U.S. patent number 3,917,893 [Application Number 05/438,970] was granted by the patent office on 1975-11-04 for polyamide yarn.
This patent grant is currently assigned to Allied Chemical Corporation. Invention is credited to Kimon Constantine Dardoufas, Robert Moore Marshall, Sung Kun Pak.
United States Patent |
3,917,893 |
Marshall , et al. |
November 4, 1975 |
Polyamide yarn
Abstract
An improved polyamide yarn is prepared by first applying to the
yarn an aqueous emulsion of an oxidized polyethylene wax having an
average molecular weight between about 1,000 and about 3,000, and
containing between about 3 percent and about 9 percent oxygen by
weight, thereafter heating said yarn to a temperature between about
100.degree.C. and about 175.degree.C., and then applying to said
yarn a composition comprising an aqueous dispersion of colloidal
silica and a polyethylene glycol ester of a C.sub.6 to C.sub.18
aliphatic acid, said polyethylene glycol having a molecular weight
of about 200 to 600. The yarn is particularly useful for industrial
purposes such as braided hose, rope belts, etc.
Inventors: |
Marshall; Robert Moore
(Chester, VA), Pak; Sung Kun (Chester, VA), Dardoufas;
Kimon Constantine (Richmond, VA) |
Assignee: |
Allied Chemical Corporation
(New York, NY)
|
Family
ID: |
23742770 |
Appl.
No.: |
05/438,970 |
Filed: |
February 4, 1974 |
Current U.S.
Class: |
428/395;
427/393.5; 428/475.5; 252/8.84; 252/8.61; 57/250; 427/416 |
Current CPC
Class: |
D06M
15/00 (20130101); D02G 3/404 (20130101); D06M
11/79 (20130101); D06M 15/227 (20130101); D02G
3/447 (20130101); Y10T 428/2969 (20150115); Y10T
428/31739 (20150401) |
Current International
Class: |
D02G
3/40 (20060101); D02G 3/44 (20060101); D02G
3/22 (20060101); D06M 15/227 (20060101); D06M
11/00 (20060101); D06M 11/79 (20060101); D06M
15/00 (20060101); D06M 15/21 (20060101); P02J
003/00 (); D01H 013/30 () |
Field of
Search: |
;117/139.5A,139.5CQ,76T,72,138.8N ;252/8.6 ;57/14C ;428/395,474
;427/385,416 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Husack; Ralph
Attorney, Agent or Firm: Kelly; Fred L.
Claims
We claim:
1. A continuous filament polyamide yarn which is first coated with
a first finish composition consisting essentially of 30 to 60 parts
by weight of white mineral oil having a boiling point of between
265.degree.C. and 330.degree.C., 25 to 50 parts by weight of an
ethoxylated phosphated oleyl alcohol, 2 to 10 parts by weight of a
sulfonated succinic acid ester of oleyl alcohol, and 5 to 10 parts
by weight of an oxidized polyethylene wax having an average
molecular weight between about 1,000 and about 3,000 and containing
3 to 6 percent of oxygen by weight; then coated with a second
finish composition consisting essentially of 60 to 70 parts by
weight of an aqueous dispersion of colloidal silica containing
about 25 to 50 weight percent silica in the form of a stable silica
sol, and 30 to 40 parts by weight of a polyethylene glycol ester of
a C.sub.6 -C.sub.18 aliphatic acid, said polyethylene glycol having
a molecular weight of about 200 to 600, and the weight ratio of
said silica to said polyethylene glycol ester being between 0.45
and 0.70; said yarn being coated with an effective amount of said
first finish composition to provide a water-resistant oxidized
polyethylene wax coating thereon of between 0.05 and about 2
percent by weight of the yarn, and said second finish composition
being applied to the yarn in an amount sufficient to supply between
about 0.1 percent and about 0.6 percent of silica based on the
weight of the yarn, whereby processing of said yarn through coning
operations is improved.
2. The yarn of claim 1 wherein the polyethylene glycol ester is the
monopelargonate ester of polyethylene glycol having a molecular
weight of about 200 to 600.
3. The yarn of claim 1 wherein the polyamide is polycaproamide.
Description
BACKGROUND OF THE INVENTION
This invention relates to finished polyamide yarns. More
particularly, it relates to multifilament synthetic polyamide yarns
having applied finishes which enable the yarns to be satisfactorily
processed and utilized in the commercial production of braided
hose, rope, drive belts, and other industrial cord
applications.
Polyamide yarns, for example polycaproamide yarns, tend to develop
high electrostatic charges and excessive tensions when running over
guides, tension gates and other objects during processing and
subsequent handling so that the utilization of unfinished polyamide
yarns in textile production is unsatisfactory. Moreover, polyamide
yarns have different physical characteristics than most other
filament forming polymers and conventional finishes are not
suitable to provide the optimum combination of lubrication and
bundle cohesion to overcome processing problems.
U.S. Pat. No. 3,103,448 relates to the treatment of synthetic
continuous filament polyamide yarn, and more particularly to a
process for rendering such yarns more durable when fabricated into
cord or rope, and, in particular, more resistant to wet and dry
chafing abrasion when processed into such commodities. Said patent
features applying to the yarn a water-resistant coating of an
oxidized polyethylene wax having an average molecular weight
between about 1,000 and about 3,000 and an oxygen content between
about 3 percent and about 9 percent by weight.
Although U.S. Pat. No. 3,103,448 has made a major contribution to
this art, polyamide yarn treated in accordance with the process of
the patent does not have satisfactory yarn-to-yarn friction
properties required for coned package formation. Accordingly, for
many industrial uses it would be highly desirable to modify the
yarn finish to provide improved balance of yarn-to-yarn friction
and cohesion required for good package formation in rewinding the
yarn onto cones, without adversely affecting the wet and dry
chafing abrasion properties of cord or rope fabricated from the
yarn.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an improved finish for
polyamide yarn which enables the use of the yarn for industrial
purposes such as braided hose, rope belts, etc.
It is still another object of this invention to provide an improved
finish for polyamide yarn which provides a balance of yarn to yarn
friction and cohesion required for good package formation in
rewinding the yarn on cones.
These and other objects are accomplished in accordance with this
invention whereby an improved polyamide yarn is prepared by first
applying to the yarn an aqueous emulsion of an oxidized
polyethylene wax having an average molecular weight between about
1,000 and about 3,000, and containing about 3 to 9 percent,
preferably 3 to 6 percent of oxygen, by weight, thereafter heating
said yarn to a temperature between about 100.degree.C. and about
175.degree.C. to form a water-resistant coating thereon, and then
applying to said yarn a composition consisting essentially of 60 to
90 parts by weight of an aqueous dispersion of colloidal silica,
preferably containing about 25 to 50 weight percent silica in the
form of a stable silica sol, and 10 to 40 parts by weight of a
polyethylene glycol ester of a C.sub.6 -C.sub.18 aliphatic acid,
said polyethylene glycol preferably having a molecular weight of
about 200 to 600.
Preferably, the polyamide yarn is coated with sufficient aqueous
emulsion of the oxidized polyethylene wax to provide a
water-resistant wax coating thereon of between 0.05 percent and
about 2 percent by weight of the yarn. Preferably, the second
finish composition is applied to the yarn in an amount sufficient
to supply between about 0.1 percent and about 5 percent of silica
based on the weight of the yarn. The finish compositions may be
diluted with water to a water content up to about 80 weight percent
of the diluted composition. The finish compositions are applied to
the polyamide yarn by any known means, including bath, spray,
padding, kiss roll application or the like.
Oxidized polyethylene wax materials suitable for use in the present
invention are described in U.S. Pat. No. 3,060,163 according to
which normally solid, hard, waxy polymers of ethylene, which are
saturated aliphatic compounds characterized by a recurring
--CH.sub.2 -- group and which have average molecular weights
between about 1,000 and about 3,000, especially
polyethylene/alkanol telomers of this character, are subjected, in
the liquid phase, to the action of an oxygen-containing gas to
cause reaction of at least about 5 pounds of oxygen per 100 pounds
of wax, desirably between about 5 pounds and about 17 pounds of
oxygen, per 100 pounds of wax, i.e., to provide an oxidized
polyethylene wax containing at least about 3 percent, desirably
between about 3 percent and about 9 percent of oxygen by weight,
based on the weight of the oxidized wax, and acid numbers of not
more than about 50, preferably between about 10 and about 45. The
oxidized polyethylene/isopropanol telomer waxes prepared according
to the above method containing between about 3 percent and about 6
percent oxygen and having average molecular weights between about
1,000 and about 3,000, melting points between about 90.degree.C.
and about 110.degree.C., acid numbers between about 10 and about
20, are especially preferred. The preferred oxidized wax products
are characterized by an extremely low incidence of, or in many
cases, substantially complete absence of ester groups. Thus, the
saponification number (which measures both acid and ester groups)
is substantially identical to or only slightly greater than the
acid number (which measures only acid groups) so that these
products all have an extremely low or zero ester number
(saponification number minus acid number) and have ratios of
saponification number to acid number of about 1 to about 1.2 and
not more than about 1.5.
The waxy ethylene polymers which are oxidized as above described,
may themselves be prepared by any suitable known methods, for
example by subjecting ethylene, either alone, or in the presence of
a co-reactant to temperatures between about 150.degree.C. and about
300.degree.C. and pressures ranging from about 500 p.s.i. to about
7,000 p.s.i. as disclosed in U.S. Pat. Nos. 2,683,141 and
2,504,400.
In carrying out the process according to the present invention, the
oxidized polyethylene wax as described, is emulsified in water by
known methods using any suitable emulsifying agent. In general, we
prefer to melt the polyethylene wax together with the emulsifying
agent and then pour the melted wax gradually with stirring into hot
water at a temperature slightly below the boiling temperature.
Concentration of the wax component in the emulsion is not critical,
and will be adjusted to provide the desired coat weight on the yarn
under the particular application conditions employed.
The colloidal silica dispersions or sols used in accordance with
the present invention may be prepared by reacting an acid, such as
a mineral acid capable of forming salts by reaction with silicates,
with a water-soluble silicate in the manner customarily employed to
form silica gel, and washing the resulting gel with water to remove
electrolytes. The gel is then treated with a weak aqueous solution
of a substance capable of forming hydroxyl ions and, after removing
the gel from solution, heating the gel while avoiding evaporation
of water until the gel is converted to a sol.
Aqueous dispersions of colloidal silica prepared in the above
manner are particularly adapted for the purposes of the invention.
It is possible, however, to prepare the colloidal dispersions or
sols as described above, then to acidify them and use them in a
slightly acid condition, when desired. Other types of colloidal
solutions or sols of silica may also be used. For example, the sols
may be prepared by reacting water-soluble silicates with an acid
and subjecting the acidified silicate to treatment with alcohol
and/or cooling to remove the electrolyte, as described in U.S. Pat.
No. 2,285,449 and U.S. Pat. No. 2,285,477. It is also possible to
use sols prepared by treatment of an alkali silicate with an
ion-exchange material as described in U.S. Pat. No. 2,244,325.
The concentration of the colloidal dispersion of silica used is
relatively unimportant, as it is possible to employ a wide variety
of solution strengths depending on the type of apparatus used or
the degree of pick-up which is possible in the particular apparatus
employed. Normally, commercially available aqueous dispersions of
colloidal silica are employed, preferably containing 25% to 50%
silica. As indicated above, such dispersions of colloidal silica
may be diluted with water if desired.
The ethylene glycols having average molecular weights above about
200 are usually classified as polyethylene glycols, HO(CH.sub.2
CH.sub.2 O).sub.n H, where n is equal to or greater than 4. They
are water-white liquids at ambient temperature up to molecular
weights of about 700. Polyethylene glycols having molecular weights
of about 200-600 are preferred for use in the present invention.
The commercially available polyethylene glycols are actually
mixtures of many polyethylene glycols. The polyethylene glycols are
prepared commercially by the addition of ethylene oxide to either
water, ethylene glycol, or diethylene glycol containing a small
amount of sodium hydroxide catalyst. The principal derivatives of
the polyethylene glycols are the mono- and diesters, especially the
aliphatic acid esters. These esters are manufactured by typical
esterification techniques with esterification temperatures often
reaching 150.degree.-200.degree.C. The esters of the invention are
preferably monoesters of aliphatic acids having 6-18 carbon atoms.
Preferred aliphatic acids of the invention include, for example,
stearic acid, palmitic acid, lauric acid, pelargonic acid and
capric acid.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As indicated hereinabove, the present invention is an improvement
over U.S. Pat. No. 3,103,448, which patent is incorporated herein
by reference.
In accordance with the present invention, the oxidized polyethylene
wax emulsion may be applied to the yarn either alone, or together
with other additives commonly applied to yarns as yarn finishes to
improve their processability, for example, antistatic agents,
mineral oil, silicones, etc. The instant coating differs from the
usual spin finish additives, however, in that it produces a
permanent finish rather than being washed out and removed as are
the usual spin finishes applied for improving processability. In
general, we prefer to apply the oxidized polyethylene wax emulsion
as a spin finish, and find it especially adapted for treatment of
polyamide filaments including nylon 6, polycaprolactam,
filaments.
Any suitable emulsifying agent may be used in preparing the
oxidized polyethylene wax emulsions used in the process of our
invention. Mixtures of higher fatty acids, for example C.sub.12 to
C.sub.20 saturated aliphatic acids with volatile amines such as
morpholine, methoxy propylamine, 2-amino-2-methyl-1-propanol. etc.
may be used as emulsifiers as may also the long chain alkyl aryl
sulfonates such as keryl benzene sodium sulfonate, dodecyl benzene
sodium sulfonate, alkyl aryl polyether alcohols. Also useful are
the general class of non-ionic emulsifiers especially the
condensation products of ethylene oxide with hydrophobic material
such as a long chain aliphatic alcohol, acid, ester, ether or alkyl
phenol. These products are characterized by containing as the
hydrophilic portion of the molecule, a plurality of oxyethylene
moieties as illustrated in the formulae below.
1.
R--O--(CH.sub.2 --CH.sub.2 O).sub.x --CH.sub.2 --CH.sub.2 OH
wherein R is an alkyl group having from 12 to 22 carbon atoms or an
alkyl phenol residue wherein the alkyl group contains from 6 to 13
carbon atoms inclusive and wherein x is at least 4 especially
between about 6 and about 40.
Commercial examples of products in this group include "Triton
X-100" wherein R is an alkyl phenol residue wherein the alkyl group
is isooctyl and wherein x is 7 to 9; "Triton X-102" wherein R is an
isooctyl phenol residue and x is 11; "Tergitol NPX" wherein R is
ethylhexyl phenol residue and x is 8 to 9, "Neutronic 600" wherein
R is nonyl phenol residue and x is 9; "Emulphor ELN" wherein R is
dodecyl phenol residue and x is 19.
2. Condensation products of fatty acids and polyethylene glycols
having the general formula
RCOO--(CH.sub.2 CH.sub.2 O).sub.x CH.sub.2 CH.sub.2 OH
wherein R is a long chain alkyl group having from 12 to 18 carbon
atoms inclusive and x is an integer from 8 to 40 inclusive.
3. Polyoxyethylene derivatives of hexitol anhydride or sorbitol
fatty acid esters such as "Tween 80".
4. Polyoxyethylene ethers
R--O(CH.sub.2 CH.sub.2 O).sub.x CH.sub.2 CH.sub.2 OH
wherein R is an alkyl group having from 6 to 18 carbon atoms and x
is an integer from 4 to 40 inclusive, or the corresponding
phosphated derivatives.
In accordance with one preferred embodiment of the invention, an
improved polyamide is prepared by first applying to the yarn an
aqueous emulsion of a composition consisting essentially of 30 to
60 parts, desirably 40 to 50 parts, by weight, of white mineral oil
having a boiling point of between 265.degree.C. and 330.degree.C.,
25 to 50 parts, desirably 30 to 40 parts, by weight, of an
ethoxylated phosphated oleyl alcohol, 2 to 10 parts, desirably 4 to
8 parts, by weight, of a sulfonated succinic acid ester of oleyl
alcohol, and 5 to 10 parts, desirably 4 to 8 parts, by weight, of
an oxidized polyethylene wax having an average molecular weight
between about 1,000 and about 3,000, and containing about 3 to 6
percent of oxygen by weight, thereafter heating the yarn to a
temperature of about 100.degree.C. to 135.degree.C. to form a
water-resistant coating thereon, and then applying to said yarn a
composition consisting essentially of 60 to 90 parts by weight of
an aqueous dispersion of colloidal silica containing about 25 to 50
weight percent silica in the form of a stable silica sol, and 10 to
40 parts by weight of a polyethylene glycol ester of a C.sub.6
-C.sub.18 aliphatic acid, said polyethylene glycol having a
molecular weight of about 200 to 600.
In order to demonstrate the invention, the following examples are
given. They are provided for illustrative purposes only and are not
to be construed as limiting the scope of the invention, which is
defined by the appended claims. In these examples, parts and
percentages are by weight.
EXAMPLE 1
A reactor equipped with a heater and stirrer was charged with a
mixture of 1,520 parts of e-caprolactam and 80 parts of
aminocaproic acid. The mixture was then flushed with nitrogen and
was stirred and heated to 255.degree.C. over a 1 hour period at
atmospheric pressure to produce a polymerization reaction. The
heating and stirring was continued at atmospheric pressure under a
nitrogen sweep for an additional 4 hours in order to complete the
polymerization. Nitrogen was then admitted to the reactor and a
small pressure was maintained while the polymer was extruded from
the reactor in the form of a polymer ribbon. The polymer ribbon was
subsequently cooled, pelletized, washed and then dried. The polymer
was a white solid having a relative viscosity of about 55 to 60 as
determined by a concentration of 11 grams of polymer to 100
milliliters of 90 percent formic acid at 25.degree.C.
(ASTMD-789-62T).
The polycaproamide pellets were melted at about 285.degree.C. and
then melt-extruded under a pressure of about 1,500 p.s.i.g. through
a 204-orifice spinnerette, to produce a 6,300-denier yarn. The yarn
was passed over a spin-finish roll to apply a spin finish, then
collected at about 5,000 feet per minute and then drawn over a
heated pin at 100.degree.-135.degree.C. to about 5 times its
extruded length to produce a 1,260-denier yarn. The spin finish
thus applied was prepared by mixing 4 parts of water with a
composition consisting of 48.2 percent of white mineral oil having
a boiling point between 265.degree.C. and 330.degree.C., 38.4
percent of phosphated oleyl alcohol ethoxylated with about 7 mols
of ethylene oxide, 6.6 percent of sulfonated succinic acid ester of
oleyl alcohol, and 6.8 percent of oxidized polyethylene wax
consisting of a polyethylene/alkanol telomer wax having an average
molecular weight between about 1,000 and about 2,000, an oxygen
content of about 3 percent, melting point 213.degree.-221.degree.F.
and acid number 14-17. Wet pick up of the water-diluted composition
on the fiber was 5 percent based on the weight of fiber; this
finish, after heating and drawing the fiber as described above,
provided a water-resistant coating on the yarn. Then, the yarn was
further treated with an over-finish composition, as described
below.
The silica sol used in preparing the overfinish was a commercially
available colloidal aqueous silica dispersion having the following
analysis:
Solids, weight percent 30
Water, weight percent 70
Specific gravity at 25.degree.C. 1.2
pH at 25.degree.C. 9.9
Mol ratio SiO.sub.2 /Na.sub.2 O 90
A mixed over-finish composition of 70 parts of the above-described
aqueous dispersion of silica and 30 parts of a monopelargonate
ester of 400 molecular weight (9-10 ethylene oxide units)
polyethylene glycol was prepared, and this composition was applied
as an overfinish to the above-described yarn by means of a kiss
roll prior to coning. Sufficient finish was applied to provide
about 0.3% of silica based on the weight of the yarn. The finish
was found to be a significant aid in processing the yarn through
the coning operation. The condition of the coned package was
excellent. The finished yarn gave excellent performance in braiding
and winding operations during manufacture of industrial rope.
In a comparative test wherein the above-described spin finish
composition was applied to the yarn but the over-finish composition
was not applied, the condition of the coned package was relatively
poor.
In the following examples, the procedure of Example 1 was followed
except that application of the silica-containing over-finish
composition was modified to determine optimum concentrations,
components, component ratios, etc.
EXAMPLE 2
In accordance with the procedure of Example 1, an over-finish
composition was prepared and applied to the polyamide yarn as
described in Example 1 except that the over-finish composition was
diluted with an equal weight of water. The yarn was found to have
only slightly better coning properties than the overfinished yarn
of Example 1.
EXAMPLE 3
An over-finish composition was prepared and applied to the
polyamide as described in Example 1 except that 20 parts of the
polyethylene glycol monopelargonate was combined with 80 parts of
the silica dispersion. The yarn was found to have relatively poor
coning properties as compared to the overfinished yarn of Example
1.
EXAMPLE 4
An over-finish composition was prepared and applied to the
polyamide yarn as described in Example 1 except that 40 parts of
the polyethylene glycol monopelargonate was combined with 60 parts
of the silica dispersion. This fiber was found to have relatively
good coning properties but not equal to the overfinished yarn of
Example 1.
EXAMPLE 5
An over-finish composition was prepared and applied to the
polyamide yarn as described in Example 1 except that 30 parts of a
monolaurate ester of 400 molecular weight polyethylene glycol was
substituted for the monopelargonate ester used in Example 1. The
yarn was found to have coning properties slightly inferior to those
of the overfinished yarn of Example 1.
EXAMPLE 6
An over-finish composition was prepared and applied to the
polyamide yarn as described in Example 1 except that the
composition was applied to the yarn in amount sufficient to provide
0.28% to 0.6% silica based on the weight of the yarn. In each case,
the condition of the coned package was excellent, and the finished
yarn gave excellent performance in braiding and winding operations
during manufacture of industrial rope.
Discussion
The above examples demonstrate that the instant finish system
provides a water-resistant finish combined with a finish having
exceptional filament cohesive properties. The over-finish enables
the use of these yarns for industrial purposes such as braided
hose, rope belts, etc. without need of twisting to control loose
filaments. In addition, it provides the proper balance of yarn to
yarn friction and cohesion required for good package formation in
rewinding yarn on cones. Particularly preferred results were
obtained when the over-finish was incorporated on the yarn in an
amount to supply about 0.1% to 0.6% silica based on the weight of
the yarn. The examples show that for optimum coning properties, the
weight ratio of said silica to polyethylene glycol ester on the
yarn should be between about 0.45 and 0.7. Particularly preferred
results were obtained with use of the monopelargonate ester of 400
molecular weight polyethylene glycol.
* * * * *