TECHNICAL FIELD
[0001] The present invention relates to a polyamide-46 multifilament and a sewing thread
for airbag.
BACKGROUND ART
[0002] Multifilaments of polyamide 6 (also referred to as "polycaprolactam") and polyamide
66 (also referred to as "polyhexamethylene adipamide") have higher strength and elongation
and superior fluff quality as compared with general-purpose multifilaments of polyester,
polypropylene, or the like, and are therefore used in a wide variety of applications
such as airbags, tire cords, sewing threads, transmission belts, ropes, and fishing
nets.
[0003] Among the above-described applications, polyamide 66 has been used for many years
in the field of sewing threads from the viewpoint of high mechanical properties and
heat resistance thereof.
[0004] In contrast to polyamide 66, polyamide 46 has a higher melting point and higher
heat resistance, and therefore is excellent in dimensional stability in high temperature,
and therefore is a material particularly suitable for a sewing thread for airbags,
and a technique for improving strength by improving spinning and drawing conditions
is disclosed (Patent Document 1).
[0005] In addition, a technique for improving dimensional stability in high temperature
(Patent Documents 2 and 3) has also been disclosed, and an invention for further improving
the characteristics of polyamide 46 has been reported so far.
[0006] However, almost no technique for improving the stretchability of a polyamide-46 multifilament
has been disclosed, and no technique for achieving both thermal dimensional stability
and stretchability has been disclosed so far.
[0007] As a method for imparting stretchability to a general-purpose polyamide multifilament,
for example, a method is disclosed in which a polyamide multifilament of a partially
drawing yarn is used as a sheath yarn, and is subjected to a taslan process with the
polyamide multifilament of a core yarn (Patent Document 4). However, such a conventional
stretchability developing technique is an original yarn design that impairs strength,
and is difficult to apply to industrial applications requiring high strength.
[0008] Conventional techniques do not provide a polyamide-46 multifilament suitable for
sewing threads for airbag with all of high strength, high thermal dimensional stability,
and excellent stretchability.
[0009] Then, in view of the development trend of airbags, weight reduction and compactness
are required as a recent trend of airbags, and with the compactness of inflators,
generated gas tends to have higher temperature and higher output.
[0010] However, the increase in temperature of the gas causes an increase in thermal damage
to the airbag base fabric, and also causes a loss in mechanical properties of the
sewing thread, particularly tends to stretch under a high-temperature atmosphere,
and thus increases gas leakage due to an opening of the sewing portion.
[0011] In addition, the increase in gas output tends to increase the pressure due to the
gas at the time of deploying the airbag, leading to an increase in gas leakage from
the base fabric of the airbag, particularly from the sewing portion, causing such
a problem that the performance as the airbag cannot be satisfied.
[0012] In order to solve this problem, various kinds of sewing thread for airbags have been
proposed (Patent Documents 5 and 6). In Patent Document 5, a sewing thread for airbags
containing 50% or more of a fiber material having a melting point of 300°C or more
is examined, and an extremely high retention ratio of heat resistance is clearly shown.
On the other hand, the high-temperature dimensional stability is not specified, and
the stretchability of the sewing thread is not studied.
[0013] Patent Document 6 shows that setting the elongation for the sewing thread and the
elongation for the base fabric within specific ranges improves the followability of
the sewing thread to the inflatable base fabric when the airbag is deployed, and the
air permeability of the sewing portion is suppressed, but the stretchability of the
sewing thread is not considered. Furthermore, the high-temperature dimensional stability
of the sewing thread when the airbag is deployed has not been studied.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0015] An object of the present invention is to provide a polyamide-46 multifilament having
high strength, high-temperature dimensional stability, and excellent stretchability
and suitable for the sewing thread for airbags having mechanical properties capable
of suppressing air leakage from an airbag sewing portion due to a high-temperature
and high-output gas as described above.
SOLUTIONS TO THE PROBLEMS
[0016] The present invention has been intensively studied to solve the above problems, and
mainly has the following configurations.
- (1) A polyamide-46 multifilament having the following physical properties.
When a degree of elongation after 10 times of stretching at a strength of 6.0-9.0
cN/dtex, an elongation of 15-30%, and an environment at 100°C is set to E10(100°C),
E10(100°C) < 1.0%, and when an elongation at a load of 2.0 cN/dtex and ordinary temperature
is M (R.T.), and the elongation at a load of 2.0 cN/dtex and an environment at 100°C
is set to M (100°C), M (100°C) - M (R.T.) < 0.5%.
- (2) The polyamide-46 multifilament according to (1), having the following physical
properties.
When the degree of elongation after 10 times of stretching at ordinary temperature
is set to E10(R.T.), and the degree of elongation after 10 times of stretching at
ordinary temperature after heat treatment at 120°C for 24 hours is set to E10' (R.T.),
E10' (R.T.) - E10(R.T.) ≤ 0%. When the elongation at a load of 2.0 cN/dtex and ordinary
temperature is set to M (R.T.), and the elongation at a load of 2.0 cN/dtex and ordinary
temperature after heat treatment at 120°C for 24 hours is set to M' (R.T.), M' (R.T.)
- M (R.T.) ≤ 0%.
- (3) The polyamide-46 multifilament according to the above (1) or (2), having a total
fineness of 300-2300 dtex and a single filament fineness of 2-20 dtex.
- (4) The polyamide-46 multifilament according to any one of (1) to (3), wherein sulfuric
acid relative viscosity ηr is 3.0 < ηr < 4.5.
- (5) A sewing thread for airbags, including the polyamide-46 multifilament according
to any one of the above (1) to (4).
EFFECTS OF THE INVENTION
[0017] Using the polyamide-46 multifilament of the present invention for sewing an airbag
can suppress air leakage from an airbag sewing portion due to a high temperature and
a high output gas during deployment of the airbag.
BRIEF DESCRIPTION OF THE DRAWING
[0018] Fig. 1 is a schematic view of one embodiment of a step of producing the polyamide-46
multifilament (melting step is omitted).
EMBODIMENTS OF THE INVENTION
[0019] Hereinafter, the polyamide-46 multifilament of the present invention will be described.
[0020] In order to achieve the above object, the polyamide-46 multifilament of the present
invention is made of a polyamide resin. The polyamide resin is a polyamide resin containing
polyamide 46 as a main component. The polyamide 46 having a high melting point contained
as a main component can provide a multifilament having high heat resistance.
[0021] It is preferable to use a polyamide resin the 98% by mass or more of which among
the total mass of the polyamide resin excluding additives described later is made
of polyamide 46, and it is more preferable that the polyamide resin includes only
polyamide 46.
[0022] The polyamide resin may be a copolymerized polyamide obtained by copolymerizing polyamide
46 with another polyamide, and polyamide 6, polyamide 66, polyamide 610, or polyamide
612 may be used as another polyamide to be copolymerized. The polyamide resin may
be a mixture of polyamide 46 and another polyamide.
[0023] The sulfuric acid relative viscosity of the polyamide resin is preferably 3.3-5.0,
more preferably 3.5-4.5. The polyamide resin having a sulfuric acid relative viscosity
exceeding 5.0 contributes to deterioration of stringiness, and frequently induces
yarn breakage and fluffing during drawing process. The polyamide resin having a sulfuric
acid relative viscosity of less than 3.3 is difficult to provide the polyamide-46
multifilament having a predetermined sulfuric acid relative viscosity ηr to be described
later. The sulfuric acid relative viscosity refers to a value measured by a method
described in the section of Examples described later.
[0024] The polyamide resin in the present invention may contain additives such as an end-capping
agent including monocarboxylic acid, a matting agent including titanium oxide, a polymerization
catalyst or heat stabilizer including a phosphorus compound, and an antioxidant or
heat stabilizer including a copper compound and a halide of an alkali metal or an
alkaline earth metal as components other than polyamide, as necessary.
[0025] The content ratio of the additive contained in the polyamide resin is preferably
less than 5% by weight, and more preferably less than 3% by weight. If the content
ratio of the additive is 5% by weight or more, the strength of the multifilament is
reduced.
[0026] In addition, among the additives described above, particularly the heat stabilizer
having a function of suppressing thermal degradation of the polymer is contained in
an amount of preferably 250-7000 ppm, more preferably 500-5000 ppm. The heat stabilizer
may be used singly or in combination of two or more. If the content of the heat stabilizer
is less than 250 ppm, the suppression of thermal degradation of the polymer is limited,
and the stretch characteristics and dimensional stability after aging at a high temperature
tend to be slightly impaired. On the other hand, adding the heat stabilizer in an
amount of more than 7000 ppm decreases the strength and elongation of the fiber.
[0027] The sulfuric acid relative viscosity ηr of the polyamide-46 multifilament of the
present invention is preferably 3.0 < ηr < 4.5, more preferably 3.3 < ηr < 4.2, and
still more preferably 3.5 < ηr < 4.0. Setting the sulfuric acid relative viscosity
ηr within such a range can produce the polyamide-46 multifilament having sufficient
crystal orientation with good yarn productivity.
[0028] The total fineness of the polyamide-46 multifilament of the present invention is
preferably 300-2300 dtex, and more preferably 400-1700 dtex. Setting the total fineness
to 300 dtex or more cab suppress the generation of fuzz during thermal drawing. Furthermore,
the melting time of the polymer is not excessively prolonged, and thus thermal decomposition
of the polymer can be suppressed. In addition, setting the total fineness to 2300
dtex or less can provide the polyamide-46 multifilament excellent in mechanical properties
without impairing uniformity of cooling after melt-spinning.
[0029] The number of single fibers of the polyamide-46 multifilament of the present invention
is preferably 30-350, more preferably 50-250. If the number of the single fiber is
less than 30, the single filament fineness is increased, the cooling efficiency during
melt spinning is lowered, and the flexibility of the multifilament is lost. In addition,
if the number of the single fiber is more than 350, the single filament fineness becomes
thin, and fuzz is easily generated.
[0030] In addition, the cross-sectional shape of the single fiber is not particularly limited.
In addition to a round cross section, cross sections having various shapes such as
a flat shape, a polygonal shape, different shapes including a Y shape and an X shape,
and a hollow shape can be adopted. Fibers having a plurality of cross-sectional shapes
may be mixed.
[0031] The strength of the polyamide-46 multifilament of the present invention is 6.0-9.0
cN/dtex, more preferably 7.0-9.0 cN/dtex. It has been found that the strength range
is an essential range for obtaining the polyamide-46 multifilament having stretchability
due to the crystal orientation of polyamide 46, and is an essential characteristic
for a polyamide multifilament for a sewing thread for airbags. If the strength is
less than 6.0 cN/dtex, not only the durability as a sewing thread for airbags is insufficient,
but also the crystal orientation is lowered, thus failing to provide the polyamide-46
multifilament having stretchability. If the polyamide-46 multifilament having a strength
of more than 9.0 cN/dtex is to be obtained, mechanical drawing at a high ratio is
required, failing to provide a sufficient elongation as a sewing thread for airbags.
[0032] The elongation (breaking elongation) of the polyamide-46 multifilament of the present
invention is 15-30%, and more preferably 18-28%. If the elongation is in such a range,
a polyamide multifilament suitable for a sewing thread for airbags is obtained. Furthermore,
it has been found that due to the amorphous orientation of polyamide 46, the range
of the elongation amorphous is essential for obtaining the high-temperature dimensional
stability. If the elongation is less than 15%, impact absorption due to expansion
and contraction becomes insufficient when a load is applied to the airbag sewing portion,
and durability as a sewing thread cannot be maintained. Furthermore, the orientation
of the amorphous portion becomes excessively large, failing to provide the polyamide-46
multifilament having the high-temperature dimensional stability. If the polyamide-46
multifilament having an elongation of more than 30% is to be obtained, sufficient
strength as a sewing thread for airbags fails to be obtained.
[0033] The polyamide-46 multifilament of the present invention has less than 1.0% of a
degree of elongation after stretching 10 times under an environment at 100°C, E10(100°C),
more preferably less than 0.8%. Within such a range, returning after expansion by
the pressure at the time of deploying the airbag is good, the followability of the
sewing thread to the inflatable base fabric is good, and the internal pressure retention
performance is improved. If E10(100°C) is 1.00 or more, reduction of air leakage from
the sewing portion is insufficient.
[0034] In the polyamide-46 multifilament of the present invention, the difference between
the elongation under a load of 2.0 cN/dtex at ordinary temperature, M (R.T.), and
the elongation under a load of 2.0 cN/dtex at 100°C, M (100°C), (M (100°C) - M (R.T.))
is less than 0.5%, more preferably less than 0.3%, and still more preferably less
than 0.1%. Within such a range, the dimensional stability as the sewing thread is
not impaired even under a high-temperature atmosphere at the time of deploying the
airbag, so that the filling effect can be exhibited. If the numerical value (M (100°C)
- M (R.T.)) is 0.5% or more, it means that the sewing thread easily stretches due
to heat reception in airbag deployment, which causes misalignment of the sewing portion
and is insufficient for reducing air leakage.
[0035] In the polyamide-46 multifilament of the present invention, the difference between
the degree of elongation after stretching 10 times at ordinary temperature, E10(R.T.)
and the degree of elongation after heat treatment at 120°C for 24 hours when the fiber
is subjected to 10 times of tensile tests at ordinary temperature, E10'(R.T.), (E10'
(R.T.) - E10(R.T.)) is preferably 0% or less. Within such a range, it is possible
to suppress the stretch characteristic loss due to the aging in the sewing thread,
the process of sewing, and the airbag storage environment.
[0036] In the polyamide-46 multifilament of the present invention, the difference (M' (R.T.)
- M (R.T.)) between the elongation M (R.T.) under a load of 2.0 cN/dtex at ordinary
temperature and the elongation M' (R.T.) under a load of 2.0 cN/dtex at ordinary temperature
after heat treatment at 120°C for 24 hours is preferably 0% or less. Within such a
range, it is possible to suppress deterioration in dimensional stability due to the
aging in the sewing thread, the process of sewing, and the airbag environment.
[0037] Fig. 1 schematically shows a machine for direct spinning and drawing preferably used
in the present invention. Hereinafter, an embodiment of the method for producing a
polyamide-46 multifilament of the present invention will be described with reference
to Fig. 1 as an example.
[0038] The polyamide-46 multifilament of the present invention is preferably produced by
melt spinning, and as described above, the sulfuric acid relative viscosity of the
polyamide 46 chips used for melt spinning is preferably 3.3-5.0, more preferably 3.5-4.5.
Within such a range, it is possible to stably obtain the polyamide-46 multifilament
having a high strength in a state where stringiness is good.
[0039] The moisture content of the polyamide 46 chips is preferably 1300 ppm or less, more
preferably 800 ppm or less. Adjusting the chip moisture content to such a value can
maintain the sulfuric acid relative viscosity of the polyamide-46 multifilament of
the present invention within the range, and thus can achieve the strength level of
the original thread required for the sewing thread for airbags. If the chip moisture
content exceeds 1300 ppm, hydrolysis is promoted during polymer melting, and high
strength cannot be obtained due to insufficient crystal orientation. In addition,
the stretchability of the polyamide-46 multifilament is lost, failing to achieve the
E10(100°C) as defined in the present invention.
[0040] The polyamide 46 chips are melted, kneaded and spun by an extruder spinning machine,
and the melting is preferably performed in a vacuum environment. Under a vacuum environment,
the pressure at the chip supply port of the extruder is preferably less than 5 kPa,
and more preferably less than 3 kPa (hereinafter, a pressure of less than 5 kPa is
defined as under vacuum).
[0041] Unlike other aliphatic polyamides which are thickened at the time of melting to produce
a high-molecular-weight product, the polyamide 46 has a property of decomposing at
the time of melting to produce a low-molecular-weight product. The decomposition mechanism
can be roughly classified into thermal decomposition, oxidative decomposition, and
hydrolysis, and melting under vacuum eliminates oxygen in water and air, and limits
the decomposition mechanism only to thermal decomposition, and thus can suppress decomposition
of the polymer. Suppressing decomposition during melting can maintain the high molecular
weight of the polymer constituting the multifilament, and thus can produce a highly
crystal-oriented polyamide-46 multifilament. If the pressure is 5 kPa or more under
vacuum, hydrolysis during melting fails to be suppressed, and high strength fails
to be obtained due to insufficient crystal orientation. As a result, it is difficult
for the polyamide-46 multifilament to achieve the stretchability E10(100°C) defined
in the present invention.
[0042] The spinning temperature is set to 10-50°C higher than the melting point of the polymer
chip, and melt spinning is performed from a spinneret 1 having discharge holes of
preferably 30-350, more preferably 50-250.
[0043] It is preferable that a range of 5-300 cm from immediately below the spinneret 1
is surrounded by a heating hood 2, and the melt-spun yarn is passed through a high
temperature atmosphere of -30-+30 °C relative to the chip melting point. The high-temperature
atmosphere for passing is more preferably a melting point of -30-+15°C.
[0044] Slowly cooling the spun yarn through a high-temperature atmosphere surrounded by
the heating hood 2 without immediately cooling the spun yarn allows the molecular
orientation of the melt-spun polyamide-46 polymer to be relaxed and the molecular
orientation uniformity among the single fibers to be enhanced, and thus can increase
the strength of the polyamide-46 filament.
[0045] On the other hand, if cooling is performed immediately without passing through the
high-temperature atmosphere, the orientation of the undrawn yarn is enhanced, and
the variation in the orientation degree among the single fibers is increased. Such
an undrawn yarn loses its drawability, and as a result, the highly crystal-oriented
polyamide-46 multifilament of the present invention may not be obtained.
[0046] The undrawn yarn that has passed through the above step is cooled and solidified
by blowing air at 10-80°C, preferably 10-50°C by a cross flow cooling device 3. A
case where the cooling air temperature that is less than 10°C is not preferable because
a large cooling device is required in this case. If the cooling air exceeds 80°C,
an air volume is required, and single fiber swaying increases, and thus collision
or the like between the single fibers occurs, which causes deterioration of yarn productivity.
[0047] The undrawn yarn that has been cooled and solidified is preferably subjected to multi-stage
drawing, particularly two-stage or three-stage drawing. Specifically exemplifying
the case of three-stage drawing in Fig. 1, first, an oil agent is applied to the cooled
and solidified undrawn yarn by an oil supply device 4, and the undrawn yarn is taken
up by a take-up roller (1FR) 6. The take-up roller is typically non-heated.
[0048] Thereafter, the yarn is wound in the order of a feeding roller (2FR) 7, a first drawing
rollers (1DR) 8, a second drawing roller (2DR) 9, a third drawing roller (3DR) 10,
and a relaxing roller (RR) 11, subjected to heat treatment and drawing treatment,
and wound around a winder 12. The surface of 2FR is preferably a mirror surface, and
the surfaces of 1DR, 2DR, 3DR, and RR are preferably a satin surface.
[0049] The first-stage drawing is performed between 2FR and 1DR, and the temperature of
2FR (surface temperature of the roller) is 60-90°C and the temperature of 1DR is 100-225°C.
The second-stage drawing is performed between 1DR and 2DR, and the temperature of
2DR (surface temperature of the roller) is 150-230°C. The third-stage drawing is performed
between 2DR and 3DR, and the temperature of 3DR (the surface temperature of the roller)
is 180-240°C.
[0050] Herein, in the production of the polyamide-46 multifilament of the present invention,
it is important that the draw ratio in the third-stage drawing step, that is, the
final drawing step is 1.00-1.10 times, and the draw ratio is more preferably 1.00-1.05
times.
[0051] As described in Patent Document 1 or 2, the polyamide-46 polymer is known to have
a significantly higher crystallization rate than conventional aliphatic polyamides
such as polyamide 66 and polyamide 6. That is, it is easily expected that the crystallization
of the fiber is sufficiently advanced after the first-stage drawing with a high draw
ratio or after the second-stage drawing. There is no room for drawing the fiber again
in such a final drawing step.
[0052] Setting the drawing in the final drawing step within the above range can provide
a multifilament in which the amorphous orientation is suppressed from becoming excessive
and which exhibits the high-temperature dimensional stability. If the draw ratio is
larger than the above range, the amorphous orientation increases, and thus the multifilament
is easily thermally shrunk. Such a multifilament deteriorates the high-temperature
dimensional stability, and cannot achieve M' (R.T.) - M(R.T.) defined in the present
invention. If the draw ratio is lower than 1.00 times, the tension is lowered, and
thus yarn swinging is large and yarn making becomes difficult.
[0053] Thus, the polyamide-46 multifilament of the present invention can be obtained.
[0054] If the sewing thread for airbags using the polyamide-46 multifilament of the present
invention is produced, the sewing thread for airbags can be produced by a known processing
method.
EXAMPLES
[0055] Hereinafter, the present invention will be described in more detail with reference
to Examples. However, the present invention is not to be construed as being limited
to the aspects specifically shown in Examples. The definition and measurement method
of each characteristic in the present invention are as follows.
[Sulfuric acid relative viscosity]
[0056] 1 g of a sample was dissolved in 100 ml of 98% sulfuric acid, and measurement was
performed at 25 °C using an Ostwald viscometer. An average value of two measurements
was used.
[Total fineness and single filament fineness of multifilament]
[0057] Measurement was performed according to JIS L1090 (1999).
[Strength and elongation for multifilament]
[0058] Tensile strength and a degree of elongation measured by the method of JIS L1013 (1999)
were defined as strength and elongation. Measurement was performed under conditions
of a gauge length of 250 mm and a tensile speed of 300 mm/min using a Tensilon universal
tester RTG-1250 with a high and low temperature tank manufactured by A & D Co., Ltd.
The measurement was performed 5 times for each sample, and an average value thereof
was obtained.
[Degree of elongation after stretching 10 times]
[0059] There was repeated a specified number of times an operation of holding a multifilament
having a gauge length of 250 mm with a chuck of a Tensilon universal tester RTG-1250
with a high and low temperature tank manufactured by A & D Co., Ltd, pulling the multifilament
at a speed of 300 mm/min until a load of 2.0 cN/dtex was reached, and then returning
the multifilament to the original chuck interval at a speed of 300 mm/min.
[0060] In the repeated tensile test, the elongation when a load of 0.1 cN/dtex was shown
in the return operation of the 10th cycle was defined as a degree of elongation E10
after stretching 10 times.
[0061] Herein, the measured value at ordinary temperature is represented as E10(R.T.), the
measured value under an environment of 100°C as E10(100°C), and the measured value
at ordinary temperature after the heat treatment as E10' (R.T.), and the heat treatment
was performed in an environment at 120°C for 24 hours.
[0062] The measured value is an index indicating the stretchability of the multifilament,
and as the E10(100°C) is smaller, the return after tension at a high temperature is
better, indicating that the stretchability is excellent at a high temperature.
[0063] A value obtained by subtracting E10(R.T.) from E10' (R.T.) is an index indicating
a change in stretchability after aging at a high temperature.
[Elongation under load of 2.0 cN/dtex]
[0064] In the SS curve at the time of measuring the strength and elongation, the elongation
when a load of 2.0 cN/dtex was applied was extracted. The average value of values
extracted from five measurement samples for strength and elongation was defined as
M.
[0065] Herein, the measured value at ordinary temperature is represented as M (R.T.), the
measured value under an environment of 100°C as M (100°C), and the measured value
at ordinary temperature after the heat treatment as M' (R.T.), and the heat treatment
was performed in an environment at 120°C for 24 hours.
[0066] A value obtained by subtracting M (R.T.) from M (100°C) is an index indicating the
high-temperature dimensional stability.
[0067] A value obtained by subtracting M (R.T.) from M' (R.T.) is an index indicating a
change in dimensional stability after aging at a high temperature.
[Yarn productivity]
[0068] In the step of melt-spinning a polyamide 46 polymer, drawing the spun undrawn yarn
in multiple stages, and drawing in at least the first drawing step and the final drawing
step, yarn breakage and fuzz amount when production was performed as in the following
Examples and Comparative Examples were evaluated as follows.
S: The yarn breakage in 1 hour is less than 0.1 times, and the number of fuzzes at
10,000 m is less than 1.
A: The yarn breakage in 1 hour is 0.1 times or more, and the number of fuzzes at 10,000
m is 1 or more.
B: Yarn breakage frequently occurs, and raw yarn collection is impossible.
(Example 1)
(Method for producing polyamide-46 multifilament)
[0069] The production step shown in Fig. 1 was used.
[0070] A 5 wt% aqueous solution of copper acetate as a heat stabilizer was added to and
mixed with a polyamide 46 chip (Stanyl (registered trademark), melting point 292°C)
having a sulfuric acid relative viscosity of 3.9, and 70 ppm as copper relative to
the polymer weight was added and adsorbed.
[0071] Then, a 50 wt% aqueous solution of potassium iodide and a 20 wt% aqueous solution
of potassium bromide were each added and adsorbed so as to be 1000 ppm as potassium
relative to the polymer weight, and the chip moisture content was adjusted to 700
ppm by a known drying facility.
[0072] The polyamide 46 chips were melted at 305°C under vacuum in an extruder spinning
machine.
[0073] The molten polymer was weighed so as to have a total fineness of 940 dtex by a gear
pump, filtered through a 20 p metal nonwoven fabric filter in a spinning pack, and
spun from the spinneret 1 having 136 round holes. The heating hood 2 having a heating
hood length of 15 cm was placed 3 cm below the spinneret surface, and heated so that
the incylinder atmospheric temperature was 300°C and the spun yarn passed through
the atmosphere at 300°C. The incylinder atmosphere temperature is an air temperature
at a portion 1 cm away from the inner wall at the center of the heating hood length.
[0074] The cross flow cooling device 3 for blowing air from one direction was attached immediately
below the heating hood, and cold air at 20°C was blown at a speed of 35 m/min to the
yarn that had passed through the heating hood to cool and solidify the yarn, and then
an oil solution was applied to the yarn with the oil supply device 4.
[0075] An undrawn yarn to which the oil solution had been applied was wound and taken up
in 1FR6 rotating at a surface speed of 600 m/min, and then drawn at a total draw ratio
of 4.70. The take-up yarn was continuously stretched by 5% between the take-up roller
6 and 2FR7 without being wound up once, and then successively drawn in the first stage
at a rotation speed ratio of 3.27 times, then drawn in the second stage at a rotation
speed ratio of 1.30 times, and finally drawn in the third stage at a rotation speed
ratio of 1.05 times, and then wound up at a speed of 2600 m/min.
[0076] The roller surfaces of 1FR and 2FR were mirror finished, and 1DR, 2DR, 3DR, and RR
were satin finished. The roller temperatures of 1FR were non-heated, 2FR was 80°C,
1DR was 175°C, 2DR was 180°C, 3DR was 230°C, and RR was 150°C.
[0077] Such melt spinning and drawing provided the polyamide-46 multifilament. The obtained
fiber properties were evaluated and shown in Table 1.
(Example 2)
[0078] The procedure was performed in the same manner as in Example 1, except that the third
stage draw ratio (final draw ratio) was changed as shown in Table 1 at the time of
spinning the polyamide-46 multifilament.
(Example 3)
[0079] The procedure was performed in the same manner as in Example 1, except that the total
fineness of the polyamide-46 multifilament was changed as shown in Table 1.
(Example 4)
[0080] The procedure was performed in the same manner as in Example 1, except that the total
fineness and total draw ratio of the polyamide-46 multifilament were changed as shown
in Table 1.
(Example 5)
[0081] The procedure was performed in the same manner as in Example 1, except that the total
fineness, total draw ratio, and final draw ratio of the polyamide-46 multifilament
were changed as shown in Table 1.
(Examples 6 and 7)
[0082] The procedure was performed in the same manner as in Example 1, except that the total
draw ratio and final draw ratio of the polyamide-46 multifilament were changed as
shown in Table 1.
(Example 8)
[0083] The procedure was performed in the same manner as in Example 1, except that a heat
stabilizer (copper acetate, potassium iodide, and potassium bromide) was not added
at the time of preparing the polyamide 46 chips.
(Comparative Examples 1 and 2)
[0084] The procedure was performed in the same manner as in Example 1, except that the final
draw ratio was changed as shown in Table 1.
(Comparative Example 3)
[0085] The procedure was performed in the same manner as in Example 1, except that melt
spinning in an extruder spinning machine was performed under normal pressure.
(Comparative Example 4)
[0086] The procedure was performed in the same manner as in Example 1, except that the total
fineness and total draw ratio of the polyamide-46 multifilament were changed as shown
in Table 1.
(Comparative Examples 5 and 6)
[0087] The procedure was performed in the same manner as in Example 2, except that the total
draw ratio of the polyamide-46 multifilament was changed as shown in Table 1.
(Comparative Example 7)
[0088] The procedures was performed in the same manner as in Example 1, except that a polyamide
66 polymer having a sulfuric acid relative viscosity of 3.8 was melt-spun at 280°C
under vacuum using an extruder spinning machine.
(Comparative Example 8)
[0089] The procedure was performed in the same manner as in Example 1, except that a polyamide
6 polymer having a sulfuric acid relative viscosity of 3.8 was melt-spun at 260°C
under vacuum using an extruder spinning machine.
[Table 1-1]
|
Unit |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
Comparative Example 1 |
Material polymer |
- |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
Whether heat stabilizer contains or not |
- |
Yes |
Yes |
Yes |
Yes |
Yes |
Yes |
Yes |
No |
Yes |
Environment in the melt spinning process |
- |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Total draw ratio |
Times |
4.70 |
4.70 |
4.70 |
4.20 |
4.20 |
4.10 |
5.10 |
4.70 |
4.70 |
Final draw ratio |
Times |
1.05 |
1.00 |
1.05 |
1.05 |
1.08 |
1.00 |
1.00 |
1.05 |
1.20 |
Total fineness |
dtex |
940 |
940 |
1400 |
470 |
470 |
940 |
940 |
940 |
940 |
Breaking strength |
cN/dtex |
7 . 4 |
7.6 |
7.4 |
7.4 |
7.3 |
6.6 |
8.2 |
7 . 4 |
6.9 |
Elongation at break |
% |
20.8 |
21.4 |
19.7 |
20.6 |
20.2 |
25.2 |
18.3 |
21.0 |
20.2 |
Sulfuric acid relative viscosity ηr |
- |
3.6 |
3.6 |
3.7 |
3.6 |
3.6 |
3.7 |
3.5 |
3.6 |
3.6 |
Residual elongation rate after stretching 10 times at 100°C E10 (100°C) |
% |
0.60 |
0.60 |
0.70 |
0.60 |
0.80 |
0.80 |
0.30 |
0.60 |
0. 90 |
Difference of elongation at 2.0 cN/dtex between 100°C and room temperature |
% |
0.00 |
-0.10 |
0.10 |
0.00 |
0.20 |
-0.25 |
0.30 |
0.00 |
0.70 |
Difference of residual elongation after stretching 10 times between before and after
heat treatment |
% |
-0.80 |
-0.60 |
-0.40 |
-0.40 |
-0.40 |
-0.60 |
-0.40 |
0.30 |
-0.40 |
Difference of elongation at 2.0 cN/dtex between before and after heat treatment |
% |
-1.50 |
-1.30 |
-1.10 |
-1.10 |
-0.40 |
-1.50 |
-1.30 |
1.20 |
0.30 |
Yarn productivity |
- |
S |
S |
S |
S |
S |
S |
S |
S |
A |
PA 46: polyamide 46, PA 66: polyamide 66, PA 6: polyamide 6 |
[Table 1-2]
|
Unit |
Comparative Example 2 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
Comparative Example 6 |
Comparative Example 7 |
Comparative Example 8 |
Material polymer |
- |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA4 6 |
PA66 |
PA6 |
Whether heat stabilizer contains or not |
- |
Yes |
Yes |
Yes |
Yes |
Yes |
Yes |
Yes |
Environment in the melt spinning process |
- |
Under vacuum |
Under normal pressure |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Under vacuum |
Total draw ratio |
Times |
4.70 |
4.70 |
4.20 |
3.60 |
5.40 |
5.10 |
5.10 |
Final draw ratio |
Times |
0.90 |
1.05 |
1.05 |
1.00 |
1.00 |
1.05 |
1.05 |
Total fineness |
dtex |
- |
940 |
235 |
940 |
- |
940 |
940 |
Breaking strength |
cN/dtex |
- |
5.7 |
5.8 |
5.7 |
- |
8.6 |
8.1 |
Elongation at break |
% |
- |
22.2 |
20.4 |
28.9 |
- |
22.1 |
22.0 |
Sulfuric acid relative viscosity ηr |
- |
- |
3.1 |
3.3 |
3.7 |
- |
3.7 |
3.7 |
Residual elongation rate after stretching 10 times at 100°C E10 (100°C) |
% |
- |
1.25 |
1.20 |
1.15 |
- |
1.20 |
1.30 |
Difference of elongation at 2.0 cN/dtex between 100°C and room temperature |
% |
- |
0.20 |
0.20 |
-0.35 |
- |
0.70 |
0.90 |
Difference of residual elongation after stretching 10 times between before and after
heat treatment |
% |
- |
-1.50 |
-1.4 0 |
-1.50 |
- |
0.40 |
0.10 |
Difference of elongation at 2.0 cN/dtex between before and after heat treatment |
% |
- |
-1.10 |
-1. 00 |
-1.10 |
- |
2.10 |
2.50 |
Yarn productivity |
- |
B |
A |
A |
S |
B |
S |
S |
PA 46: polyamide 46, PA 66: polyamide 66, PA 6: polyamide 6 |
[0090] The production conditions in Examples 1 to 6 and Comparative Examples 1 to 8 and
the results of evaluating the physical properties of the obtained polyamide-46 multifilament
are shown in Table 1.
[0091] As is clear from Table 1, the polyamide-46 multifilament of the present invention
has high strength, high thermal dimensional stability, and excellent stretchability.
[0092] On the other hand, the conventional aliphatic polyamide multifilament shown in Comparative
Examples 7 and 8 has high strength, but has low stretchability and insufficient high-temperature
dimensional stability. When applied as the sewing thread for airbags, it is impossible
to suppress misalignment and improve internal pressure retention performance.
[0093] In Comparative Example 3, hydrolysis is promoted by melting under normal pressure,
resulting in the multifilament having low crystal orientation. Therefore, a multifilament
fails to have high strength, and the stretchability is disadvantageous.
[0094] In Comparative Example 4, the polymer retention time in the spinning machine becomes
longer with the decrease in the polymer discharge amount, and thus, thermal deterioration
tends to occur during melting. The strength of the polyamide-46 multifilament was
reduced, and E10(100°C) exceeded 1.0.
[0095] Furthermore, as in Comparative Example 1, when the final draw ratio in the final
drawing step is more than 1.10 in the production of the polyamide-46 multifilament
having high strength, the amorphous orientation increases, thus resulting in the multifilament
easily undergoing thermal shrinkage. Therefore, it was confirmed that the high-temperature
dimensional stability M (100°C) - M (R.T.) was more than 0.5. On the other hand, in
Comparative Example 2, the final draw ratio in the final drawing step was less than
1.0, and thus yarn breakage frequently occurred, and raw yarn collection was difficult.
[0096] Examples 2 and 6 and Comparative Example 5 were examples in which the crystal structure
of the polyamide-46 multifilament was controlled, but the crystal orientation was
smaller as the draw ratio was shifted to low draw ratio, and the influence on the
stretchability was confirmed. Similarly, in Examples 2 and 7 and Comparative Example
6, the amorphous orientation was increased as the draw ratio was shifted to high draw
ratio, and the influence on the high-temperature dimensional stability was confirmed.
In Comparative Example 6, the high draw ratio resulted in deterioration of the yarn
productivity.
INDUSTRIAL APPLICABILITY
[0097] The polyamide-46 multifilament of the present invention has high strength and high
heat resistance, and is suitable for sewing thread for the sewing thread for airbags.
Furthermore, excellent high-temperature dimensional stability and stretchability induce
a sewing portion filling effect in use of the sewing thread for airbags. It is possible
to provide an airbag that achieves reduction of air leakage from a sewing portion
due to a high-temperature and high-output inflator and improvement in internal pressure
retention performance, which have been problems heretofore.
DESCRIPTION OF REFERENCE SIGNS
[0098]
- 1: Spinneret
- 2: Heating hood
- 3: Cross flow cooling device
- 4: Oil supply device
- 5: Yarn
- 6: Take-up roller (1FR)
- 7: Feeding roller (2FR)
- 8: First drawing roller (1DR)
- 9: Second drawing roller (2DR)
- 10: Third drawing roller (3DR)
- 11: Relaxing roller (RR)
- 12: Winder