close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3094380

код для вставки
United States Patent 0 "
CC
3,094,371
Patented June 18, 1963
1
2
3,094,371
sisting of H and CH3. The substantially water-soluble
heat-curable aminoplast resin and the water-soluble ther
TEXTILE TREATMENT WITH AMINOPLAST AND
POLYACRYLAMIDES AND THE TEXTILE S0
TREATED
William Julius Van Loo, Jr., Middlesex, and Theodore F.
Cooke, Martinsville, NJ., assignors to American Cyan
anéiid Company, New York, N .Y., a corporation of
M’ ne
No Drawing. Filed June 13, 1957, Ser. No. 665,606
6 Claims. (Cl. 8-1162)
The present invention relates to a process of textile
?nishing, and particularly to a process for textile ?nish
moplastic polyamide are present in the aqueous solution
in weight ratios of from 3 to 10% of the former to 1 to
10% of the latter, and the solution is applied so as to add
at least about 3% of the aminoplast and at least about 1%
of the polyamide based on the dry weight of the textile
material. Thereafter, the textile material is subjected to
elevated temperatures to dry the material and cure the
10 polyamide and aminoplast in intimate association.
Textile materials that contain groups which are reac~
tive with the melhylol groups or the group de?ned herein
ing ‘for imparting durable hand modi?cations to textile
above as -CH2OH or the alkoxy alkyl group hereinabove
materials with speci?c emphasis on imparting durable
de?ned as —CH3—O—R wherein R is a saturated ali
stiffness to such materials. The invention further relates 15 phatic radical containing from I to 4 carbon atoms, in
to the compositions employed in such a process and to
clude cellulosic materials, principal among which are
the materials so treated.
cotton and rayon, though other textile materials that have
Heretofore, in the textile ?nishing industry, ?nishes
reactive groups which are capable of entering into a reac
have been applied to textile materials which, in addition
tion with the treating composition of the present inven
to imparting dimensional stability, wrinkle recovery and 20 tion may be treated to some advantage.
various other properties thereto have incidentally im
The present invention is, however, particularly e?ec
parted a stilt" hand or stiffness to the treated fabric. In
tive and concerned principally with textile materials that
most instances, this quality has only limited durability to
contain cellulosic materials which include mixtures of
home laundering cleaning processes or dry cleaning, de
such materials with other natural and synthetic ?bers,
pending upon the nature of the treated fabric.
In many instances, certain types of textile materials,
such as, for example, viscose rayon, which are used, as
for example, in ladies’ evening wear or in ladies’ petti
25 which do or do not contain groups reactive with either
of the groups, —-CH20H or CH2—O—R.
Both the heat-curable, at least difunctional aminoplast
resin and the thermoplastic polyamide are preferably
coats, the quality of durable stiifness is highly desirable.
substantially fully water soluble and therefore applied to
Conventional textile treating resins, as for example, 30 the textile material as a true aqueous solution. Thus,
melamine-formaldehyde condensates, urea-formaldehyde
when the aminoplast resin and the polyamide are in the
condensates, including the cylic ureas, such as ethylene
urea, 1,2-propylene urea, 1,3-propylene urea, and the like,
treating bath or solution they are believed to be substan
tially unreacted with each other, and to be present therein
as separate entities or, if co-reacted, to be so to only the
durable stiliness to the treated fabric, require the usage 35 slightest extent, or to an extent which does not signi?
of such high resin solids as to signi?cantly increase the
cantly affect the solubility of the total mixture in water.
cost of the treated material and in addition the employ
While the heat-curable aminoplast is substantially water
ment of high solids tends to destroy certain other desir
soluble and preferably monomeric, degrees of polymeriza
able characteristics of the treated material. For example,
tion which are not inconsistent with the substantially
high resin solids concentrations on certain textile ma 40 water-soluble characteristics of the material are tolerable.
terials, in addition to rendering the material sti?, greatly
So long as the aminoplast resin is not hydrophobic, it may
diminish the materials’ tensile strength. Thus, while high
be used in the present invention.
resin solids may increase such properties as wrinkle re
The aminoplast resin of the present invention, in addi
covery and dimensional stability, properties such as tensile
tion to being substantially water soluble and heat curable,
strength loss, tear strength, and the like are severely dam 45 must be at least difunctional, i.e. contain at least two
aged.
methylol groups or at least two alkoxy alkyl groups, or a
An object of the present invention is to provide a com
methylol and an alkoxy alkyl group, both of which are
position and a process for treating textile material there
at least theoretically reactive with both the polyamide and
with, whereby said treated material has good dimensional
the reactive group of the textile material, and in par
stability, wrinkle recovery, and a durable quality of stilt 50 ticular cellulosic textile materials.
when employed principally for the purpose of imparting
ness or a stilt hand.
A further object is to provide a process for treating
Suitable examples of such aminoplast resins include
urea-formaldehyde condensates, including thiourea and the
cyclic ureas, e.g. ethylene urea, l,2-propylene urea, 1,3
such material and a material so treated, in which the
quality of durable stilfncss is not achieved at the sacri?ce
propylene urea, and the like. Additionally, melamine
of the quality of {tensile strength of the treated material. 55 formaldehyde condensates and speci?cally the polymeth
These and other objects and advantages are accom
ylol melamine derivatives such as dimethylol, tri, tetra,
plished by a process for treating textile materials that
penta and hexamethylol melamine derivatives and the like.
contain groups reactive with a functional group selected
In addition, polymethylol guanamines and substituted
from the group ’_CH2OH and —CH2—-0-R, wherein
guanamines, dimethylol succinamide, the dimethylol de
R is a saturated aliphatic radical containing from 1 to 4 60 rivatives of thio(bis)alkamides and the like are intended
carbon atoms, which comprises treating such materials
to be included.
with an aqueous solution comprising (1) a substantially
These and other representative aminoplast resinous
materials may be used either alone or in combination
water-soluble, heat-curable, at least difunctional ami
with one another, and as their formaldehyde condensates
noplast resin, and (2) a water-soluble thermoplastic poly
65 or as their alkylated (etheri?ed) formaldehyde conden
amide containing recurring units of the formula:
sates as, for example, in the case of urea, the dimethylated
R!
dimethylol urea, in which alkylation or etheri?cation is
—CHa-(.L1—
=0
IIIH:
wherein R’ is a member selected from the group com
achieved with saturated aliphatic alcohol containing from
1 to 4 carbon atoms.
When alkylated derivatives are
70 used, the monohydric alcohol of the etherifying alkyl
group is ‘believed to be split off under the conditions of
cure of the present process.
3,094,371
It is believed to be essential to the present invention
that the aminoplast be at least difunctional in the present
where the aminoplast resin is dimethylol ethylene urea
and 1% of polyacrylamide is employed, it has been deter
process in order that the individual molecule of the par
mined that in order to achieve a durable stiffness that
about 6% of the ‘aminoplast is required on the fabric. In
ticular material be theoretically capable of reacting under
conditions of cure with both the textile material to be
treated and with the thermoplastic polyamide compound.
The water~soluble thermoplastic polyamide containing
distinction, when 5% polyacrylamide has been applied to
the fabric, it has been determined that about 3% of the
dirncthylol ethylene urea may be applied and durable
stiffness will be achieved. In general, it appears that the
more polyacrylamide that is applied to the fabric, the
the recurring units above identi?ed are either polyacryl
amide or polymethacrylamide. These materials may
range in molecular weight ‘from about 50,000 to about 10 less aminop-last resin is required to achieve the same dur
ability of stiffness. This generality is, however, subject
5,000,000 and higher. Those between about 100,000‘ and
to limitation in that the treated fabric must contain from
1,000,00 molecular weight have been used with uniformly
3 to 10% of the aminoplast and from 1 to 10% of the
good success. The molecular weight of the polyamide is
polyacrylamide, based on the dry weight of the fabric,
of signi?cance in that those having very low molecular
to achieve acceptable durable stiffness. In general, the
weight, for example, those having a molecular weight
term “acceptable durable stiffness” may be de?ned as
below 50,000, will not produce the desirable stillness when
that percentage of stillness which is retained in a treated
used in combination with aminoplast resins. The prin
cipal limitation with respect to very high molecular weight
material after a 10-cminute process wash (de?ned more
fully hereinafter) and it should be a value of about 50%
found that where high molecular weight polyamides as, 20 or more of the initial stiffness achieved through treatment
with a composition.
for example, those having a molecular weight of more
If the percentage of the arninoplast on the textile fabric
than 1,000,000, that the viscosity of the treating solution
is significantly in excess of the upper limit indicated
renders it more di?icult to work with.
above, the treated material would have good initial stiff
As a general rule, the intrinsic viscosity is an indication
of the relative molecular weight of the polyamide. Thus, 25 ness and would have good qualities of wrinkle recovery
and dimensional stability, but poor tensile strength. In
the viscosity of the solution increases as the molecular
addition, the durability of such stillness is generally not
weight increases. As is well known, if one of the values,
polyacry'lamides is a practical one.
Thus, it has been
its. either the intrinsic viscosity or the molecular weight
of the polyamide, is known, the other may be calculated
employing the equation:
good.
When the polyamide is employed in amounts in excess
30 of the upper limit, as it is de?ned hereinabove, the treated
material would have a good initial and durable sti?ness,
but other desirable properties, such as, for example,
where [1;] equals intrinsic viscosity, M equals average
wrinkle recovery and dimensional stability, are of a low
molecular weight, and K and a are known constants for
order. Furthermore, the viscosity of the treating com
the given polymer. In the case of polyacrylatmide, K has 35 position may be too high, with increasing processing
a value of 3.73 X10"4 and a=0.66.
di?iculties.
Polyamides suitable for use in the present invention
When the textile material has been treated with the
should have intrinsic viscosities of from between about
aqueous solution of the aminoplast resin and the thermo
0.4 to about 7.0, as measured in a l-N sodium nitrate
plastic polyamide, the material is subjected to elevated
solution. These intrinsic viscosities are determined by 40 temperatures in order to dry the same and to ellect a cure
dissolving various known amounts of the polymer in a
of the treating composition.
l-N sodium nitrate solution and introducing these solu
Drying and curing may be achieved either separately
tions into an Ostwald pipette. The time required for these
or simultaneously. In order to dry as a separate step,
solutions to pass through a ?xed distance in the pipette
temperatures of the order of from 175 to 275 ° F. may be
is then measured and this value and the densities of these
employed. In order to cure thereafter, times for from
solutions are then divided by the time required for the sol
4 minutes to 1/5 minute at from 300 to 450° F. may be
vent to so pass through the same ?xed distance and its
employed. If it is desired to dry and cure in a single
density. In addition, the same data is obtained for the
operation, times ‘for from 10 minutes to 3 minutes at
water present in the solvent, so that the viscosity of the
from 275° F. to 450° F. may be employed.
polymer may be corrected for both the nitrate and water.
The aqueous treating solution of the present invention
The resulting corrected values are termed the relative 50 may be applied by any one of the conventional resin
viscosities. These relative viscosities are then plotted
?nishing techniques well known to those skilled in the art.
against the concentration of the solutions from which
they are obtained and the resulting curve or line is ex
Thus, for example, the treating composition may be ap
plied as by spraying, dipping, immersion, or padding.
tnapolated to 0 concentration, at which value the intrinsic
Normally, the resin composition is applied employing
55
viscosity is read and obtained.
between 1.6 to 25% of catalyst based on the weight of
A critical feature of the present invention resides in the
the aminoplast component of the mixture. Examples
relative weight ratios between the aminoplast resin and the
of suitable catalysts include the ammonium salts like am
polyam-ide in the composition that is applied to the textile
monium chloride, amine salts like triethylamine hydro
material. The two components should be applied in
chloride, alkanolamine salts like triethanolamine hydro
60
weight ratios of from 3 to 10% of the aminoplast and
chloride, metal salts such as magnesium, zinc and alumi
from 1 to 10% of the polyamide, based on the weight
num chlorides, zinc nitrate, and free acids such as oxalic
of the dry textile material. It has further been determined
and the like. These may be employed singly or in com
that at least about 1% of the polyamide, based on the
bination with one another.
dry weight of the fabric, must be present in order to im
A particularly desirable narrower aspect of the present
65 invention relates to the treatment of textile materials
part the quality of durable stiffness to the fabric.
Thus, between about 4 and 20% of the combined resin
with an aqueous solution having a pH adjusted to from
solids should be applied to the textile material to achieve
between 1 and 3.5 with an acid acting curing catalyst
the desirable property of durable stillness without serious
having an ionization constant of at least 10*. Examples
ly adversely a?’ecting other characteristics of the treated
70 of such suitable catalysts are acetic acid, acrylic acid,
material.
adipic acid, ammonium acid sulfate, ammonium trihydro
Within the ranges indicated above with respect to the
gen pyrophosphate, chloroacetic, citric, dichloroacetic,
weight ratios of the essential elements applied to the tex
tile fabric, wide variations exist, depending upon which
arninoplast and concentration thereof and which concen
formic, glutaric, glycolic, lactic, maleic, malic, malonic,
methyl acid pyrophosphate, oxalic, phosphoric, suocinic,
tration of polyamide is employed. Thus, for example, 75 sulfanilic, and tartaric acid. These acids and acid salts,
3,094,371
5
the exception that the temperature of washing was 100’
and others having an ionization constant of at least 10-5
may be employed singly or in combination with one an
other. These acids are employed in amounts sutlicient
F. and no soda ash was employed.
The e?ect of washing generally is to break down the
stiffness of any fabric, whether it be treated or not. If
to adjust the pH of the aqueous solution to between the
the ?nish of the treated material were not durable, little
above said 1 and 3.5 pH.
stiffness would be observed after a 10-minute wash and
Employment of aqueous solutions containing acid act
less after 1 hour of washing. The fact that high stiffness
ing catalysts having ionization constants of at least 10-5,
values are obtained after 7 hours of washing clearly indi
when applied to textile materials, enables the textile ma
cates durability of the ?nish.
terial to be dried and cured in a single operation, at times
In Table Ii infra, polyacrylamides of varying molecular
of from between 10 minutes and 5 minutes, at from 175 10
weights were employed with various thermosetting amino_
to 275"’ F. This is a signi?cant advantage in that normal
plast resins on cotton and rayon. The treating compo
dry and cure times and temperatures, whether performed
sition (aminoplast resin plus polyacrylamide) was ap
separately on the treated material or simultaneously, may
plied so as to impart 15% solids to the textile fabric con
be greatly reduced. Thus, for example, where the tex
tile material has been treated with an aqueous solution 15 sisting of 10% of aminoplast resin and 5% of the poly
acrylamide. The polyacrylamide varied in the viscosity,
containing from 2.5 to 5% of polyacrylamide and 10%
as indicated in the said table, and these resin polyacryl
of dimethylol ethylene urea having a pH of 3, adjusted
amide mixtures were applied and cured as indicated in
thereto with phosphoric acid, the material may be dried
the key accompanying the said table. The results of the
and cured in a single operation for 5 minutes at 250° F.
to impart good properties to the treated material and an 20 indicated tests are in miligrams and are otbained on a
Gurley stiffness tester.
outstanding durable sti? hand.
In order that the present invention may be more fully
Table 11
understood, the following examples are given primarily
by way of illustration. No details therein should be con
strued as limitations on the present invention, except as 25
Cotton
Rayon
Treatment
they appear in the appended claims.
EXAMPLE 1
Initial
80" x 80" cotton percale was padded through an aque
l-hr.
wash
Initial
l-hr.
wash
10% methglated ureaformaldehyde
ous pad bath solution containing 5% polyacrylamide and 30 $123298‘)
AtNzl. 6)(1r1tl'insic
viscosity__
8 0n
_________________
10% of dimethylol succinamide. The pad bath of the
10% dimetlhlylol ethylene urea plus
5%
PA
I
(intrinsic
viscosity
aqueous solution had been adjusted to 3 with phosphoric
PAM about 2.0)_____._______--___
acid. Thereafter, the treated fabric was run through a
10% dimethylol suecinarnide plus 5%
Péthi 2(l‘jgtrlnsic
viscosity PAM i
padding roll, adjusted to obtain a 100% wet pick-up.
a on
. ________________________ -_
The cloth was dried and cured in a single operation for 35 109’? methylated methylol melamine
211
97
385
20
2
218
127
484
182
170
127
328
245
p us 5% PAM I (intrinsic viscosity
5 minutes at 250° F.
PAM about 0.12) ________________ __
rayon.
l2
______ __
30
...... ..
10% dimethylol suonlnaxnlde plus 5%
EXAMPLE 2
A process similar to that employed in Example 1 was
followed, except that the material to be treated was viscose
PAM 1 (intrinsic viscosity PAM
about 6) _________________________ __
184
Untreated ......................... __
12
101
______________ -.
______ -_
30
...... -.
I HsPOl to pH 3.0 in bath as catalyst. Cloths dried and cured in one
=
operation for 5 min. at 250° F
In order to ascertain the durability of the sti?'ness im
1127 magnesium chloride. emplo ed as cats] st. 010 h d d
225°
cure 1.5 min. at 350° F.
y
y
t a tie at
parted to the textile material, the materials were tested
by a Gurley stiffness tester, which gives the results in
milligrams. The higher the value, the greater the still 45 The above table indicates that the above combinations
in the respective percentages employed therein will pro
ness. A full description of the Gurley stiffness tester
and the method for employing the same, which is a modi
?ed Cantilever Bending Method may be found in the
Federal Speci?cation CCC—T-1916, “Textile Test Meth
ods," Method 5202. The two treated samples and an 60
untreated control were so treated.
The following are
the results in which the larger the number of milligrams
the greater the sti?ness.
Table I
mg.
‘ "'
not greatly influenced by the intrinsic viscosity and thus
the molecular weight of the polyacrylamide component.
As will be noted, a composition employing very low vis
cosity was not effective as a stiffening agent.
‘The above table further indicates that e?ective durable
stiffness can be accomplished with polyacrylamide and
55 resins such as dimethylol succinamide or dimethylol
Cotton,
Untr
duce a durable stillness on cotton and rayon, and that
within wide limits the degree of this durable sti?ness was
Viscose
rayon, mg.
.
11
12
Treated but unwashed ...................... ._
10 minute wash ............................. --
198
129
378
281
After 7 hours of washing ..................... ..
67
210
ethylene urea at low curing temperatures, i.e. 250° F. or
less, when a free acid catalyst such as phosphoric acid was
employed and the bath pH was 3.0 or lower.
In order to prove the signi?cance of the combination
60 of resinous materials employed in the present invention,
equal solids concentrations of an aminoplast resin and
a medium molecular weight polyacrylamide (M.W. of
about 500,000) were applied independently to spun vis
cose challis and ?lament nylon twill (IS-ounce) sepa
It will he noted from the above table that the present
treatment is particularly effective on rayon cellulosic ma 65 rately, and then equal solids involving the combination
of the said aminoplast resin and the medium molecular
terials, but is also highly e?ective on cotton cellulosic
weight polyacrylamide were applied to similar textile ma
material, and that both are vastly superior to the untreated
terials. These applications were made on a laboratory
control.
padder, obtaining a pick-up of approximately 100% on
In the above example, the wash durability test com
prised washing the textile fabrics in 0.1% soap and 0.1% 70 the viscose and 70% on the nylon twill. 12% of mag
nesiu-m chloride was employed as a latent acid curing
soda ash at 160° F. for 10 minutes, followed by rinsing,
catalyst, based on the amount of the thermosetting resin
centrifuging, and pressing between each wash cycle.
in all cases. The treated fabrics were dried for 2 min
Where 1 hours of washing have been indicated, the above
utes at 225° F. and cured 4 minutes at 290° F.
cycle was repeated continuously for 7 hours. The same
Portions of the treated nylon and viscose cloths were
series of washes was carried out on the rayon piece with 75
3,094,371
7
8
subjected to a l~hour rayon wash consisting of washing in
0.1% soap at 100° F. for 45 minutes, followed by rins
ing in water at 1000 F. for 10 minutes and 5 minutes in
separate cycles. The cloths were then spun dried and
stillness of the combination was extremely durable to
washing with about 75% of the imparted stiifness re
tained after washing. It is also apparent that the resin
pressed on a Hoffman steam press.
than either the resin or polyacrylamide alone. The addi
polyacrylamiide combination caiused less strength loss
The washed and
unwashed portions of the fabric were then subjected to
Gurley sti?’ness tests and Scott tensile tests. These Scott
tensile tests are fully described in “A.S.T.M. Standards
tion of V: of the strength loss obtained with polyacryl
amide alone and We of the strength loss obtained with the
resin alone, since these are the proportions used in the
on Textile Materials," “American Society for Testing
combination, would be double the observed loss in
Materials," November 1953. The results of these tests 10 strength obtained with the combination. The combina
are shown in Table III.
tion of resin and polyacrylamide is therefore synergistic
in durability of stiifness and retained tensile strength.
Table III
In order to determine the minimum eifective amount
of polyacrylamide which must be present on the treated
15 textile fabric, a series of experiments were run in which
Gurley stiiincssl
the concentration applied varied in amounts from be
Tensile,l
initial
tween 0.l% and 5%, based on the weight of the treated
Initial
l-hr.
fabric. The treated fabric was spun viscose challis and
Wash
the polyacrylamide imparted thereto 'was dried for 3
14. 5
13.9
84 20 minutes at 300° F. In addition to the wash procedure
SPUN VISOOSE CIIALLIS
Treatment
355. 8
111. 0
9. 6
33. 4
84. 4
11. 7
74
91
99
FILAMENT NYLON TWILL (1.5 OZ.)
5.25% resin A _____________________________ __
5.25% pulywcrylamide _____________________ __
21. 1
13. 9
15.0
6. 1
3.6% resin A plus 1.75% polyacrylamide._..
12. 2
8.9
92
87
89
Untreated ________________________________ __
3. 3
5. 0
88
described hereinabove, portions of the treated fabric
were subjected to
Absorption tester
lowed by drying
25 third cycle. The
hereinabove.
three dry-cleaning cycles in a Dynamic
for 20 min. each in Varsol No. 2, fol
and steam pressing at the end of the
physical properties were determined as
Table IV
EFFECT OF CONCENTRATION OF POLYACBYLAMIDE ON
PROPERTIES OF SPUN VISCOSE CHALLIS
30
I Total warp plus ?lling.
N0'rl:.—12% magnesium chloride employed on Resin A solids. Cloths
dried 2 min. at 225° F. and cured 1 min. at 290° F. Resin A-Trimethoxy
trirneth ylol melamine.
Gurley sti?ness l
Polyacrylamide (medium
viscosity) concentration
(percent)
Initial
Table III indicates that no signi?cant durable sti?ness
was produced on ?lament nylon by any of the treatments.
With respect to the viscose, n0 signi?cant durable stiif
l-hr.
wash
30.0
19. 2
35. 6
62. 2
200. 2
ness was imparted ‘by resin A alone, and while a high
order of stiffness Was imparted by the poiyacrylamide
Tensile,l
initial
3 dry
cleanings
17. 5
15. 0
14. 2
18. 6
17.2
28. 9
16. 3
16. 7
55. 5
205. 7
112
97
96
90
70
when employed alone, this stiii’ness was not signi?cantly 40
1 Total warp plus ?lling.
durable to washing. Where the combination of poly
acrylainide and resin was employed, the stiffness o'b—
Table IV indicates that the degree of sti?ness imparted
tained was about 1/3 that obtained from the application
is proportional to the concentration of polyacrylamide on
of polyacrylamide alone, and since only Va as much poly
the fabrics, and that a minimum of about 1% polyacryl
acrylamide was employed in the combination, the order 45 amide is necessary to substantially increase the initial
stiffness of the fabric.
‘
of sti?’ness obtained was proportional. Moreover, the
Table V
COMPARISON OF POLYAORYLAMIDE-RESIN OOMBINATIONS
1% Polyacrylamide
Gnrley sti?ness l
Tensile strength,‘
intial
Molar ratios 1
Percent resin solids
Initial
A
B
Washed
O
A.
B
0
43. 3
55. 6
43. 9
____ _.
79
6B
82
.... .
.... -_
73. 3
73. 3
66. B
62. 2
25. 0
19. 5
31. 7
16.1
89
99
94
105
14. 5
14. 5
36. 7
19. 5
16. 7
16. 1
16. 4
l6. 1 __._.-
75
81
86
01
90
68. 8
12. 8
64. 4
...................... __
(62. 2)
A
B
98
1
l5. 6
(l5. 3)
92
90
0
__--__
87
(90)
.----
6% Polyau'ylamide
' lAminoplast Resin olyacrylamido.
g.
1Nora.-A=
Total warpqplus
?ilfi‘n
r imethory trlmethylol melamine; B=d1methylo1ethlene urea; O=trimethory pentamethylol
melamine.
3,094,371
10
as much initial stitl'ness and stiffness after washing, when
employed at equivalent solids as that obtained when the
polyacrylamide-resin combination of Table V1 is em
In the next study, the amounts of various resins re
quired to eifect durability of the sti?ness imparted by
either ‘1 or 5% of a polyacrylamide (M.W. of about
500,000) were determined. Since polyacrylamide is a
ployed.
The term “intimate association" is employed herein with
reference to the drying and curing of the aminoplast and
polyamide together, in view of the lack of certainty with
respect to the manner in which the aminoplast and poly
multiple of
amide may react under curing conditions with each other
10 or the textile material. It is intended to include all such
variations.
Although the present invention has been described with
particular reference to the treatment of cotton and viscose
Applications were made as before to viscose challis of a
rayon, and more speci?cally cotton and rayon fabrics, the
number of appropriate molar combinations. Physical
properties were determined as before but the dry clean 15 treatment herein described may also be applied to other
textiles which are principally composed of cellulose or
ing tests were omitted.
regenerated cellulose, for example, linen, hemp, jute,
The results shown in Table V indicate that the durability
ramie, sisal, viscose rayons, cuprammonium rayons, and
of stiffness imparted by polyacrylamide is increased as the
mixtures thereof, with each other or with non-cellulosic
ratio of resin to polyacrylamide is increased. Table V
further indicates that where the amount of aminoplast 20 ?bers, such as, for example, nylon, polyester ?bers,
acrylics, and the like.
resin employed is signi?cantly less than about 3% solids
the molecular weight of this unit (71) was employed in
determining molar ratios of resin and polyacryiarnide.
based on the weight of the textile fabric, a desirable
durable sti?ness is not obtained.
Heretofore, various polymeric materials have been em
The terms “textile" and "textile materials” as used
generally herein and in the appended claims, include with
in their meaning ?laments, ?bers, threads, yarns, twisted
ployed for purposes of imparting sti?ness to textile fabrics. 25 yarns, etc. as such, or in woven, non-woven or otherwise
One such polymeric material is commercial polyvinyl al
formed fabrics, sheets, clothes, and the like.
cohol. In order to illustrate the superiority of the com
bination of the present invention over the combination of
composition set forth hereinabove, namely the aminoplast
‘In addition to the essential components of the treating
resin and the polyamide, and the acid acting curing cata
following experiments were run in which polyvinyl alcohol 30 lyst, other additives which are not inconsistent and do not
destroy the effect of the essential components of the pres
(Elvanol 51-05) and a polyacrylamide having an average
ent invention may be added therewith, as for example,
molecular weight of about 500,000 were mixed in vary
softeners, antistatic agents, ?llers, pigments, dyes, and the
ing amounts with thermosetting resins A and B, which are
like, may be incorporated into the treating solution and
trimethoxy trimethylol melamine and dimethoxy dimethyl
ol ethylene urea, respectively. These resinous mixtures 35 applied simultaneously with the resin composition of the
present invention.
were prepared and employed in the relative concentrations
We claim:
indicated in the said table. In all cases, the polyvinyl
1. A process for treating textile materials containing
alcohol and polyacrylamide were employed in amounts of
groups reactive with the group —CH2OH to impart dur
5% based on the weight of the textile material, which was
spun viscose rayon challis.
40 able sti?’ness thereto which comprises treating said ma
commercial sti?ening materials with aminoplast resins, the
Table VI
COMPARISON OF POLYACRYLAMIDE AND POLY VINYL ALCOHOL
Gurley stillness
Tensile strength,
Initial
Initial
Molar ratiol
PVA
A
Percent
resin
1/1 ............................ __
12-11/5"
1/10_--.
.
.
.
120--
157.6
124.3
129.9
10
4
0
PAM
B
Percent
resin
126.5
10
A
Percent
resin
_____________ _.
PVA
B
305.3
Percent
resin
10
............. __ 244.6
10
272.4
5
122.1
2.5
224.2
3.5 ............. __
102.1
1.25 ------------- -. 278.0
1
_____ --
ntreated ...... _.
Washed
.-__
(son)
.
183.5
0.9
............................ -.
PAM
A
B
A
B
____ ._
58.9
_____ ..
188.7
87.7 ---- -_ 186.5
175.4
68.8 15.4
73.3 ..... -_
61
15.8 ..... -_
27.8
.... -.
81
(17.5)
PVA
PAM
A
B
A
.a-
61
_...
48
56 __-_ 67
76 85 72
83
85 .-__
49
__
..... -- -_-. --..
74
B
-___
(1 2)
1 Aminoplastlpolymer.
terial with an aqueous solution consisting essentially of
The results of Table VI indicate that polyvinyl alcohol,
( l) a substantially water-soluble, heat-curable, at least di
a commercial sti?'ening agent, imparts only about 50%
of the sti?ness obtained with polyacrylamide in equivalent 65 functional aminoplast, (2) a water-soluble thermoplastic
polyamide selected from the group consisting of poly
applications.
acrylamide, polymethacrylamide and mixtures thereof,
Table VI further indicates that when the concentration
and (3) an acid acting curing catalyst for said aminoplast.
of aminoplast resin imparted to the textile material falls
said (1) and (2) being present in aqueous solution in
signi?cantly below the 3% minimum required that the
property of durable stiffness is signi?cantly reduced.
70 weight ratios of from 3 to 10% of the former and 1 to
10% of the latter, wherein at least 1% of the polyamide
Solvitose HDF, a modi?ed starch frequently employed
is applied to the material based on its dry weight and
as a sti?ening agent for cellulosic textile materials, was
thereafter subjecting said material to elevated temperatures
also mixed with aminoplast resin A and aminoplast resin
to cure (I) in intimate association with (2).
B in a manner similar to that set forth hereinabove in
2. A process for treating textile materials containing
connection with Table VI. The results of this comparison 75
groups reactive with the group —CH2OH to impart dill"
indicate that Solvitose HDF imparts approximately 36
3,094,371
11
12
aldehyde condensate, (2) a water-soluble polyacrylamide,
able stillness thereto which comprises treating said ma
and (3) an acid acting curing catalyst having an ionization
terial with an aqueous solution consisting essentially of
constant
of at least 104’, said (1) and (2) being present
( l) a substantially water-soluble, heat-curable, at least di
in said aqueous solution in weight ratios of from 3 to
functional melamine-formaldehyde condensate, (2) a
water-soluble thermoplastic polyamide selected from the Wt 10% of the former and l to 10% of the latter, wherein
at least 1% of the polyacrylamide is applied to the ma
group consisting of polyacrylamide, polymethacrylamide
terial based on its dry weight, and thereafter subjecting
and mixtures thereof, and (3) an acid acting curing cata
lyst for said melamine-formaldehyde condensate, said (1)
and (2) being present in aqueous solution in weight ratios
said material to elevated temperatures to cure (1) in in
timate association with (2).
5. A composition of matter suitable for imparting dur
of from 3 to 10% of the former and 1 to 10% of the 10
able stitfness to cellulosic textile materials which consists
latter, wherein at least 1% of the polyamide is applied
to the material based on its dry weight and thereafter
subjecting said material to elevated temperatures to cure
(1) in intimate association with (2).
3. A process for treating cellulosic textile material con
taining groups reactive with the group -—CI-I2OH to im~
part durable stiffness thereto which comprises treating said
material with an aqueous solution having a pH of from
about 1 to 3.5 comprising (1) a substantially water
soluble, heat-curable, at least difunctional aminoplast, (2)
a water-soluble thermoplastic polyamide selected from the
essentially of an ‘aqueous solution containing (1) from
between 3 and 10% of a substantially water-soluble, heat
curable, at least difunctional aminoplast and (2) from
1 to 10% of a Water-soluble thermoplastic polyarnide se
lected from the group consisting of polyacrylamide, poly
methacrylamide and mixtures thereof.
6. A cellulosic textile fabric having a durable stiff
?nish that consists of an intimately associated mixture of
from 3 to 10% of a water-insoluble, heat-cured amino
plast and from 1 to 10% of a polyamide selected from
the group consisting of polyacrylamide, polymethacryl
amide and mixtures thereof.
and mixtures thereof, and (3) an acid acting curing cata
lyst having an ionization constant of at least 10-5, said
References Cited in the ?le of this patent
(1) and (2) being present in said aqueous solution in 25
weight ratios of from 3 to 10% of the former and 1 to
UNITED STATES PATENTS
10% of the latter, wherein at least 1% of the polyamide
2,173,005
Strain _______________ __ Sept. 12, 1939
is applied to the material based on its dry weight, and
2,313,742
Engelmann __________ ._.. Mar. 16, 1943
thereafter subjecting said material to elevated tempera
group consisting of polyacrylamide, polymethacrylamide
tures to cure (l) in intimate association with (2).
30
4. A process for treating cellulosic textile material con
taining groups reactive with the group —CH2OH to im
part durable stiffness thereto which comprises treating said
material with an aqueous solution having a pH of from
about 1 to 3.5 comprising (1) a substantially water
soluble, heat-curable, at least difuctional melamine-form
2,355,265
2,524,111
2,653,140
2,810,624
2,819,237
2,886,474
2,971,931
Bock ________________ __ Aug. 8, 1944
La Piana ______________ __ Oct. 3, 1950
Allenby ______________ __ Sept. 22, 1953
Wardell ______________ .__ Oct. 22,
Daniel ________________ __ Jan. 7,
Kline ________________ __ May 12,
Glade ________________ __ Feb. 14,
‘Y t
1957
1958
1959
1961
13
1h
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,094,371
June 18, 1963
William Julius Van Loo, Jr., et a1.
It is hereby certified that error appears in the above numbered pat~
ent requiring correction and that the said Letters Patent should read as
corrected below.
Columns 7 and 8,Table V, sixth column, line 2 thereof, for
"48.3" read —~ 42.3 -——; columns 9 and 10, Table VI, first column,
lines 2 and 3 thereof, for "/2" and "11/5", respectively, read
-— 1/2 —- and-~1/5 -—,
respectively;
same Table VI,‘ third column,
10
same columns 9 and 10,
line 4 thereof,
for "0" read ~
——.
Signed and sealed this 24th day ‘of December 1963.
(SEAL)
Attest:
ERNEST W. SWIDER
Attesting Officer
EDWIN L. REYNOLDS
Ac ting Commissioner of Patents
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,094,371
June 18, 1963
William Julius Van Loo,
Jr. ,
et al .
It is hereby certified that error appears in the above numbered pat-
‘
ent requiring correction and that the said Letters Patent should read as
corrected below.
Columns 7 and 8, Table V, sixth columnI
line 2 thereof, for
columns
9
and
10,
Table
VI , first column,
lines 2 and 3 thereof, for "/2" and "11/5", respectively,
read
"43. 3" read -— 42.3 ——;
--
1/2
-~ and --1/5 --,
respectively; same columns 9 and 10,
lsame Table VI ,' third column,
line 4 thereof, for "0" read ——
Signed and sealed this 24th day of December 1963.
SEAL
(Attest:
)
ERNEST W. SWIDER
Attesting Officer
EDWIN L. REYNOLDS
Ac 1; ing Commissioner of Patents
1
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 010 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа