dura
age” signi?es the advantage in length (or width)
tion that the treated textile material when sub
gained by use of the described process over that
jected to the Federal CCC-T-191A test exhibits
of a swatch which has not been subjected to the
a substantial reduction in shrinkage in compari
process, i. e. after both have been scoured and
son to the untreated sample of the same ma
terial. vThose temperature-time conditions giv
ing the optimum stability against shrinkage wlil
normally be selected. Selection and choice for
optimum results is not con?ned to this step but
is equally applicable to the conditions in each 45
of the steps and the process as a whole how
wash tested.
-
EXAMPLE 1
100% spun viscose rayon fabric treated
The impregnating solutions had the following
compositions:
ever.
After the curing or baking step the textile ma
terial is washed without tension, dried, and
?nally framed to the dimensions indicated in a
preliminary wash test. In same cases, overfeed
devices in the ?nal tentering operation are em
ployed, but in other cases, it is necessary to ap
ply some warpwise batching tension to counter
act supercontraction in the previous drying op
eration. However the steps outlined in this par
agraph are not part of the present invention, al
though they are supplemental operations before ,
the textile material is put into industrial chan
nels or trade.
Solutions
Components
No. A
Glyoxal, 30 per cent technical ___________ "grams"
MgSiFdEhO _______________________________ __do_-_.
Water-
Hang
a
No. B
70
20
1
The magnesium silico?uoride was dissolved in
water at about 38°‘ C. (higher temperatures might
vresult in some hydrolysis). A. wetting agent
may advantageously be added to these respective
baths to reduce the time necessary for complete
saturation, as was'done in this example.
If desired the “hand" or “body” of the goods
treated can be modi?ed in the direction of either
Two samples of the above fabric were impreg
softness or a stiffer ?nish at will by the intro
nated on a padder with the above solutions No.
duction to the impregnation bath of suitable
A and No. B respectively. Each of them was
agents, such as cation softeners for the former 65 then squeezed to a liquor retention of 100%, based
effect, or such vegetable or animal colloids as
on the weight of dry goods, and then dried with
starches, gums, glues, gelatins and modi?ed
out tension at about 100° C. Care was exercised
starches for the latter effect. But the process of
to avoid over-drying (8% to 10% moisture should
this invention is carried out in the absence of any
remain in the goods at this point).
phenolic or amidic compounds capable of form 70
After drying, the samples were each divided
ing resinous bodies with aldehydes‘ under the
into two parts (A-l, A-2 and 3-4. 3-2) and cured _
conditions employed. Therefore, fabrics treated
by my method show no tendency toward chlorine
retention.
.
'
as follows:
A-1 and B-1 ____________ -_6 minutes at 138° C.
Fabrics of the natural cellulosic type or of the 75 A-2 and B-2 __________ -_6 minutes at 127° C.
3,521,328
7
8
The samples were thereupon washed, rinsed
Warp tensile strength, pounds
and dried. They were then laundered together
with the check sample by the accelerated l-hour
Check
54
#1 (after 3rd wash) _____________________ __ 59
wash test described in Federal Speci?cation
#2 (after 3rd wash) _______ __' ____________ .._ 53
CCC-T-191A. The following shrinkages were
observed based upon the measurements:
Conclusion
Again, excellent permanency against shrink
Warp shrinkage (in percentages)
age was obtained, with no appreciable loss in‘
tensile strength.
.
_
Gainover
Samp1a Idanti?eation
1°
nxammn 3
Traded
141°“ @1312‘:
an
~ “TM”
s on
ured "“h ‘
age!
Shrink
,Samples of mercerized cotton fabric
age
The impregnating solutions had the following
15 compositions in grams by weight:
-0.0
________ -_
—-4.1
—3.2
—3.4
4.9
5.8
5.6
-2.6
6.6
Components
e1
,
No. 1
h _______________________ __
__
Hallstatt???......................... £33..
lMeasured from scoured dimensions.
1 Measured from original dimensions.
Tensile strength (lbs. grab-test)
\
No. 2
’21
20 Water ____________________________________ _-liters_-
The samples were subjected to tensile strength
measurements. the values 0! which were:
l81
The two solutions were made up, the samples
of the fabric immersed therein, squeezed to 100%
20V retention and dried at about 100° C., similar to
Dry
Check
A-l.-.
.
.... __
s-1_-
Example 1. They were then baked for 21/2 min
utes at 150° C., the same temperature as in Ex
Wet
- ample 2. They were then washed and dried as in
40
15
4s
1s
4a
1a
A-2. . .
46
15
13-2. _
43
15
Example 1.
Warp shrinkage, per cent
Sample Identi-
Conclusions
?cation
A considerable degree of permanent stabiliza
tion against shrinkage was obtained (see “gain
over compressive shrinkage" column) without
any loss in tensile strength.
Successive
Tmated l'hour wash“ I
802:?“
15‘;
2nd
Total
Gain Over
Compres
8mg“?
“3
Shrinkage
sion
—5.1
—l.3
—1.
—6.4
.......... __
—-3. 2
--3.3
—-0. 6
-—0.6
-0. 8
—0.8
—4. 0
—4.0
2. 4
2.4
40
EXAMPLE 2
1 Measured from scoured dimensions.
, 1 Measured lrom original dimensions.
100% spun rayon fabric treated
The impregnating solutions had the follow-7
ing compositions:
45
The samples were then subjected to tensile
strength measurements. _
Tensile strength (lbs., grab-test)
Components
No. 1
No. 2
Check ___
___ 54
#1 _____________________________________ __ 49
Glyoxal 3
tech _______________________ -_grams__
70
20
#2 _____________________________________ __ 44
to???
l
Conclusions
MgSiF|.ilH% _____________________________ __d
Water. _
Cotton was also permanently stabilized consid
The two solutions were made up, the samples
erably, using a silico?uoride catalyst, with only
of the fabric (designated No. l and No. 2 re 55 slight loss of strength. This is in marked con
spectively) wetted with the above solutions re
trast with losses of about 50% when oxalic is
spectively, squeezed to 100% retention and dried
used as in the prior art under the same condi
at about 100° C. as in Example 1. They were
tions as herein.
then cured for 31/2 minutes at 150 C. They were '
EXAMPLE 4
then rinsed, scoured and dried and tested as in
Example 1. In this case, laundering shrinkage
Spun viscose rayon fabric treated
was measured from the scoured dimensions.
The wetting solution had the following com
position: 70 gms. of glyoxal (30% tech.), 15 gms.
65 magnesium silico?uoride (MgSiFs'6H20) and
0.2 gm. “Igepal CTA extra” (:1 commercial poly
Warp shrinkage (in percentage)
Successive 1 hr.
Sample
Treated
Ideati?Bclznd d
0
on
n
ure
~
washes 1
1st
2nd
3rd
Total
$323132?”
Shrm’lp
,
Shrinkage
age
ethylene condensation product manufactured by
sion
General Dyestuff Corporation of New York city)
.
per liter of water.
70
Cheek_____
—7.5
—l.4
— .
N0. 1 ---- __
N0. 2 ____ .__
—3. 9
—3. 3
—0. 7
+0. 6
—0. 6
—o. 6
1 Measured irom scoured dimensions.
I Measured irom original dimensions.
—4.2
-ll.7
__________ __
0
0
—3. 9
—3. 3
7. 8
8. 4
Three di?erent types of spun viscose rayon
fabrics designated Quality A, Quality B and Qual
ity C, were impregnated with this solution,
squeezed to 100% pick-up of solution and dried
as in Example 1. They were then baked for 3
75 minutes at 150° C.
2,621,828
10
The samples were then washed, rinsed, scoured I
and dried as in Example 2.
mentioned. In this case laundry shrinkage was
measured from treated dimensions.
Warp‘ shrinkage, percent
Warp shrinkage, per cent
Successive 1 hr.
m s?plctel Tagged
en
ca on mum,
Gain over
washes‘
m
Sam plo
s'ggtgllb cogioilalms-
2nd
m
age,
shrinkage
"
check
2d
3d
4th
5th
-5.s
-5.s
-1.a
-7.4
-s.o
10 #1 _____ _- —0.4
-o.1
-11.4
#2
Quality A,
treated .... _-
0
+0.5
0
-3.1
118
Gain Over
'
if!"
Shrinkage
—s.o __________ __
+0.6
-0.6
--0.6
7.4
—0.6
-1.1
-1.1
6.9
.
as
Quality B,
qchplprt
-1.5
.
-s.1
'l‘otal2
Shrink- mgg’rfes'
lst
Check__
Quality 4,
Successive l-hr. washesl
éggggi-
lMeasuredfrom scoured dimensions.
B
—l2. 2
y
’ Measured from scoured dimensions.
-
'
marginal- -e.4 +0.6 +0.1 +0.1
QghLk Y
-
-s.1
. »
0.5 15
_6_2
by employing the silico?uoride catalysts which I
Quality 0,
“°”t°d----
From the above examples, it will be seen that
have described, I have succeeded in obtaining
*°'_1 ‘H13 +04 +0'‘ . “0'6
5'6
rayon and cotton fabrics stabilized against laun
1 M med H m mm d dim Signs 1
dry shrinkage, without appreciable diminution in
, Mgsmd “gm original dlmgsionsz 29 the tensile strength or abrasion resistance ofthe
fabric. ' 0n the other hand,“ baking such fabrics
Qualities A and C were then subjected to both
which have been impregnated with an aqueous
tensile strength and abrasion resistance meas
urements, the value of which were:
Tensile
Strength Abrasion Re
(Warp,
sistance
lbs. Grab (Taber
Cycle)
solution of oxalic acid and glyoxal of 1.0-2.5 pI-I
\and containing the corresponding quantity of
25 glyoxal per volume, followed by squeezing and
drying wherein the treating conditions corre
Test)
C uality A, check ____________________ __
_71
G uality A, trcated_ - -
--
71
275
300
G uality 0, check____.
__
62
275
125
130
300
Quality 0, treated __________________ __
63
125
130
30
spond in each, result in severe damage to cotton
such as a- loss of 30-60% in tensile strength or
even more; and it frequently reduces the tensile
strength of rayon by as much as 10 to 25%. This
deleterious effect is described further in my U. S.
Patent #2,484,545 of October 11, 1949, and my
copending U. S. Patent application Ser. No.
750,159, ?led May 23, 1947.
Conclusions
Because high temperatures in forming the solu»
35
It is quite apparent that the spun viscose rayon
tions and in the wetting step may cause partial
fabrics have been quite satisfactorily rendered
hydrolysis of the metallic silico?uoride such tem
permanently stable against progressive shrinkage,
peratures should be avoided. Because an excess
of glyoxal and also of the silico?uoride are harm
while the tensile strength and abrasion resist
ance has not been lessened.
‘0 ful to' cellulosic ?bers, the minimum quantity of
each which will produce the desired shrinkage re
EXAMPLE 5
duction without ' decrease in tensile strength
Spun rayon fabric treated
The impregnating solution had the following
should be used, taking into account the time and
temperature.
.
composition: '70 gms. of 30% tech. glyoxal, 10 gms. 45 In the claims the term "short chain aliphatic
aci ” embraces those not above four ‘carbon
of sodium silico?uoride per liter of water.
atoms.
I
A sample of the above fabric was impregnated
It will be realized by those skilled in the art
with this solution at 40° C., squeezed to 100%
that changes may be made in the process herein
pick-up of solution and dried as in Example 1.
It was then baked at 300° C. for 3 minutes.
60 before described without departing from the scope
of the claims.
It was then washed, rinsed, scoured and dried
as in the previous Examples 1 to 4, its tensile
Having described my invention, ‘what I claim
strength measured as in those examples or in its
and desire to secure by Letters Patent protection
abrasion resistance as in Example 4.
EXAMPLE6
.
is:
_
‘5
100% 'spun rayon fabric treated
The impregnating solutions had the following
compositions: .
.
.
1. In the process of stabilizing a textile ma
terial against shrinkage upon washing in hot
aqueous solutions without signi?cant loss in ten
sile strength and abrasion resistance, the steps
of impregnating textile materials of the group
consisting of natural cellulose, regenerated cellu
lose, and mixtures with each other and up to sub
QuantiQuanti
ties
ties
Components
’ stantially 50% of cellulose esters of a short chain
aliphatic organic acid, with an aqueous liquid
Glyoxal 307 tech ___________________ __grams-_
MgSiFabHzOo
do
ZnSiFaGHzO
dn____
70
15
as
“Igepal C-TA” ________________________ “510.-.-
0.5
0.5
Water ________________________________ __htcrs__
1
1
containing substantially 1.0 to 10.0% glyoxal and
2 a water-soluble metallic silico?uoride in an
amount of at least substantially 0.3%, each by
weight, on the basis of the treating solution and
a 100% pick-up based on the dry weight of‘ the
The samples of the above fabric -(designated
goods, mechanically removing surplus impregnat
#1 and #2 respectively) were impregnated with 70 ing liquid, then drying the textile material after
the above solutions respectively which had been
said liquid removal, and curing it at a tempera
made up as in Ex. 1. They were then squeezed
ture above substantially 100° C. for a period of
and dried as in Ex. 1. They were then cured at
time inversely related to the temperature until
150° C. for 3% minutes. This was followed by the
there is a substantial reduction in shrinkage in
rinsing, scouring and washing steps as previously 75 comparison with the un-treated textile material.
2,021,328
2. In the process oi’ stabilizing a textile ma
terial against shrinkage upon washing in hot
aqueous‘ solutions without signi?cant loss in ten
sile strength and abrasion resistance, the steps of
up based on the dry weight of the goods, me
_ chanically removing surplus impregnating liquid,
then drying the textile material after said liquid
removal, and curing it at a temperature between
100° C. and 150° C. substantially, for a period of
impregnating textile materials of the group con
sisting of natural cellulose, regenerated cellulose
and mixtures with each other and up to sub
stantially 50% of cellulose esters of a short chain
aliphatic organic acid, with an aqueous liquid
containing substantially 1.0 to 10.0% glyoxal and 10
time inversely related to the temperature until
there is a substantial reduction in shrinkage in
comparison with the untreated textile material.
6. In the process of stabilizing a textile mate
rial against shrinkage upon washing in hot aque
a highly water-soluble metallic silico?uoride in
ous solutions without signi?cant loss in tensile
amount of substantially 0.3-3.0%, each by weight,
strength and abrasion resistance, the steps of
impregnating textile materials oi the group con
sisting of natural cellulose, regenerated cellulose
on the basis of the treating solution and a 100%
pick-up based on the dry weight of the goods.
mechanically removing surplus impregnating
15 and mixtures with each other and up to substan
liquid, then drying the textile material after said
liquid removal, and curing it at a temperature
tially 50% of cellulose acetate, with an aqueous
between 100° C. and 150° C. substantially, for 'a
glyoxal and 0.3% to 3.0% of a silico?uoride of a
period of time inversely related to the tempera
member of group 1128. of the periodic table
(magnesium group) each by weight, on the basis
of the treating solution and a 100% pick-up based
on the dry weight of the goods, mechanically re
ture until there is a substantial reduction in
shrinkage in comparison with the untreated tex
tile material.
solution containing substantially 1.0% to 10.0%
3. In the prooem of stabilizing a textile ma
moving surplus impregnating liquid, then drying
terial against shrinkage upon washing in hot
aqueous solutions without signi?cant loss in ten
of impregnating textile materials of the group
the textile material after said liquid removal, and
curing it at a temperature between 100° C, and
150‘? C. substantially, for a period of time in
versely related to the temperature until there
consisting 01' natural cellulose, regenerated cellu
is a substantial reduction in shrinkage in com
sile strength and abrasion resistance, the steps
parison with the untreated textile material.
'7. In the process of stabilizing a textile mate
stantially 50% of cellulose acetate, with an aque 30
rial against shrinkage upon washing in hot aque
ous solution containing substantially 1.0% to
ous solutions without signi?cant loss in tensile
10.0% glyoxal and 0.3% to 3.0% oi.’ magnesium
strength and abrasion resistance, the steps of
silico?uoride each by weight, on the basis of the
impregnating textile materials of the group con
treating solution, and a 100% pick-up based on
the dry weight 01' the goods, mechanically remov
sisting of natural cellulose,’ regenerated cellulose
ing surplus impregnating liquid, then drying the
and mixtures with each other and up to sub
stantially 50% of cellulose esters of a‘ short chain
textile material after said liquid removal, and
curing it at a temperature between 100° C. and
aliphatic organic acid, with an aqueous solution
150° C. substantially, for a period 01’ time inversely
containing substantially 1.0 to 10.0% glyoxal and
lose and mixtures with each other and up to sub
related to the temperature until there is a sub
a silicoiluoride of a member of group VIII of the
stantial reduction in shrinkage in comparison
with the untreated textile material.
periodic table (iron group) in amount of sub
stantially 0.3-3.0% each by weight, on the basis
of the treating solution and a 100% pick-up
based on the dry weight of the goods, mechan
4. In the process of stabilizing a textile ma
terial against shrinkage upon washing in hot
aqueous solutions without signi?cant loss in ten
sile strength and abrasion resistance, the steps
of impregnating textile materials of the group
consisting of natural cellulose, regenerated cellu
lose and mixtures with each other and up to sub
stantially 50% of cellulose acetate, with an aque
ous solution containing substantially 1.0% to 3.0 %
of glyoxal and 0.5% to 1.5% of magnesium sili
co?uoride each by weight, on the basis of the
treating solution and (a 100% pick-up based on
ically removing surplus impregnating liquid,
then drying the textile material after said liquid
removal, and curing it at a temperature betweenv
100° C, and 150° C. substantially, for a period of
time inversely related to the temperature until
there is a substantial reduction in shrinkage in
comparison with the untreated textile material.
8. In the process of stabilizing a textile mate
rial against shrinkage upon washing in hot aque
ous solutions without significant loss in tensile
the dry weight of the goods, mechanically remov 55 strength and abrasion resistance, the steps of
ing surplus impregnating liquid then drying the
impregnating textile materials of the group con
textile material after said liquid removal, and
sisting of natural cellulose, regenerated cellulose
curing it at between 130° and 150° C. substanr
and mixtures with each other and up to sub
tially, for substantially 2 minutes to 6 minutes,
stantially 50% of cellulose acetate, with an aque
the time being inversely related to the tempera 60 ous solution containing substantially 1.0 to 10.0%
ure.
5. In the process of stabilizing a textile mate
glyoxal and 03-30% of a silico?uoride of a
member of group VIII of the periodic table (iron
group) each by weight, on the basis of the treat
ing solution and a 100% pick-up based on- the
rial against shrinkage upon washing in hot aque
ous solutions without signi?cant loss in tensile
strength and abrasion resistance, the steps of 05 dry weight of the goods, mechanically removing
impregnating textile materials of the group con
surplus impegnating liquid, then drying the tex
sisting of natural cellulose, regenerated cellulose . tile material after said liquid removal, and our
and mixtures with each other and up to substan
ing it at a temperature between 100° C. and 150°
tially 50% of cellulose esters of a short chain
C, substantially, for a period of time inversely
aliphatic organic acid, with an aqueous liquid 70 related to the temperature until there is a sub
containing substantially 1.0 to 10.0% glyoxal and
stantial reduction in shrinkage in comparison
with the untreated textile material.
a silico?uoride of a member of group IIB of the
periodic table (magnesium group) in amount of
9. In the process of stabilizing a textile mate
substantially 0.3—-3.0%, each by weight, on the '
rial against shrinkage upon washing in hot aque
basis of the treating solution and a 100% pick 75 ous solutions without signi?cant loss in ‘tensile
2,591,898
l4
strength and abrasion resistance, the steps of
impregnating textile materials of the group con
sisting of natural cellulose, regenerated cellulose
and mixtures with each other and up to sub
stantially v50% of cellulose esters of a short chain
aliphatic organic acid, with an aqueous liquid
containing substantially 1.0 to 10.0% glyoxal and
manganese siiico?uoride in amount of substan
tiaily, 0.3-3.0% each by weight, on the basis of
the treating solution and a 100% pick-up based
on the dry weight of the goods, mechanically re
moving surplus impregnating liquid, then drying
the textile material after said liquid removal,
_‘
,
.
UNITED STATES PATENTS
Number
1,016,928
1,483,519
1,514,067
2,233,402
Name
Date
Bishop .......... .._ Feb. 13,
Phair ___________ .._ Feb. 12,
Phair ___________ .. NOV. 4,
Cresswell ........ .. Mar. 4,
1912
1924
1924
1941
2,412,832
Pfe?er _______ ...'....... Dec. 17, 1946
2,436,076
Pfe?er .......... .. Feb. 17, 1948
FOREIGN’ PATENTS» '
Number
585,679
Country
-
Date
Great Britain .... ...'. Rb, 19, 1947
OTHER ‘REFERENCES
and curing it at a temperature between 100° and
Rayon
Textile
Monthly‘ for August 1946. mes
150° C. substantially, for a period of time in- 15
51
(405)
and
52
(408)
.
versely related to the temperature until there is
a substantial reduction in shrinkage in compari
son with the untreated textile material,
-
LEO BEER.
aarnaancas men
The following references are of record in the
?le of this patent:
' 1