JPH01254005A - Stay for fixing antenna - Google Patents

Abstract

PURPOSE:To improve resistance to corrosion, weather-proof, creepage resistance and shock resistance by making the stay with a molecule oriented forming made of polyolefin with ultrahigh molecular weight having a specific limit viscosity. CONSTITUTION:The stay is made of a molecule oriented forming made of a polyolefin with ultrahigh molecular weight whose limit viscosity [eta] is at least 4dl/g. Then as the polyolefin with ultrahigh molecular weight forming the molecule oriented forming, polyethylen with ultrahigh molecular weight, polypropylen with ultrahigh molecular weight, poly-1-butene with ultrahigh molecular weight or 2 kinds or over of alpha-polyolefin copolymer with ultrahigh molecular weight is used. Moreover, the molecule oriented forming made of the polyolefin with ultrahigh molecular weight is light in weight with high strength, and excellent water resistance and salt water resistance are obtained. Thus, the corrosion resistance, weather-proof, resistance to creepage and shock resistance are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stay for fixing an antenna, and more specifically, it is made of a molecularly oriented molded product of ultra-high molecular weight polyolefin, is lightweight, has high strength, and has excellent water resistance. Rather than being cast like metal stays, more specifically, it is made of a molecularly oriented molded product of ultra-high molecular weight ethylene/α-olefin copolymer.
Moreover, the present invention relates to an antenna fixing stay that has excellent weather resistance and creep resistance.

Antennas such as TV antennas are usually installed outdoors, such as on roofs, but in this case, wire-like objects called stays are used to secure the antennas to buildings. .

Conventionally, metal wires have been used as antenna fixing stays, but these metal stays are heavy and tend to rust and break when used for a long period of time.

To solve these problems, antenna fixing stays made of aromatic polyamide fibers such as Kevlar or ultra-high molecular weight polyethylene fibers have begun to be used.

However, antenna fixing stays made of aromatic polyamide fibers such as Kevlar have had a serious problem of poor weather resistance.

It is already known that a molecularly oriented molded article having high elastic modulus and high tensile strength can be obtained by forming ultra-high molecular weight polyethylene into fibers, tapes, etc. and stretching the fibers. For example, in Japanese Patent Application Laid-Open No. 56-15408,
Spinning dilute solutions of ultra-high molecular weight polyethylene and drawing the resulting filaments is described. Also,
JP-A-59-130313 discloses that ultra-high molecular weight polyethylene and wax are melt-kneaded, the kneaded product is extruded, cooled and solidified, and then stretched, and JP-A-59-187614 describes , it is described that the above melt-kneaded product is extruded, drafted, cooled and solidified, and then stretched.

The present invention aims to solve the problems associated with the prior art as described above, and does not rust like metal stays, and has weather resistance, creep resistance, and The purpose is to provide an antenna fixing stay with excellent impact resistance.

The antenna fixing stay according to the present invention has a limiting viscosity [η]
It is characterized by being made of a molecularly oriented molded body of ultra-high molecular weight polyolefin having a molecular weight of at least 5 dJ/tr, and further has an intrinsic viscosity [η] of at least 5 dl/+.
r, and the content of α-olefins having 3 or more carbon atoms is on average 0.1 to 20 per 1000 carbon atoms. It is characterized by

Since the antenna fixing stay according to the present invention is made of a molecularly oriented molded product of ultra-high molecular weight polyolefin or ultra-high molecular weight ethylene/α-olefin copolymer as described above, it does not rust like metal stays. Moreover, it has excellent weather resistance, creep resistance, and impact resistance.

BEST MODE FOR CARRYING OUT THE INVENTION The antenna fixing stay according to the present invention will be specifically explained below.

First, the molecularly oriented molded product of ultra-high molecular weight polyolefin, particularly the molecularly oriented molded product of ultra-high molecular weight ethylene/α-olefin copolymer, constituting the antenna fixing stay according to the present invention will be explained.

The molecularly oriented molded product used in the present invention is a molecularly oriented molded product of an ultra-high molecular weight polyolefin or a molecularly oriented molded product of an ultra-high molecular weight ethylene/α-olefin copolymer.

Specifically, the ultra-high molecular weight polyolefin constituting the molecularly oriented molded article of the present invention includes ultra-high molecular weight polyethylene,
Examples include ultra-high molecular weight polypropylene, ultra-high molecular weight poly-1-butene, and ultra-high molecular weight copolymers of two or more types of α-olefins. This molecularly oriented molded article of ultra-high molecular weight polyolefin is lightweight, has high strength, and has excellent water resistance and salt water resistance.

Further, as the ultra-high molecular weight ethylene/α-olefin copolymer constituting the molecularly oriented molded article of the present invention, ultra-high molecular weight ethylene/propylene copolymer, ultra-high molecular weight ethylene/
1-butene copolymer, ultra-high molecular weight ethylene/4-methyl-1-pentene copolymer, ultra-high molecular weight ethylene/1-hexene copolymer, ultra-high molecular weight ethylene/1-octene copolymer, ultra-high molecular weight Ethylene and carbon atoms such as ethylene/1-thecene copolymer from 3 to 20, preferably from 4 to 1
An example is an ultra-high molecular weight ethylene/α-olefin copolymer with 0 α-olefin. In this ultra-high molecular weight ethylene/α-olefin copolymer, the number of α-olefins having 3 or more carbon atoms is 0.1 to 20, preferably 0.5 to 10, and more preferably 0.5 to 10 per 1000 carbon atoms of the polymer. It is contained in an amount of 1 to 7.

Molecularly oriented molded products obtained from such ultra-high molecular weight ethylene/α-olefin copolymers have particularly excellent impact resistance and creep resistance compared to molecularly oriented molded products obtained from ultra-high molecular weight polyethylene. This ultra-high molecular weight ethylene/α-olefin copolymer is lightweight, has high strength, and has excellent wear resistance, impact resistance, and creep resistance.
Excellent weather resistance, water resistance, and salt water resistance.

The ultra-high molecular weight polyolefin or ultra-high molecular weight ethylene/α-olefin copolymer constituting the molecularly oriented molded product of the present invention has an intrinsic viscosity [η] of 5 dO/g or more, preferably in the range of 7 to 30 dj/g. The molecularly oriented molded product obtained from this copolymer has excellent mechanical properties and heat resistance. That is, since molecular terminals do not contribute to fiber strength and the number of molecular terminals is the reciprocal of the molecular weight (viscosity), a material with a large intrinsic viscosity [η] gives high strength.

The density of the molecularly oriented molded product of the present invention is 0.940 to 0.9
90g/- preferably 0.960-0.985sr/-
, where the density is the usual fAsTHD 1505)
Accordingly, measurements were carried out using the density gradient tube method. The density gradient tube at this time was prepared by using carbon tetrachloride and toluene, and the measurements were carried out at room temperature (23° C.).

Dielectric constant of the molecularly oriented molded product of the present invention (IKHz, 23°C)
is 1.4 to 3.0 preferably 1.8 to 2.4,
Positive electric loss tangent (IKHz + 80℃) is 0.050 to 0
．． 008%, preferably 0.040 to 0.010%. Here, the dielectric constant and the positive electric dissipation tangent were measured by ASTHD 150 using a film-like sample obtained by closely aligning fibers and a tape-like molecular oriented material in one direction.

The stretching ratio of the molecularly oriented molded article of the present invention is 5 to 80 times, preferably 10 to 50 times.

The degree of molecular orientation in the molecularly oriented molded product of the present invention is
When the ultra-high molecular weight polymer of the present invention is a drawn filament, which can be determined by linear diffraction method, birefringence method, fluorescence polarization method, etc. (1939), where Ho is the half-width (°) of the intensity distribution curve along the Debye ring of the strongest paratropic surface on the equator. The degree of orientation (F) defined as ) is 0.90 or more, especially 0.9
From the viewpoint of mechanical properties, it is desirable that the molecules be oriented so that the number of particles is 5 or more.

Furthermore, the molecularly oriented molded product of the present invention has excellent mechanical properties, for example, in the form of a drawn filament,
an elastic modulus of more than a, especially more than 30 GPa, and 1.2 GPa
In particular, it has a tensile strength of 1.5 GPa or more.

The impulse voltage breakdown value of the molecularly oriented molded product of the present invention is 1
10-250 KV/nan preferably 150-220
KV/rsth. The impulse voltage breakdown value was measured using the same sample as in the case of permittivity, and was measured on a copper plate with yellow @(
25 m + nφ) JIS type electrode, increase the voltage while applying negative impulses in steps of 2 KV/3 times, and measure.

When the molecularly oriented molded product of the present invention is a molecularly oriented molded product of an ultra-high molecular weight ethylene/α-olefin copolymer, this molecularly oriented molded product has extremely excellent 1litWI impact resistance, breaking energy, and creep resistance. It has the characteristic of being The characteristics of these molecularly oriented molded products of ultra-high molecular weight ethylene/α-olefin copolymers are expressed by the following physical properties.

The breaking energy of the molecularly oriented molded product of ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is 8 kg-
m/r or more, preferably 10 kg-m/g or more.

Moreover, the molecularly oriented molded article of the ultra-high molecular weight ethylene/α-olefin copolymer of the present invention has excellent creep resistance. In particular, it has outstanding creep resistance at high temperatures, which corresponds to the conditions that promote creep at room temperature.
% breaking load, the atmospheric temperature is 70°C, and the creep calculated as elongation (%) after 90 seconds is 7% or less, especially 5
% or less, and the creep rate (ε, sec ”) after 90 seconds to 180 seconds is 4 x 10-4 sec-
' or less, especially less than 5 x 10' sec -1.

Among the molecularly oriented materials of the present invention, ultra-high molecular weight ethylene/α
-The molecularly oriented olefin copolymer has the above-mentioned room-temperature properties, but if it also has the following thermal properties in addition to these room-temperature properties, the above-mentioned room-temperature properties can be further improved. However, it is preferable because it also has excellent heat resistance.

The molecularly oriented molded product of the ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention has at least one crystal melting peak at a temperature at least 20°C higher than the original crystal melting temperature (Tn) of the copolymer. The heat of fusion based on (Tp) is 15% or more, preferably 20% or more, particularly 30% or more.

Ultra-high molecular weight ethylene copolymer original crystal melting temperature (TT
I) is by completely melting this molded body and then cooling it.
A method of raising the temperature again after bringing the molecular orientation in the molded body to the M phase, a so-called second heating method in a differential scanning calorimeter.
It can be found by running.

To explain further, in the molecularly oriented molded article of the present invention, there is no crystal melting peak at all in the above-mentioned crystal melting temperature range inherent to the copolymer, or even if it exists, it exists only as a slight tailing. Crystal melting peak (
Tp) is generally within the temperature range Ti+20°C to T11+50
℃, especially in the region of TI+20℃ to TI+100℃, and this peak (Tp) often appears as multiple peaks within the above temperature range, that is, this crystal melting peak (Tp) is the temperature range T11
High temperature side melting peak ('rp1) at ÷35℃~T11+100'C and temperature range TLIl-1-20℃~T
Imo often appears separated into two peaks, the low-temperature side melting peak ('rp 2) at 35°C, and depending on the manufacturing conditions of the molecularly oriented molded product, Tpl and Tp2 may further consist of multiple peaks. There is also.

These high crystal melting peaks ('rp, 'rp
2) significantly improves the heat resistance of molecularly oriented molded products of ultra-high molecular weight ethylene/α-olefin copolymers and contributes to strength retention or elastic modulus retention after high-temperature thermal history. I think that the.

Also, high temperature lI in the temperature range Tn+35℃~Tn+100℃
l! The total heat of fusion based on the I melting peak ('rp1) is desirably 1.5% or more, particularly 3.0% or more based on the total heat of fusion.

In addition, as long as the sum of the heat of fusion based on the high temperature 1111 melting peak (Tpl) satisfies the above value, if the high temperature side melting peak ('rp1) does not stand out as a main peak, that is, a collection of small peaks. Even if the peak becomes large or broad, the heat resistance may be slightly lost, but the creep resistance is excellent.

The melting point and heat of crystal fusion in the present invention were measured by the following method.

The melting point was determined using a differential scanning calorimeter as follows.

A DSCII type (manufactured by PerkinElmer) was used as a differential scanning calorimeter. The sample is approximately 3■4 m+ x 4 +u+
, and was restrained inward by wrapping it around an aluminum plate having a thickness of 0.2a++n. The sample was then wrapped around an aluminum plate and sealed in an aluminum pan to serve as a measurement sample. Additionally, the empty aluminum pan that is usually placed in the reference holder was filled with the same aluminum plate used for the sample to maintain heat balance. First, the sample was held at 30°C for about 1 minute, and then the temperature was raised to 250°C at a heating rate of 10°C/min.
Melting point measurement at the second temperature increase was completed. Subsequently, the temperature was held at 250°C for 10 minutes, then the temperature was lowered at a rate of 20'C/min, and the sample was further held at 30°C for 10 minutes.

Then, the second temperature increase was made to 250°C at a heating rate of 10°C/min.
At this time, the melting point measurement during the second temperature increase (second run) was completed. At this time, the maximum value of the melting peak was taken as the melting point. When it appears as a shoulder, a tangent is drawn at the inflection point immediately on the low-temperature side and the inflection point immediately on the high-temperature side of the shoulder, and the intersection is taken as the melting point.

In addition, from the straight line (baseline) connecting the 60°C and 24C'C points on the endothermic curve and the original crystal melting temperature (Tn) of the ultra-high molecular weight ethylene copolymer, which is determined as the main melting peak at the second temperature increase, Perpendicular lines are drawn to the points with high °C, and the low-temperature side surrounded by these is based on the crystal melting (Tll) inherent to the ultra-high molecular weight ethylene copolymer, and the high-temperature side is the photograph of the molded article of the present invention. The heat of fusion of each crystal was calculated from these areas. Also, Tpl and T
The heat of fusion based on the melting of O2 was also determined according to the method described above.
The part surrounded by the perpendicular line from +20°C and the perpendicular line from TIl+35°C was taken as the heat of fusion based on the melting of Tl)2, and the high temperature side part was similarly calculated as the heat of fusion based on the melting of Tpl. .

The drawn filament of the ultra-high molecular weight ethylene/α-olefin copolymer of the present invention has a strength retention rate of 95% or more and an elastic modulus retention rate of 90% or more after being subjected to a heat history of 5 minutes at 170°C. In particular, it has an excellent heat resistance of 95% or more, which is completely unrecognizable in conventional drawn polyethylene filaments.

One day of molecular orientation of ultra-high molecular weight polyolefin.As a method for obtaining the above-mentioned drawn ultra-high molecular weight polyolefin having high elasticity and high tensile strength, for example,
6-15408 Publication 1, JP-A-58-5228, JP-A-59-130313, JP-A-59-18
The stretchability of ultra-high molecular weight polyolefin can be improved by making ultra-high molecular weight polyolefin into a dilute solution, or by adding a low molecular weight compound such as paraffin wax to ultra-high molecular weight polyolefin, as described in detail in Publication No. 7614. An example of an improved method for stretching to a high magnification can be given.

Ultra-high molecular weight ethylene/α-olefin
2 Next, the present invention will be explained below in order of raw materials, manufacturing method, and purpose for easy understanding.

黄--1 The ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention can be obtained by slurry polymerizing ethylene and an α-olefin having 3 or more carbon atoms using a Ziegler catalyst, for example, in an organic solvent. It is obtained by

As the α-olefin having 3 or more carbon atoms, propylene,
butene-1, pentene-1,4-methylpentene-1,
Hexene-1, heptene-1, octene-1, etc. are used, but among these, butene-1,4-methylpentene-1, hexene-1, octene-1, etc. are particularly preferred.
Such α-olefins are copolymerized with ethylene in such a manner that they are present per 1000 carbon atoms in the resulting copolymer. Further, the ultra-high molecular weight ethylene/α-olefin copolymer used as a base when producing the molecularly oriented product in the present invention should have a molecular weight corresponding to the above-mentioned intrinsic viscosity [η].

The α-olefin component in the ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is determined using an infrared spectrophotometer (manufactured by JASCO Corporation). Specifically, the absorbance of 1378■-1, which represents the bending vibration of the methyl group of the α-olefin incorporated into the ethylene chain, was measured using an infrared spectrophotometer, and this value was determined in advance by 13C nuclear magnetism. Using a resonance device, the amount of α-olefin in the ultra-high molecular weight ethylene/α-olefin copolymer can be determined by converting it into the number of methyl branches per 1000 carbon atoms using a calibration curve created using a model compound. Quantify.

In the present invention, when producing a molecularly oriented body from the ultra-high molecular weight ethylene/α-olefin copolymer, a diluent is blended into the copolymer. As such a diluent, a solvent for the ultra-high molecular weight ethylene copolymer or various wax-like substances having compatibility with the ultra-high molecular weight ethylene copolymer can be used.

Such a solvent has a boiling point higher than the melting point of the copolymer, more preferably 20°C higher than the melting point of the copolymer.
A solvent having a boiling point higher than that is used.

Specifically, such solvents include n-nonane, n-
- Decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane or liquid paraffin, aliphatic hydrocarbon solvents such as kerosene, xylene, naphthalene,
Tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene,
Aromatic hydrocarbon solvents such as dodecylbenzene, bicyclohexyl, decalin, methylnaphthalene, ethylnaphthalene or hydrogenated derivatives thereof, 1,1,2.2-tetrachloroethane, pentachloroethane, hexachloroethane, 1.2.3- Examples include halogenated hydrocarbon solvents such as trichloropropane, dichlorobenzene, 1.2.4-trichlorobenzene, and bromobenzene, and mineral oils such as paraffinic process oils, naphthenic process oils, and aromatic process oils.

Further, as the wax as a diluent, specifically, an aliphatic hydrocarbon compound or a derivative thereof is used.

Such aliphatic hydrocarbon compounds are mainly composed of saturated aliphatic hydrocarbon compounds, and are usually compounds called paraffin waxes having a molecular weight of 2,000 or less, preferably 1,000 or less, more preferably 800 or less.

Examples of such aliphatic hydrocarbon compounds include n-alkanes having 22 or more carbon atoms such as tocosan, tricosane, tetracosane, and triacontane, mixtures of these with lower n-alkanes as main components, petroleum So-called paraffin wax separated and purified from ethylene, medium/low pressure polyethylene wax which is a low molecular weight polymer obtained by copolymerizing ethylene and α-olefin, high pressure polyethylene wax, ethylene copolymer wax or medium・Waxes obtained by reducing the molecular weight of polyethylene such as low-pressure polyethylene and high-pressure polyethylene by thermal degradation, oxides of these waxes, oxidized waxes modified with maleic acid, waxes modified with maleic acid, etc. are used.

Examples of aliphatic hydrocarbon compound derivatives include, for example, one or more carboxyl groups, preferably one to two carboxyl groups, particularly preferably one carboxyl group, at the terminal or inside of an aliphatic hydrocarbon group (alkyl group, alkenyl group), A compound having a functional group such as a hydroxyl group, a carbamoyl group, an ester group, a meltcapto group, or a carbonyl group with a carbon number of 8 or more, preferably a carbon number of 12 to 50 or a molecular weight of 130 to 2000.
Preferably, 200 to 800 fatty acids, aliphatic alcohols, fatty acid amides, fatty acid esters, aliphatic mercaptans, aliphatic aldehydes, aliphatic ketones, etc. are used.

Examples of such aliphatic hydrocarbon compound derivatives include fatty acids such as capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, and oleic acid, lauric alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Fatty acid amides such as caprinamide, lauramide, palmitinamide, and stearylamide, fatty acid esters such as stearyl acetate, and the like are used.

The ultra-high molecular weight ethylene/α-olefin copolymer and diluent differ depending on their type, but generally 3
:97-80:20, especially 15:85-60:
A weight ratio of 40 is used. If the amount of the diluent is lower than the above range, the melt viscosity will become too high, making melt kneading and melt molding difficult, and the resulting molded product will have a markedly rough surface and is prone to stretch breakage, etc. If the amount of the diluent is larger than the above range, melt-kneading will become difficult, and the resulting molded product will have poor stretchability.

Melt kneading is generally carried out at 150 to 300°C, especially at 170 to 300°C.
It is carried out at a temperature of 270°C. If the temperature is lower than the above range, the melt viscosity will be too high and melt molding will be difficult, and if the temperature is higher than the above range, the molecular weight of the ultra-high molecular weight ethylene/α-olefin copolymer will decrease due to thermal degradation. However, it becomes difficult to obtain a crushed molded article having a high elastic modulus and high strength. The formulation is made using a Henschel mixer, V
It may be carried out by dry blending using a mold blender or the like, or it may be carried out using a single screw extruder or a multi-screw extruder.

Melt molding of a dope (spinning stock solution) comprising an ultra-high molecular weight ethylene/α-olefin copolymer and a diluent is generally performed by melt extrusion molding. Specifically, filaments for drawing are obtained by melt extruding the dope through a spinneret.

At this time, the molten material extruded from the spinneret may be drafted, that is, drawn in the molten state. Extrusion speed V of the molten resin in the Gouy orifice. The draft ratio can be defined by the following formula:

Draft ratio -v/vo...(2)
Such a draft ratio varies depending on the temperature of the mixture, the molecular weight of the ultra-high molecular weight ethylene copolymer, etc., but is usually 3 or more, preferably 6 or more.

Next, the ultra-high molecular weight ethylene α obtained in this way
- Stretching the unstretched molded olefin copolymer. Stretching is carried out so as to effectively impart at least uniaxial molecular orientation to the unstretched molded article obtained from the ultra-high molecular weight ethylene/α-olefin copolymer.

Stretching of an unstretched molded article obtained from an ultra-high molecular weight ethylene/α-olefin copolymer is generally carried out at a temperature of 40 to 160°C, particularly 80 to 145°C. Air,
Either water vapor or liquid medium can be used. However, as a heat medium, a liquid medium that is a solvent capable of eluting and removing the diluent described above and whose boiling point is higher than the melting point of the molded article composition, specifically, decalin, decane, kerosene, etc., is used. It is preferable to carry out the stretching operation in such a manner that the diluent described above can be removed, uneven stretching will not occur during stretching, and a high stretching ratio can be achieved.

The means for removing the diluent from the ultra-high molecular weight ethylene/α-olefin copolymer is not limited to the above-mentioned method, but may include a method of treating an unstretched material with a solvent such as hexane, heptane, hot ethanol, chloroform, or benzene, and then stretching it; A stretched product with high elastic modulus and high strength can also be obtained by removing the diluent in the molded product by treating the stretched product with a solvent such as hexane, heptane, hot ethanol, chloroform, or benzene.

The stretching operation can be performed in one stage or in multiple stages of two or more stages. The stretching ratio depends on the desired molecular orientation and the associated effect of increasing the melting temperature, but is generally between 5 and 5.
80 times, preferably 10 to 50 times.

In general, it is preferable to carry out the stretching operation in two or more stages, and in the -th stage, the stretching operation is carried out while extracting the diluent in the extrudate at a relatively low temperature of 80 to 120°C. From the second stage onward, it is preferable to stretch the molded body at a temperature of 120 to 160°C, and at a temperature higher than the first stage stretching temperature.

In the case of a uniaxial stretching operation, tension stretching may be performed between rollers having different circumferential speeds.

The molecularly oriented molded product thus obtained can be heat-treated under restrictive conditions if desired.

This heat treatment is generally carried out at 140-180°C, preferably at 15°C.
At a temperature of 0 to 175°C for 1 to 20 minutes, preferably 3 to 1
It can be done for 0 minutes. The heat treatment further advances the crystallization of the oriented crystal parts, shifts the crystal melting temperature to a higher temperature side, improves the strength and elastic modulus, and further improves the creep resistance at high temperatures.

In the present invention, a rope is braided from such an ultrahigh molecular weight polyolefin molecularly oriented molded product or a filamentary molecularly oriented molded product of an ultrahigh molecular weight ethylene/α-olefin copolymer, and used as a stay for fixing the antenna.

A conventionally known method is employed to braid a rope from filament-like molecularly oriented bodies.

Furthermore, the breaking energy of the antenna fixing stay of the present invention, which is braided into a rope, is 3 kt-m/or more, preferably 4 kg Hm/Ii- or more. Another feature of the molecularly oriented molded product used in the present invention is that the strength utilization rate decreases less when braided.

Generally suitable rope forms include three-strand, six-strand ropes for twisted structures, and eight-strand ropes for braided structures (commonly known as
Structures include eight ropes), 12-stroke ropes (commonly known as toer ropes), and double-braided ropes (commonly known as taffle ropes).

In addition, polyester, nylon,
Polypropylene was used, and a filament-like molecularly oriented molded body used in the present invention was used as the core blade. A uniline that uses polyester, nylon, polypropylene, etc. for the double braid or outer blade jacket, an intermediate layer such as neoprene or vinyl chloride, and the filament-like molecularly oriented molded product of the present invention as the parallel yarn core. Examples include structures such as parallel yarn cores.

In this case, the molecularly oriented ultra-high molecular weight ethylene/α-olefin copolymer has moderate elongation and high knot strength compared to the molecularly oriented ultra-high molecular weight polyethylene. I can knit. Furthermore, it is possible to obtain the effect that there is less loss when forming the rope.

As mentioned above, in the present invention, the molecularly oriented molded product of ultra-high molecular weight polyolefin and the molecularly oriented molded product of ultra-high molecular weight ethylene/α-olefin copolymer are used as antenna fixing stays. It does not rust like gold R stays and has excellent weather resistance, creep resistance, and impact resistance.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Polymerization of ultra-high molecular weight ethylene/butene-1 copolymer> Using a Ziegler catalyst and n-decane 11 as the polymerization solvent, slurry polymerization of ultra-high molecular weight ethylene/butene-1 copolymer was carried out. Ta. A monomer gas mixture with a molar ratio of ethylene and butene-1 of 97.2:2.35 was continuously supplied to the reactor to maintain a constant pressure of 5 to 2/-.0 Polymerization was a reaction. The process was completed in 2 hours at a temperature of 70°C.

The yield of the obtained ultra-high molecular weight ethylene-butene-1 copolymer powder was 1601r and f! Limiting viscosity [η) (decalin:
(135°C) was 8.2 dj/g, and the butene-1 content by infrared spectrophotometer was 1.5 per 1000 carbon atoms.

Preparation of stretched and oriented ultra-high molecular weight ethylene/butene-1 copolymer> 20 parts by weight of the ultra-high molecular weight ethylene/butene-1 copolymer powder obtained by the above polymerization and paraffin wax (melting point = 69°C, molecular weight =490) A mixture of 80 parts by weight was melt-spun under the following conditions.

3.5- as a process stabilizer to 100 parts by weight of the mixture.
Didert-butyl-4-hydroxytoluene 0,
The mixture was then extruded using a screw. (Screw diameter = 25 mm, L/D = 25, manufactured by Thermoplastics), melt-kneading was performed at a set temperature of 190°C. Subsequently, the mixed melt was melt-spun using a spinning die with an orifice diameter of 2 attached to the extruder. The extrusion melt was taken off with an air gap of 180 am at a draft ratio of 36 times, cooled and solidified in air, and undrawn fibers were obtained. Furthermore, the undrawn fibers were drawn under the following conditions.

Two-stage stretching was performed using a Godetstrol made by Ohdai. At this time, the heat medium in the first drawing tank is n-decane, and the temperature is 1
The heating medium in the 10°C1 second drawing tank was triethylene glycol, and the temperature was 145°C. The effective length of each tank was 50 cm.

During stretching, the rotational speed of the first godet roll is set to 0.
By changing the rotational speed of the third godet roll to 5 m/min, oriented m-fibers with a desired drawing ratio were obtained. The rotational speed of the second godet roll was appropriately selected within a range that allowed stable stretching. Almost all of the initially mixed paraffin wax was extracted into n-decane during stretching. Thereafter, the oriented fibers were washed with water, dried under reduced pressure at room temperature overnight, and subjected to measurement of various physical properties. The stretching ratio was calculated from the rotational speed ratio of the first godet roll and the third godet roll.

Measurement of tensile properties> Elastic modulus and tensile strength were measured at room temperature (23° C.) using a tensile test rt11m model DO3-50M manufactured by Shimadzu Corporation.

At this time, the sample length between the clamps was 100 mm, and the tensile rate was 100111 IZ minutes (100%/min strain rate).
The elastic modulus was calculated using the slope of the tangent at the initial elastic modulus. The fiber cross-sectional area required for calculation was calculated from the weight, assuming a density of 0.960z/cc.

Tensile modulus and strength retention after heat history The heat history test was conducted by placing the sample in a gear oven (Perfect Oven, manufactured by Tabai Seisakusho).

The sample was approximately 3 m long and was fixed at both ends by folding it over a piece of stainless steel with a plurality of pulleys attached to both ends. At this time, both ends of the sample were fixed to the extent that the sample did not sag, and no tension was actively applied to the sample. The tensile properties after the thermal history were measured based on the description of the measurement of the tensile properties described above.

Measurement of creep resistance〉 Creep resistance was measured using a thermal stress strain measuring device TMA/5S1.
0 (manufactured by Seiko Electronics Co., Ltd.), the sample length was 1 cm, the ambient temperature was 70° C., and 5 loads were carried out under accelerated conditions with a weight equivalent to 30% of the breaking load at room temperature. In order to quantitatively evaluate the amount of creep, the following two values were determined. In other words, the creep elongation (%) after 90 seconds after applying a load to the sample
) The value of CR90 and the value of average creep rate (sec-1) ε after 180 seconds have elapsed from the time when 90 seconds have elapsed.

Table 1 shows the tensile properties of the multifilament obtained by bundling a plurality of drawn and oriented fibers.

The original crystal melting peak of ultra-high molecular weight ethylene-butene-1 copolymer drawn filament (Sample-1) is 126.7
℃, the ratio of Tp to the total crystal melting peak area is 33.
The creep resistance was 8% CR90 = 3
, 1%, ε=3.03X10SeC'', and the elastic modulus retention after heat history at 170°C for 5 minutes was 102.
2%, the strength retention rate was 102.5%, and no deterioration in performance due to thermal history was observed.

Also, the amount of work required to break the drawn filament is 10.
3kt-m/lz, density is 0.973t/-, dielectric constant is 2.2, dielectric loss tangent is 0.024%, impulse voltage breakdown value is 180 KV/L
It was ul.

The filaments described above were then used to braid lobes as follows. Focus multifilament and Z in 6 strokes
A lobe with a lobe diameter of 9 g was obtained with a 3X12X6 structure. The end of this lobe was subjected to 11-tack ice splice processing, and the lobe characteristics were evaluated using an Amsler horizontal tensile tester (Model T-7919 manufactured by Tokyo Shokki), and the sample length between the ice splice ends. Testing was conducted at a distance of 1.5 m in both a wet state and a dry state. At this time, the temperature is room temperature (23
℃) and the tensile speed is 15 μ/min.

The results are shown in Table 2.

Polymerization of ultra-high molecular weight ethylene/octene-1 copolymer> Slurry polymerization of ethylene was carried out using a Ziegler catalyst and n-decane 11 as a polymerization solvent.

At this time, 125 ml of octene-1 as a comonomer and 40 N [IIl] of hydrogen for molecular weight adjustment were added all at once before starting the polymerization to start the polymerization. Ethylene gas was continuously supplied to the reactor to maintain a constant pressure of 5 kg/-, and the polymerization was completed at 70°C for 12 hours.

The yield of the obtained ultra-high molecular weight ethylene/octene-1 copolymer powder was 178+r, and its intrinsic viscosity [η] (decalin, 135°C) was 10.66dj/r. The mer content was 0.5 per 1000 carbon atoms.

Preparation of drawn and oriented ultra-high molecular weight ethylene/octene-1 copolymer and its physical properties> A drawn and oriented fiber was prepared by the method described in Example 1. Table 3 shows the tensile properties of the multifilament obtained by bundling a plurality of drawn and oriented fibers.

(Hereinafter, blank) The original crystal melting peak of the ultra-high molecular weight ethylene/octene-1 copolymer drawn filament (Sample-2) is 132.
Tρ and Tp for 1°C1 total crystal melting peak area
The proportions of l were 97.7% and 5.0%, respectively. The creep resistance of sample-2 is CH2O-2.0%, ε=
It was 9.50xlOsec. Further, after heat history at 170° C. for 5 minutes, the elastic modulus retention rate was 108.2%, and the strength retention rate was 102, t%. Furthermore, the amount of work required to fracture sample-2 is 10.1ksr-m/g, the density is 0.971+r/-, the dielectric constant is 262, the dielectric loss tangent is 0.031%, and the impulse voltage The destruction value was 185KV/square.

A rope of the present invention was obtained by the method described in Example 1 using Sample-2. Table 4 shows the morphology and physical properties of the rope.

Futoshi Momotsuji ultra-high molecular weight polyethylene (homopolymer) powder (intrinsic viscosity [η] = 7.42 dJl/l, Decalin, 135°C
): 20 parts by weight and paraffin wax (melting point = 69°C
, molecular weight=490): 80 parts by weight in Example 1
The fibers were melt-spun and drawn using the method described above to obtain drawn-oriented fibers. Table 5 shows the tensile properties of the multifilament obtained by bundling a plurality of drawn and oriented fibers.

Ultra-high molecular weight polyethylene drawn filament (Sample-3)
The original crystal melting peak was 135.1'C1, and the ratio of Tp to the total crystal melting peak area was 8.8%. Similarly, the high temperature side peak Tp with respect to the total crystal melting peak area
1 was less than 1%. Creep resistance is CR9o
=11.9%, ε=1, 07 x 10' 5ec
-1teatsur:, Also, the elastic modulus retention rate after 15 minutes of heat history at 170°C is 80.4%, and the strength retention rate is 78.2.
%Met. Furthermore, the amount of work required to cut sample-3 is 6
．． 8kg-m7g, density is 0.985g/-, dielectric constant is 2.3, dielectric loss tangent is 0.030%, impulse voltage breakdown value is 182 K V/r
It was am.

A rope of the present invention was obtained by the method described in Example 1 using Sample-3. Table 6 shows the shape and physical properties of the rope.

A rope was braided using the method described in Example 1 using aramid fibers (Kevlar 29-960 manufactured by DuPont) having a ratio of T500 denier/1000 filaments. Table 7 shows the rope properties.

As is clear from the above, ropes made of ultra-high molecular weight polyethylene are superior to Gevlar in the amount of work required to break, but ropes made of ultra-high molecular weight ethylene/butene-1 copolymer are even greater in the amount of work required to break. . In addition, it has excellent properties especially when hydrated and has high elongation, so it has excellent strength utilization when made into rope. From these facts, it can be seen that the rope of the molecularly oriented ultra-high molecular weight polyolefin or ultra-high molecular weight ethylene/α-olefin copolymer according to the present invention is most suitable for the antenna fixing stay.

Agent: Patent Attorney: Shunbetsu Suzuki

Claims (1)

[Claims] 1) An antenna fixing stay made of a molecularly oriented molded ultra-high molecular weight polyolefin having an intrinsic viscosity [η] of at least 5 dl/g. 2) Ultra-high molecular weight ethylene α- having an intrinsic viscosity [η] of at least 5 dl/g and containing an average of 0.1 to 20 α-olefins having 3 or more carbon atoms per 1000 carbon atoms. Antenna fixing stay made of molecularly oriented molded olefin copolymer. 3) α-olefin is butene-1, 4-methylpentene-1, hexene-1, octene-1 or decene-1
The antenna fixing stay according to claim 2. 4) The antenna fixing stay according to claim 2, wherein the content of α-olefin is on average 0.5 to 10 per 1000 carbon atoms.