U.S. patent number 3,607,610 [Application Number 04/701,615] was granted by the patent office on 1971-09-21 for crimped composite filaments of polycaprolactam or polyhexamethylene adipamide, and a terpolyamide of e-caprolactam, hexamethylenediammonium adipate, hexamethylene diammonium sebacate.
This patent grant is currently assigned to Asahi Kasei Kogyo Kabushiki Kaisha. Invention is credited to Hiroshi Chayamiti, Noboru Fukuma, Toshio Okamoto, Seizaburo Shigeta, Hiroshi Takeda.
United States Patent |
3,607,610 |
Fukuma , et al. |
September 21, 1971 |
CRIMPED COMPOSITE FILAMENTS OF POLYCAPROLACTAM OR POLYHEXAMETHYLENE
ADIPAMIDE, AND A TERPOLYAMIDE OF E-CAPROLACTAM,
HEXAMETHYLENEDIAMMONIUM ADIPATE, HEXAMETHYLENE DIAMMONIUM
SEBACATE
Abstract
Composite filaments capable of giving excellent crimped yarns
are obtained by using, in the production of polyamide composite
filaments, the terpolyamide 6/66/610 as a copolymer to be used in
combination with either nylon 6 or nylon 66. The proportions of the
individual monomers in the terpolyamide are specified in the areas
A and B in the accompanying drawing.
Inventors: |
Fukuma; Noboru (Nobeoka-shi,
JA), Chayamiti; Hiroshi (Nobeoka-shi, JA),
Okamoto; Toshio (Nobeoka-shi, JA), Shigeta;
Seizaburo (Nobeoka-shi, JA), Takeda; Hiroshi
(Nobeoka-shi, JA) |
Assignee: |
Asahi Kasei Kogyo Kabushiki
Kaisha (Kita-ku Osaka, JA)
|
Family
ID: |
26339794 |
Appl.
No.: |
04/701,615 |
Filed: |
January 30, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Jan 31, 1967 [JA] |
|
|
42/5793 |
|
Current U.S.
Class: |
428/370; 28/220;
428/395; 428/397; 525/432; 528/324; 264/172.14; 264/172.15;
264/172.18 |
Current CPC
Class: |
D01F
8/12 (20130101); Y10T 428/2973 (20150115); Y10T
428/2969 (20150115); Y10T 428/2924 (20150115) |
Current International
Class: |
D01F
8/12 (20060101); D02g 003/00 () |
Field of
Search: |
;260/857 ;264/171
;161/173,175 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Lieberman; Paul
Claims
We claim:
1. A process for producing a side-by-side or eccentric sheath-core
crimped composite filaments by melt spinning
poly-.epsilon.-carpolactam or polyhexamethylene adipamide and, a
terpolyamide comprising .epsilon.-caprolactam,
hexamethylenediammonium adipate and hexamethylenediammonium
sebacate wherein the molar composition of said terpolyamide is
within the range defined by the area A in the drawing.
2. A process for producing a side-by-side or eccentric sheath-core
crimped composite filaments by melt spinning
poly-.epsilon.-caprolactam or polyhexamethylene adipamide and, a
terpolyamide comprising .epsilon.-caprolactam,
hexamethylenediammonium adipate and hexamethylenediammonium
sebacate wherein the molar composition of said terpolyamide is
within the range defined by the area B in the drawing.
3. A side-by-side or eccentric sheath-core crimped composite
filament, one component of said filament being caprolactam, or
polyhexamethylene adipamide, the other component being a
terpolyamide of .epsilon.-caprolactam, hexamethylene diammonium
adipate, and hexamethylene diammonium sebacate, wherein the
.epsilon.-caprolactam, hexamethylenediammonium adipate and
hexamethylenediammonium sebacate are present in a molar ratio of
1-30: 30-79: 20-60, with the proviso that the total amount of the
three above components equals 100 percent.
4. A side-by-side or eccentric sheath-core crimped composite
filament, one component of said filament being caprolactam, or
polyhexamethylene adipamide, the other component being a
terpolyamide of .epsilon.-caprolactam, hexamethylene diammonium
adipate, and hexamethylene diammonium sebacate, wherein the
.epsilon.-caprolactam, hexamethylenediammonium adipate and
hexamethylenediammonium sebacate are present in a molar ratio of
85-98: 1-14: 1-14, with the proviso that the total amount of the
three above components equals 100 percent.
Description
This invention relates to polyamide-type crimpable composite
filaments and a process for their production.
There have been known composite filaments which are produced by
separately preparing two spinning solutions of polymers of a
different kind, extruding the two spinning solutions through one
spinneret, without mixing the solutions to coagulate the solutions
and then subjecting the resulting filaments to stretching. These
filaments can develop crimps by heat treatment immediately after
stretching or even after a certain period of time has elapsed after
stretching. Concerning polyamide type composite filaments, a
variety of processes have been proposed. However, there have not
been obtained composite filaments which are sufficiently
satisfactory not only in the crimping force of the filaments but
also in such properties as elasticity and bulkiness of crimped
yarns obtained therefrom.
The object of the present invention is to provide composite
filaments capable of giving crimped yarns which have the
above-mentioned properties in combination and are comparable to
textured yarns produced according to the conventional false twist
method and the like.
The above object can be achieved by the melt spinning process of
the present invention in which composite filaments are obtained by
using as one polymer, nylon 6 or nylon 66 and as the other polymer
a terpolyamide (6/66/610) comprising .epsilon.-caprolactam (6M),
hexamethylenediammonium adipate (66 salt) and
hexamethylenediammonium sebacate (610 salt), the feed molar ratios
of the components of said polyamide (6/66/610) being limited within
the ranges shown, in the accompanying drawing, by the oblique lined
areas surrounded by lines formed by connecting the points a, b, c,
d, e and a and the points f, g, h and f. The drawing is a
triangular coordinate showing the feed molar rations of the
individual monomers constituting the terpolyamide to be used in the
present invention. In the drawing, the points a, b, c, d and e of
the area A are the points at which the molar ratios of 6M:66 salt :
610 salt are 10:30:60, 30:30:40, 30:50:20, 1:79:20 and 1:39:60,
respectively, and the points f, g and h of the area B are points at
which said molar ratios are 98 : 1 : 1, 85 :14 :1 and 85 : 1 : 14,
respectively. The melting point of a terpolymer having a
composition within said area A is about 180.degree. -230.degree.
C., and that of a terpolymer having a composition within said area
B is about 180.degree. -215.degree. C.
If the amounts of 66 salt and 610 salt are outside the proportions
in said areas A and B, the terpolymer has a lowered melting point
and thus the resulting composite filaments are undesirably
deteriorated in thermal resistance. On the other hand, if the
amount of 66 salt or 610 salt is excessively small, the composite
filaments obtained develop no sufficient crimps.
Even when either nylon 6 or nylon 66 is used as the other component
to be conjugate spun, crimps of some degree may be obtained. In
view the easiness of spinning, however, it is advantageous to
conjugate spin, in combination, polymers having similar melting
point.
The terpolyamide of the present invention is obtained in such a
manner that the given amounts of 6M, 66 salt and 610 salt are mixed
together and dissolved in water, and the solution is charged in an
autoclave and is heated after the atmosphere is substituted by
nitrogen, under pressure at 200.degree. -220.degree. C. for several
hours. The temperature of the solution is elevated to 250.degree.
-300.degree. C., while gradually releasing the pressure, and same
is heated at said temperature for 15-20 hours in a nitrogen
atmosphere. The other component, i.e. nylon 6 or nylon 66 is
obtained by polymerization according to a conventional process.
Both components may be incorporated with known stabilizers,
pigments and the like.
The spinning in the present invention is effected by the use of a
spinneret for conjugate spinning. The stretching may be carried out
either at room temperature or at an elevated temperature of
50.degree. -180.degree. C. using a hot plate or the like. In this
case, there is a tendency for the crimps to become coarser and for
the bulkiness to become more favorable with increasing stretching
temperature. The type of arrangement of components may be either
side-by-side-type or eccentric sheath-core-type.
The present invention will be illustrated below with reference to
the following examples. In the examples, the term "relative"
viscosity .eta. rel. of the polymer represents the ratio between
the viscosity of a solution formed by dissolving 1 g. of polymer in
100 ml. of 95.5 percent sulfuric acid and the viscosity of the
solvent. The term "number of crimps" represents the number of
crimps formed, within a length of 25 mm., on a crimped filament
when a load of 1 mg./d. has been applied thereto, in which the
distance between a peak and an adjacent peak or a bottom to an
adjacent bottom of crimps on the crimped filament is counted as one
crimp. The "degree of crimp" is defined by the following
equation:
wherein l.sub.1 is the length of a crimped filament when an initial
load of 1 mg./d. has been applied thereto, and l.sub.2 is the
length of the filament when the initial load has been removed and a
load of 100 mg./d. has been applied in place thereof. The "crimping
force" is the number of crimps developed when a straight filament
after stretching has been treated under a load of 2 mg./d. in
saturated steam at 100.degree. C. for 15 minutes.
EXAMPLE 1
A mixture comprising 800 g. of nylon .epsilon.-caprolactam, 100 g.
of 66 salt and 100 g. of 610 salt (molar ratio of 6 :66 : 610=91.3
: 4.9 :3.8) was charged with 200 ml. of water and was fed to an
autoclave. After substituting the atmosphere with nitrogen, the
mixture was heated under pressure at 220.degree. C. for 2 hours.
Thereafter, the temperature was elevated while gradually releasing
the pressure. After the temperature had reached 280.degree. C., the
pressure was further released to atmospheric pressure, and the
mixture was heated at said temperature for 20 hours while flowing
nitrogen into the autoclave. Subsequently, the resultant material
was extruded under pressure from the autoclave, was shaped into the
form of chips by means of a cutter, and was then subjected to hot
water extraction to obtain a terpolyamide having a relative
viscosity .eta. rel. of 2.8 and a melting point of 185.degree.
C.
The thus-obtained terpolyamide and nylon 6 having .eta. rel. of 2.3
and containing 0.3 percent of titanium oxide were extruded in equal
amounts through a known side-by-side-type conjugate spinning
spinneret having 10 orifices of 0.3 mm. in diameter and were taken
up at a rate of 800 m./min. The resulting unstretched filaments
were stretched to 3.5 times at room temperature to obtain composite
stretched filaments of 50 deniers/10 filaments. The stretched
filaments were then subjected in a relaxed state to boiling water
treatment at 100.degree. C. to obtain crimped yarns high in
elasticity. The crimp properties of the crimped yarns were as
follows:
Number of crimps: 84/ 25 mm.
Crimp elongation: 196 percent
Crimping force: 18
EXAMPLE 2
The same unstretched filaments as in example 1 were stretched to
3.5 times on a hot plate at 100.degree. C. and were subjected to
the same heat treatment as in example 1 to obtain crimped yarns
high in bulkiness and excellent in hand. The crimp properties of
the crimped yarns were as follows:
Number of crimps: 46/ 25 mm.
Crimp elongation: 168 percent
Crimping force: 15
EXAMPLE 3
A mixture comprising 850 g. of 6M, 100 g. of nylon 66 salt and 50
g. of nylon 610 salt (molar ratio of 6 :66 :610=93.4 : 4.7 : 1.9)
was treated in the same manner as in example 1 to obtain a
terpolyamide having .eta. rel. of 2.5 and a melting point of
195.degree. C. This terpolyamide, and nylon 6 having .eta. rel. of
2.3 and containing 0.3 percent of titanium oxide were extruded
through a known side-by-side-type conjugate spinning spinneret
having 30 orifices of 0.3 mm. in diameter and were taken up at a
rate of 800 m./min. The resulting unstretched filaments were
stretched to 3.0 times on a hot plate at 100.degree. C. to obtain
composite stretched filaments of 140 deniers/30 filaments. The
stretched filaments were then subjected in a relaxed state to
boiling water treatment at 100.degree. C. to obtain crimped yarns
having the following crimp properties:
Number of crimps: 52/ 25 mm.
Crimp elongation: 132 percent
Crimping force: 16
EXAMPLE 4
A mixture comprising 850 g. of 6M, 75 g. of nylon 66 salt and 75 g.
of nylon 610 salt (molar ratio of 6 : 66: 610=93.5 : 3.5 : 3.0) was
treated in the same manner as in example 1 to obtain a terpolyamide
having .eta. rel. of 2.5 and a melting point of 195.degree. C. This
terpolyamide, and nylon 66 having .eta. rel. of 2.4 and containing
0.3 percent of titanium oxide were extruded through a known
side-by-side-type conjugate spinning spinneret having 10 orifices
of 0.3 mm. in diameter and were taken up at a rate of 800 m./min.
The resulting filaments were stretched to 3.0 times on a hot plate
at 100.degree. C. to obtain composite stretched filaments of 60
deniers/10 filaments. The stretched filaments were subjected to the
crimping treatment according to example 1 to obtain crimped yarns
which were excellent in hand and had the following crimp
properties:
Number of crimps: 42/ 25 mm.
Crimp elongation: 169 percent
Crimping force: 15
EXAMPLE 5
A mixture comprising 50 g. of 6M, 375 g. of nylon 66 salt and 57 g.
of nylon 610 salt (molar ratio of 6 : 66: 610=11.9 : 39.1 : 49.0)
was charged with 100 ml. of water and was fed to an autoclave.
After substituting the atmosphere with nitrogen, the mixture was
heated under pressure at 220.degree. C. for 2 hours. Thereafter,
the temperature was gradually elevated while releasing the
pressure, after the temperature had reached 280.degree. C., the
pressure was further released to atmospheric pressure, and the
mixture was heated at said temperature for 20 hours while flowing
nitrogen into the autoclave. Subsequently, the resultant was
extruded under pressure from the autoclave, was shaped into the
form of chips and was then subjected to hot water extraction to
obtain a terpolyamide having .eta. rel. of 2.5 and a melting point
of 196.degree. C.
The thus-obtained terpolyamide, and nylon 6 having .eta. rel. of
2.3 and containing 0.3 percent of titanium dioxide were extruded in
equal volumes through a known side-by-side-type conjugate spinning
spinneret having 10 orifices of 0.3 mm. in diameter and were taken
up at a rate of 800 m./min. The resulting unstretched filaments
were stretched to 3.5 times at room temperature to obtain composite
stretched filaments of 50 deniers/10 filaments. The stretched
filaments were subjected in a relaxed state to boiling water
treatment at 100.degree. C. to obtain crimped yarns high in
elasticity and strong in tenacity. The crimp properties of the
yarns were as follows:
Number of crimps: 76/ 25 mm.
Crimp elongation: 296 percent
Crimping force: 22
EXAMPLE 6
The same unstretched filaments as in example 5 were stretched to
3.5 times on a hot plate at 100.degree. C. and were subjected to
the same heat treatment as in example 5 to obtain crimped yarns
high in bulkiness. The crimp properties of the yarns were as
follows:
Number of crimps: 37/ 25 mm.
Crimp elongation: 118 percent
Crimping force: 15
EXAMPLE 7
A mixture comprising 60 g. of 68-caprolactam, 470 g. of nylon 66
salt and 470 g. of nylon 610 salt (molar ratio of 6 : 66 : 610=14.0
: 47.2 : 38.8) was treated in the same manner as in example 5 to
obtain a terpolyamide having .eta. rel. of 2.6 and a melting point
of 190.degree. C. This terpolyamide, and nylon 6 having .eta. rel.
of 2.3 and containing 0.3 percent of titanium dioxide were extruded
through a known side-by-side-type conjugate spinning spinneret
having 30 orifices of 0.3 mm. in diameter and were taken up at a
rate of 600 m./min. The resulting unstretched filaments were
stretched to 3.0 times to obtain composite stretched filaments of
140 deniers/30 filaments. The filaments were then subjected in a
relaxed state to boiling water treatment at 100.degree. C. to
obtain crimped yarns having the following properties:
Number of crimps: 60/ 25 mm.
Crimp elongation: 190 percent
Crimping force: 17
EXAMPLE 8
A mixture comprising 98.7 g. of 6M, 342 g. of nylon 66 salt and 261
g. of nylon 610 salt (molar ratio of 6 : 66 : 610=29.1 : 43.5 :
27.4 ) was treated in the same manner as in example 5 to obtain a
terpolyamide having .eta. rel. of 2.3 and a melting point of
205.degree. C. This terpolyamide was used as a core component, and
nylon 66 having .eta. rel. of 2.3 and containing 0.3 percent of
titanium dioxide was used as a sheath component. The two components
were extruded, in a copolymer to nylon 66 ratio of 1 : 2, through a
known conjugate spinning spinneret and were taken up at a rate of
800 m./min. to obtain so-called kidney-type composite unstretched
filaments. The filaments were stretched to 3.5 times on a hot plate
at 100.degree. C. to form stretched filaments of 70 deniers/18
filaments. The stretched filaments were then subjected to boiling
water treatment at 100.degree. C. to obtain crimped yarns high in
bulkiness
The crimp properties of the crimped yarns were as follows:
Number of crimps: 25/25 mm.
Crimp elongation: 98 percent
Crimping force: 10
* * * * *