JPH0252507A - Parabolic antenna - Google Patents

Abstract

PURPOSE:To make the parabolic antenna light in weight, to attain high intensity and to improve the heat resistance and water resistance by using a fibrous molecule oriented forming body made of an ultrahigh molecule weight polyolefin having a limit viscosity of a specific value and a matrix resin as a low dielectric constituent of the parabolic antenna. CONSTITUTION:The fibrous oriented forming body of ultrahigh molecule weight polyolefin whose limit viscosity is at least 5dl/g and a matrix resin are used as the low dielectric constituent of the parabolic antenna. Moreover, the low dielectric constituent comprising the fibrous molecule oriented forming body made of an ultrahigh molecule weight ethylene.alpha-olefin copolymer whose limit viscosity is 5dl/g in which the content of the alpha-olefin having 3 or over of the carbon number is 1-20 in average per 1000 carbon number and the matrix resin constitutes the parabolic antenna.

Description

[Detailed Description of the Invention] The present invention relates to a parabolic antenna, and more specifically,
It is made of a low dielectric composition consisting of an ultra-high molecular weight polyolefin fibrous molecularly oriented molded product or a fibrous molecularly oriented molded product that is a combination of ultrahigh molecular weight ethylene and α-olefin, and a matrix resin, and is lightweight and has high strength. This invention relates to a parabolic antenna that has excellent weather resistance, water resistance, and low dielectric property.

Parabolic antennas are required to be lightweight, have high strength, have a low dielectric constant, and have excellent weather resistance and water resistance. Composite materials made of epoxy resin and glass fiber have traditionally been used for such parabolic antennas, but parabolic antennas made of these composite materials are heavy, have a relatively high dielectric constant, and have poor strength. There were many points that needed improvement.

The present inventors conducted intensive research to solve the above-mentioned problems and found that if a parabolic antenna is manufactured from a low dielectric composition consisting of a molecularly oriented cloth of ultra-high molecular weight polyolefin and a matrix resin, the above problems can be solved. The present invention has been completed by discovering that the above problems can be solved at once.

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 purpose of the present invention is to solve the problems associated with the prior art as described above. The purpose is to provide a parabolic antenna that is dielectric.

The parabolic antenna according to the present invention is made of a low dielectric composition comprising a fibrous molecularly oriented molded article of ultra-high molecular weight polyolefin having an intrinsic viscosity [η] of at least 5 dll/g and Madnox resin. It is characterized by

Further, the parabolic antenna according to the present invention has an intrinsic viscosity [η]
is at least 5d, Q/+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 being composed of a low dielectric composition consisting of a oriented molecular structure and a matrix resin.

The parabolic antenna according to the present invention has a low dielectric property and is composed of a fibrous molecular oriented body of an ultra-high molecular weight polyolefin or a fibrous molecular oriented body of an ultra-high molecular weight ethylene/α-olefin copolymer as described above, and a matrix resin. It is made of a composition, is lightweight, has high strength, has excellent weather resistance and water resistance, and has low dielectricity.

Below, the parabolic antenna according to the present invention will be explained in detail.

First, the fibrous molecularly oriented molded article of ultra-high molecular weight polyolefin and the fibrous molecularly oriented molded article of ultra-high molecular weight ethylene/α-olefin copolymer used in the composition for forming the parabolic antenna according to the present invention will be described.

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 product of ultra-high molecular weight polyolefin is lightweight, has high strength, has excellent weather resistance, water resistance, and salt water resistance, and has low dielectricity.

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 polyethylene/1-octene copolymer, ultra-high molecular weight Ethylene and carbon atoms such as ethylene/1-decene copolymer from 3 to 20, preferably 4
Ultra-high molecular weight ethylene α- with ~10 α-olefins
An example is an olefin copolymer. In this ultra-high molecular weight ethylene/α-olefin copolymer, the α-olefin having 3 or more carbon atoms has 1000 carbon atoms in the polymer.
It is contained in an amount of 0.1 to 20 pieces, preferably 0.5 to 10 pieces, and more preferably 1 to 7 pieces.

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. There is. Moreover, this ultra-high molecular weight ethylene/α-olefin copolymer is lightweight, high strength, and has excellent abrasion resistance, impact resistance, and creep resistance, as well as 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 article of the present invention has an intrinsic viscosity [η] of 56 J/g, 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 0.960-0.98!5t/c
It is xA. Here, the density is determined by the usual method (ASTHD 150
5), it was measured by the density gradient tube method. The density gradient tube at this time was prepared by using carbon tetrachloride and toluene, and the measurement was performed 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 (IKH2, 80℃) is 0.050 to 0.0
0.08% preferably 0.040 to 0.08%. 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, birefringence, fluorescence spectroscopy, etc., for example, Yukichi Go, Teru Kubo Part 2 Industrial Chemical Journal Vol. 39, 992 (1939), where Ho is the half-power width (°) of the intensity distribution curve along the Debye ring of the strongest paratropic surface on the equator. The degree of orientation (F) defined by .) 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, as mentioned above, the molecularly oriented molded product of the present invention has excellent mechanical properties, such as an elastic modulus of 20 GPa or more, especially 30 GPa or more in the form of a drawn filament, and an elastic modulus of 1.2 GPa or more, especially 1.2 GPa or more. It has a tensile strength of 5 GPa or more.

The impulse voltage breakdown value of the molecularly oriented molded product of the present invention is 1
10~250 KV/nna preferably 150~
220 KV/am. The impulse voltage breakdown value was measured using the same sample as in the case of dielectric constant, using a brass (25 amφ) JIS type electrode on a copper plate, and increasing the voltage while applying a negative impulse in steps of 2 KV/3 times.

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 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 8hg-
m/g 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.
The creep rate calculated as the elongation (%) after 90 seconds at an atmospheric temperature of 70°C is 7% or less, especially 5% or less, and the creep rate (ε, sec) is 4 X 10-4Sec-
' or less, especially 5 X 10' sac -1 or less.

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 has poor 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 melted at a temperature at least 20°C higher than the original crystal melting temperature (Tm) of the copolymer. The polymer has a peak (Tp), and the heat of fusion based on this crystal melting peak (Tp) is 15% or more, preferably 20% or more, particularly 30% or more of the total heat of fusion of the polymer.

The original crystal melting temperature (Ta) of ultra-high molecular weight ethylene copolymer
n), the molded body is once completely melted and then cooled,
A method of raising the temperature again after relaxing the molecular orientation in the compact, the 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 very slight tailing. . Crystal melting peak (
TO) is generally within the temperature range Tlo-4-20°C to Tll
1+50℃, especially 'rm+20℃~'r'111+10
The 7' peak is expressed in the 0°C region, 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 'T'In+35°C to 'r+n-+
High temperature side 1+1ellll"-/ at -1oo°C
('I'l) 1) ,! l: , temperature range TI+20
The low temperature side melting peak (T
It often appears as two peaks, TI) and TO2, and depending on the manufacturing conditions of the molecularly oriented molded product, TI) and TO2 may further consist of multiple peaks.

These high crystal melting peaks (TI), TI) 2
) significantly improves the heat resistance of molecularly oriented molded products of ultra-high molecular weight ethylene/α-olefin copolymers, and also contributes to the 6 strength retention rate or elastic modulus retention rate in high-temperature thermal B sliding contact. It appears to be.

Also, temperature range TI +35'C~Tn+ +100°
The total heat of fusion based on the high temperature side melting peak ('rp 1) of C is 1.5% or more, especially 3.0%, based on the total heat of fusion.
% or more is desirable.

In addition, as long as the sum of the heat of fusion based on the high temperature side melting peak (Tpl) satisfies the above value, if the high temperature side melting peak (Tpl) does not stand out as a main peak, in other words, it is a collection of small peaks. Alternatively, even if the peak becomes 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 determined 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■4111111×
The alignment direction was restrained by wrapping the film around an aluminum plate having a thickness of 0.2+ nm. Next, the sample, which had been temporarily wrapped with aluminum, was sealed in an aluminum pan and used as a measurement sample. In addition, the same aluminum plate used for the sample was sealed in an empty aluminum pan, which is usually placed in the reference boulder, to maintain the heat balance. First, the sample was held at 30°C for about 1 minute, and then heated to 250°C at a heating rate of 10°C/min.
The melting point measurement during the first temperature increase was completed. Continue to 250
The sample was held at 30°C for 10 minutes, then lowered at a cooling rate of 20°C/min, and the sample was held at 30°C for another 10 minutes. The temperature was raised to 250° C. at a rapid rate, and at this time, the second melting point measurement at y1 temperature (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, the straight line (
Baseline) and second J? Draw a perpendicular line to a point 20°C higher than the original crystalline melting temperature (Tn+) of the ultra-high molecular weight ethylene copolymer, which is determined as the main melting peak at humid temperature, and draw a perpendicular line to a point 20°C higher than the ultra-high molecular weight ethylene copolymer's original crystal melting temperature (Tn+), which is determined as the main melting peak at humid temperature, and draw the part on the low temperature side surrounded by these lines to the ultra-high molecular weight ethylene copolymer. It is based on the original crystal melting (T11) of coalescence, and the high temperature side part is based on the crystal melting (Tp) that expresses the function of the molded article of the present invention, and the heat of each crystal fusion is calculated from these areas. did. Also, Tpl and T
I) The heat of fusion based on the melting of 2 was also determined according to the above method, and T
The part surrounded by the perpendicular line from 11+20°C and the perpendicular line from Tn-)-35°C was taken as the heat of fusion based on the melting of Tp2, and the high temperature side part was calculated in the same way as the heat of fusion based on the melting of TIEl. .

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.

Iq of molecular orientation acid 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, JP-A No. 5
Publication No. 6-15408, Japanese Unexamined Patent Publication No. 58-5228,
JP-A-59-130313, JP-A-59-187
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. 614, etc. An example of an improved method for stretching to a high magnification can be given.

Ultra-high molecular weight ethylene/α-olefin copolymer”
The primary ultra-high molecular weight ethylene
The method for producing a molecularly oriented molded product of an α-olefin copolymer will be explained below in the order of raw materials, production method, and purpose for easy understanding.

凰--J■ The ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is obtained by slurry polymerizing ethylene and an α-olefin having 3 or more carbon atoms in an organic solvent using a Ziegler catalyst. It can be 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-methylbenzone-1, hexene-1, octene-1, etc. are particularly preferred.
Such α-olefins are copolymerized with ethylene in the amount stated above per 1000 carbon atoms of 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 at 1378 cm-', which represents the bending vibration of the methyl group of the α-olefin contained in the ethylene chain, was measured using an infrared spectrophotometer, and this value was calculated in advance from the 13C nucleus. Quantify the amount of α-olefin in the ultra-high molecular weight ethylene/α-olefin copolymer by converting to the number of methyl atoms per 1000 carbon atoms using a calibration curve created using a model compound using a magnetic resonance apparatus. do.

Method 1 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° higher than the melting point of the copolymer.
A solvent having a boiling point higher than C or higher is used.

Specifically, such solvents include n-nonane, n-
- Decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane or liquid paraffin, aliphatic hydrocarbon compounds such as kerosene, xylene, naphthalene,
Tetralin, butylbenzene, p~cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene,
Aromatic hydrocarbon solvents such as dodecylbenzene, bicyclohexyl, decalin, methylnaphthalene, ethylnaphthalene or their hydrogenated derivatives, 1,1,2.2-tel
- Halogenated hydrocarbon solvents such as lachloroethane, pentachloroethane, hexachloroethane, L2,3-trichloropropane, dichlorobenzene, 1.2.4-trichlorobenzene, bromobenzene, paraffinic process oil, naphthenic process oil, aromatic Examples include mineral oils such as family 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.

Specifically, such aliphatic hydrocarbon compounds include n-alkanes having 22 or more carbon atoms such as tocosan, tricosane, tetracosane, and 1-heriacontane, or mixtures containing these as main components with lower n-alkanes; So-called paraffin wax separated and refined from petroleum, medium/low-pressure polyethylene wax, high-pressure polyethylene wax, ethylene copolymer wax, or low-molecular-weight polymer obtained by copolymerizing ethylene or ethylene with a specific α-olefin. Waxes obtained by reducing the molecular weight of polyethylene such as medium- and low-pressure polyethylene and high-pressure polyethylene by thermal degradation, oxides of these waxes, oxidized waxes modified with maleic acid, and waxes modified with maleic acid are used.

In addition, 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 end 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 getons, etc. are used.

Examples of such aliphatic hydrocarbon compound derivatives include
Water contains fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid.
Aliphatic alcohols such as lauric alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, fatty acid amines such as caprinamide, lauramide, valmitinamide, and stearylamide, fatty acid esters such as stearyl acetate, and the like are used.

Ultra-high molecular weight ethylene/α-olefin copolymer and diluent differ depending on their type, but numerically 3
297-80: 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. On the other hand, 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 performed at 150 to 300°C, #, ¥ 17
It is carried out at a temperature of Q~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 molded article having poor cavity elastic modulus and high strength. The blending may be carried out by dry blending using a Henschel mixer, a V-type blender, or the like, or 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, draft,
That is, stretching in a molten state can also be applied.

■ Extrusion speed of molten resin in the die orifice. The draft ratio can be defined by the following formula:

Draft ratio = V/Vo (2) This 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. can.

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.

The unstretched molded product obtained from the ultra-high molecular weight ethylene/α-olefin copolymer is generally stretched at 40 to 160°C.
In particular, it is carried out at temperatures between 80 and 145°C. As a heat medium for heating and maintaining the unstretched molded body at the above-mentioned temperature, any of air, water vapor, and a liquid medium can be used.

However, as a heat medium, a liquid medium that can elute and remove the diluent mentioned 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 by using the above-mentioned diluent, since it becomes possible to remove the diluent described above, and it also prevents uneven stretching during stretching, and also makes it possible to achieve a high stretching ratio.

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 in which an unstretched product is treated with a solvent such as hexane, heptane, hot ethanol, chloroform, or benzene, and then stretched. 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.

Generally, it is preferable to carry out the stretching operation in two or more stages, in which the stretching operation is carried out at a relatively low temperature of 80 to 120°C while extracting the diluent in the extrudate, and In the subsequent stages, it is preferable to stretch the molded body at a temperature of 120 to 160°C and 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 0-175°C for 1-20 minutes, preferably 3-20 minutes.
It can be done for 10 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.

The low dielectric composition used in the present invention comprises a fibrous molecularly oriented molded product of such an ultra-high molecular weight ethylene/α-olefin copolymer and a matrix resin.

In addition, if necessary, Ma! - Surface treatment such as so-called corona discharge treatment, plasma discharge treatment, radiation (electron beam, gamma ray) irradiation treatment, ultraviolet ray irradiation treatment, etc. can be performed before mixing with RIX resin.

In the present invention, a thermoplastic resin and a thermosetting resin are used as the matrix resin.

Specifically, polyethylene, ethylene/α-olefin copolymer, polystyrene, etc. are used as the thermoplastic resin. As the ethylene/α-olefin copolymer, for example, ethylene/polycyclic olefin copolymer is preferably used, and specifically, the ethylene/polycyclic olefin copolymer is within the range of 40 to 90 mol%. A lantum copolymer (ethylene/polycyclic olefin copolymer) consisting of ethylene repeating units and repeating units represented by the following general formula [I] or general [IT] within the range of 60 to 10 mol% etc. are used.

(-Fukudai [■, [■], R1 to R1o are water atoms, halogen atoms, or carbon-hydrogen groups, and may be the same or different, and when R to R8 are repeated multiple times In this case, R5 to R8 may be the same or short.

n and rn are both 0 or a positive integer,
” is an integer of 3 or more. ) This random copolymer has an intrinsic viscosity [η] of 0.03 to 10 dJ/g measured in a decalin melt at 135°C, a crystallinity of 10% or less by X-ray diffraction, and an iodine value of is 5 or less, and the glass transition temperature (T(]) is 5
It is preferably within the range of 0 to 250°C. Among these, the limiting viscosity [η] is 0.1 to 5 dj/g, the crystallinity is 5% or less, the iodine value is 1 or less, and the glass transition temperature is within the range of 60 to 200'C. To! Particularly preferred are random copolymers containing

Further, as the thermosetting resin, specifically, epoxy (5
1 resin, unsaturated polyester resin, alkyd resin, phenol resin, urea resin, melamine resin, xylene/formaltehyde resin, etc. are used. Among these, epoxy resins and unsaturated polyester resins are preferred.

In a low dielectric composition comprising an oriented fibrous molecule of an ultra-high molecular weight ethylene/α-olefin copolymer and a matrix resin as described above, the volume content of the oriented fibrous molecule is preferably 30 to 90%. is used in 50-80% of mice, and the volume content of matrix resin is 10-70%.
Preferably it is used in an amount of 20-50%. The dielectric constant of the laminate made of this composition is 3.9 or less, preferably 3.4.
It is as follows.

Such a composition can be prepared by aligning fibrous molecular molecules in a cross or one direction and then applying matrix IMJ resin to form a grid, or by preparing fibers to an appropriate length, preferably. It may be cut into 3 to 30 pieces and mixed into the matrix resin.

The parabolic antenna according to the present invention is manufactured by a conventional method from the low dielectric composition obtained as described above.

The parabolic antenna according to the present invention as described above has an eave and high strength, is weather resistant and water-resistant, and has a low dielectric property.

The parabolic antenna according to the present invention comprises a fibrous molecularly oriented molded product of an ultra-high molecular weight polyolefin or a fibrous molecularly oriented molded product of an ultra-high molecular weight ethylene/α-olefin copolymer as described above, and a matrix resin. It is formed from a low dielectric composition consisting of the following, is lightweight, has high strength, has excellent weather resistance and water resistance, and has low dielectric property.

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> Slurry polymerization of ultra-high molecular weight ethylene-butene-1 copolymer using a Ziegler catalyst and n-decane 1 as a polymerization solvent. I did it. A mixed monomer of ethylene and butene-1 having a molar ratio of 97.2:2.35 was continuously fed into the reactor in M cycles so as to maintain a constant pressure of 51 qr/-. Polymerization was completed in 2 hours at a reaction temperature of 70°C.

The yield of the obtained ultra-high molecular weight ethylene-butene-1 copolymer powder was 160 ir, and the intrinsic viscosity [η] (decalin: 135°C) was 8.2 d, 1/1, using an infrared spectrophotometer. The butene-1 content was 1.5 per 1000 carbon atoms.

Preparation of stretched oriented product of ultra-high molecular weight ethylene-butene-1 copolymer - 1 part of 20 weight ff of ultra-high molecular weight ethylene-butene-1 copolymer powder obtained by the polymerization described in E and paraffin wax (melting point = 69 ℃, molecular weight=490>80 parts by weight, and melt-spun the mixture under the following conditions.

3.5- as a process stabilizer to 100 parts by weight of the mixture.
Di-tert-butyl-4-hydroxytoluene 0
．． 1 part by weight was added. Next, the mixture was heated to a set temperature of 190°C using a screw extruder (screw diameter = 25 + + m, L/D = 25, manufactured by Thermoplastics).
Melt-kneading was performed. Subsequently, the mixed melt was melt-spun using a spinning die with an orifice diameter of 2 sizes attached to the extruder. The extrusion melt was heated at an air gap of 180 cm
The fibers were withdrawn at a trough ratio of 6 to 1, and cooled and solidified in air to obtain undrawn fibers. 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 second drawing tank was triethylene glycol, and the temperature was 145°C. The effective length of each tank was 50 (!ID). During stretching, the rotational speed of the first godet roll was 0.5 m/min, and the third
By changing the rotational speed of the godet roll, oriented 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 is n-
Extracted into decane. After that, the oriented fibers are washed with water,
It was dried under reduced pressure at room temperature for a day and night, and then used to measure 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> The elastic modulus and tensile strength were measured at room temperature (23° C.) using a tensile tester model C350M manufactured by Shimadzu Corporation.

At this time, the sample length between the clamps was 100 m+n, and the tensile rate was 100 m+/min (100%/min strain rate).

The TyP modulus was calculated using the slope of the tangent at the initial elastic modulus. The fiber cross-sectional area required for calculation is density 0.960g/CC
It was calculated from the weight.

Tensile modulus and strength retention after thermal history The thermal durability test was carried out by leaving the specimen in a gear oven (Parts F 1-Open: manufactured by Tabadon Seisakusho).

The sample had a length of about 3 m, and was folded over a stainless steel frame equipped with a plurality of pulleys at both ends to fix both ends of the sample. 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 heat history are as described in the above-mentioned tensile 1. It was measured based on the description of the measurement of ν property.

<Measurement of creep resistance> Creep resistance g! 11 constant is thermal stress strain measuring device TMA/
'5S10 (manufactured by Seiko Electronics Co., Ltd.) was used under accelerated conditions with a sample length of 1 (at an ambient temperature of 70°C and a load equivalent to 30% of the breaking load at room temperature).The amount of creep was determined. The following two values were determined for the purpose of evaluation: the value of creep elongation (%) CR9° after 90 seconds had elapsed after applying a load to the sample, and the value of 1
This is the value of the average creep rate (Sec'') ε after 80 seconds.

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

Table 1 The original crystal melting peak of the ultra-high molecular weight ethylene-butene-1 co-IF combined drawn filament (Sample-1) was 126.
The temperature was 7° C., and the ratio of p to the total crystal melting peak area was 33.8%. In addition, the creep resistance is CR9o=
3.1%, ε = 3.03Xi o-5sec'' Therefore, no deterioration in performance due to thermal history was observed.

Also, the amount of work required to break the drawn filament is 10.
3ki・m7g, the density is 0.973g/-, the dielectric constant is 2.2, the dielectric loss tangent is 0.024%, and the impulse voltage number JJi value is 180 K V /
It was mm.

Next, a composition consisting of the drawn and oriented fibers of the ultra-high molecular weight ethylene-butene-1 copolymer prepared by the above method and a matrix resin was prepared by the following method, and then a molded plate was prepared.

First, the drawn and oriented fibers of the ultra-high molecular weight ethylene-butene-1 copolymer described above were continuously subjected to processing energy of 75 W/rrr/iin and processing speed of Jf 50 m/l 1 lin using a corona discharge device (manufactured by Tomoe Kogyo ■). Corona discharge treatment was performed. When the oxygen content on the fiber surface after treatment was analyzed by varnish strength, it was found to be an average of 10 carbon atoms per 100 carbon atoms. In addition, the tensile properties of the fibers after corona discharge treatment, tensile strength after heat history, retention of elastic modulus, creep resistance, electrical properties such as dielectric constant, dielectric loss tangent, and impulse voltage breakdown value are all measured values as described above. It was equivalent to

The corona discharge-treated ultra-high molecular weight ethylene-butene copolymer drawn fiber thus obtained was cut into a length of 15 mm.

Next, epoxy resin (base resin, trade name: formerly known as EPO)
R-140J Mitsui Petrochemical Industries (solidification) and curing agent (product name r EPOHIKoQ -640J Mitsui Petrochemical Industries?
(manufactured by Kogyo ■) in a weight ratio of 10:6 and the above cut fiber in a weight ratio of 110.2:59.8.
were placed in a stainless steel beaker and stirred uniformly to obtain a composition.

Using this composition, a molded plate with a thickness of 2 m111 and a fiber volume content of 65% was prepared by press molding at 80' CX for 2 hours, and the laminate bending strength test method (JIS K
The bending strength and dielectric constant (ASTM D 150) were measured by a method similar to 6911).

The measurement results are shown in Table 2.

Table 2 When a parabolic antenna was manufactured from the above molded plate,
A parabolic anthene with good properties was obtained.

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

At this time, octene-1 as a common substance is 125 m1
And 40 N ml of hydrogen for molecular weight adjustment was added all at once before starting the polymerization to start the polymerization. Ethylene gas was continuously supplied to the reactor so that the pressure in the reactor was maintained at a constant pressure of 5%/-, 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 g, and its intrinsic viscosity [η
35° C.) was 10.66 dJ/r, and the octene-1 comonomer content by infrared spectrophotometer was 0.5 per 1000 carbon atoms.

Preparation of Stretched Ultra-High Molecular Weight Ethylene-Octene Copolymer and its Physical Properties> Stretched oriented fibers were 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.

The original crystal melting peak of fi-GoΣ ultra-high molecular weight ethylene/octene-1 copolymer drawn filament (Sample-2) is 132.
1°C, and the ratios of 1p and Tpl to the total crystal melting peak area were 97.7% and 5.0%, respectively. Creep resistance of sample-2 is CR9o=2.0%
, ε=9.50X] 0' 5ac-1. In addition, the elastic modulus retention after 5 minutes of thermal history at 170°C is 1.
The strength retention rate was 102.1%. Furthermore, the amount of work required to break sample-2 is 10.1 kg.
-m7g, density was 0.971g/-, dielectric constant was 2.2, dielectric loss tangent was 0.031%, and impulse voltage breakdown value was 185KV/.

The ethylene/octene-1 copolymer drawn fibers prepared as described above were subjected to corona discharge treatment in the same manner as in Example 1. The oxygen content analysis value based on the varnish force on the fiber surface after treatment was an average of 10.3 carbon atoms per 100 carbon atoms. Tensile properties and heat resistance of fibers after corona discharge treatment
The electrical property values were equivalent to the values before the above-mentioned treatment.

This corona discharge treated ultra-high molecular weight ethylene/octene-1 copolymer drawn fiber was cut into fibers with a length of 15m+n, a composition was prepared in the same manner as in Example 1, and a molded plate was prepared. , bending strength, and dielectric constant were measured.

The measurement results are shown in Table 4.

1 stretch oriented fiber! Knee. Table 5 shows the tensile properties of the multifilament obtained by bundling a plurality of drawn and oriented fibers.

Hikoriichi I produced a parabolic antenna from the above-mentioned molded plate.
A parabolic antenna with good characteristics was obtained.

Ultra-high molecular weight polyethylene (homopolymer) powder (limiting viscosity [η] = 7.42 dj /l, Decalin, 135
°C): 20 parts by weight and paraffin wax (melting point = 6
9°C, molecular weight = 490): A mixture with 80 Jushabu was melt-spun and drawn by the method of Example 1, and ultra-high molecular weight polyethylene drawn filament (Sample-3) had an original crystal melting peak at 135.1°C. The ratio of TEI to the total crystal melting peak area was 8.8%. Similarly, the ratio of the high temperature side peak Tp1 to the total crystal melting peak area is 1%.
It was below. Creep resistance is CR9o=11,9
%, ε = P, 07 X 10-3 sec-1 test, and the elastic modulus retention after 1,70'C15 minutes of thermal history is 80.4%, and the strength retention is 78.2%. Met. Furthermore, the amount of work required for M cutting of sample-3 is 6.1
3w (z-m/l, density is 0.985g/d, dielectric constant is 2,3, dielectric loss tangent is 0°030%, impulse voltage breakdown value is 182 KV/IWfl
Te Atsuta.

The above-mentioned ultra-high molecular weight polyethylene (homopolymer) drawn and oriented fibers were subjected to corona discharge treatment in the same manner as in Example 1. The oxygen content analysis value based on the varnish force on the fiber surface after treatment was an average of 9.8 carbon atoms per 100 carbon atoms. Also,
The tensile properties, heat resistance, and electrical property values of the fibers after corona discharge treatment were comparable to those before treatment.

The drawn and oriented fibers of ultra-high molecular weight polyethylene (homopolymer) treated with corona discharge were cut into a length of 15 nm+m.

Using this cut fiber, a composition and a molded article were prepared in the same manner as in Example 1, and the bending strength and dielectric constant were measured.

The measurement results are shown in Table 6.

6-Once a parabolic antenna is manufactured from the above molded plate,
A parabolic antenna with good characteristics was obtained.

Ichimon■Niglass fiber chopped strand (product name Glass 1'
: I-chop strand G R-S-3A Asahi Fiber Glass (manufactured by Taiyo) 47.6 plain part, epoxy resin base material and curing agent used in Example 1: FA compound e152.
After uniformly mixing z1 parts by weight, a molded plate was prepared in the same manner as in Example 1, and the bending strength and dielectric constant were 3! established.

J! II. Results are shown in full results.

Todoroki-1-

Claims (1)

[Scope of Claims] 1) A parabolic antenna comprising a low dielectric composition comprising a matrix resin and a fibrous 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. A parabolic antenna made of a low dielectric composition made of a fibrous molecularly oriented molded product of an olefin copolymer and a matrix resin. 3) α-olefin is butene-1, 4-methylpentene-1, hexene-1, octene-1 or decene-1
The parabolic antenna according to claim 2. 4) The parabolic antenna according to claim 2, wherein the content of α-olefin is on average 0.5 to 10 per 1000 carbon atoms.