JPH01250282A - Course rope for pool - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. The present invention relates to a swimming pool course rope, and more particularly to a swimming pool course rope that is lightweight, has high strength, and has excellent chemical resistance.

Day 1 and its problems 8 Traditionally, wire ropes have been used as course ropes for swimming pools, but the chlorine disinfectants added to the pool water can cause the wire ropes to rust or become stiff. There were problems such as being heavy and difficult to handle.

The present inventors conducted research to solve the above problems, and considered using a rope made of a molecularly oriented molded product of ultra-high molecular weight polyolefin, which is lightweight and high strength, as a course rope for pools instead of wire rope. However, the rope itself, which is simply made of a molecularly oriented molded ultra-high molecular weight polyolefin, has the problem that it easily absorbs water, making the rope heavy and difficult to handle.Furthermore, when the rope is subjected to friction, it becomes fluffy. I found out that there is a problem that it is easy to use. Furthermore, if a rope itself made of a molecularly oriented molded ultra-high molecular weight polyolefin is used as a swimming pool course rope for a long period of time, there is a risk that the strength of the rope will decrease due to the chlorine-based disinfectant contained in the pool water. We found that there are some problems.

In order to further solve the above-mentioned problems, the present inventors conducted extensive research and found that the outer periphery of a rope made of a molecularly oriented molded product of ultra-high molecular weight polyolefin was made of a highly flexible resin with excellent chemical resistance. The inventors discovered that the above-mentioned problems could be solved at once by coating, and the present invention was completed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pool course rope that is lightweight, has high strength, and has excellent chemical resistance, water resistance, and scratch resistance.

Kuhadaza 11 The course rope for a pool according to the present invention is characterized in that the core member is a filament assembly made of a molecularly oriented molded product of ultra-high molecular weight polyolefin, and the outer periphery of the core member is coated with a resin. There is.

The course rope for pools according to the present invention uses a filament assembly made of lightweight and high-strength polyolefin molecularly oriented molded bodies for the core member, and the outer periphery of the core member has excellent chemical resistance and flexibility. Since it is coated with a rich resin, it is lightweight, has high strength, and has excellent chemical resistance, water resistance, and scratch resistance, and is also easy to handle.

Below, the swimming pool course rope according to the present invention will be specifically explained.

The pool course rope according to the present invention has a double structure including a core member and a coating resin layer covering the outer periphery of the core member.

L plate M The core member is configured to include a molecularly oriented molded product (drawn filament) of ultra-high molecular weight polyolefin.

As the ultra-high molecular weight polyolefin used in the present invention, specifically, ultra-high molecular weight polyethylene, ultra-high molecular weight polypropylene, ultra-high molecular weight ethylene/α-olefin copolymer, etc. are used. Among them, ultra-high molecular weight polyethylene molecularly oriented molded products obtained by stretching ultra-high molecular weight polyethylene mainly composed of ethylene or ultra-high molecular weight ethylene/α-olefin copolymers at a high magnification of 10 times or more are lightweight and It is preferably used because it also has high elasticity and high tensile strength.

In particular, ultra-high molecular weight ethylene α- used in the present invention will be described below.
A molecularly oriented molded product of an olefin copolymer, that is, a molecularly oriented molded product of an ultra-high molecular weight ethylene/α-olefin copolymer will be explained.

These are the molecularly oriented molded product used in the present invention, the molecularly oriented molded product of ultra-high molecular weight polyolefin, or the molecularly oriented molded product of 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, ultra-high molecular weight polypropylene, ultra-high molecular weight poly-1-butene, and ultra-high molecular weight polyolefins of two or more types of α-olefins. Examples include copolymers. This molecularly oriented molded product of ultra-high molecular weight polyolefin is lightweight and has high strength.
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-propylene copolymer, ultra-high molecular weight ethylene-
1-butene copolymer, ultra-high molecular weight ethylene/4-methyl-1-petene copolymer, ultra-high molecular weight ethylene/1-hexene copolymer, ultra-high molecular weight ethylene/1-octene copolymer, ultra-high molecular weight Ethylene such as ethylene/1-decene copolymer and the number of carbon atoms is 3 to 20, preferably 4 to 10
Examples include ultra-high molecular weight ethylene/α-olefin copolymers with α-olefins. This ultra-high molecular weight ethylene/α-olefin copolymer has 3 carbon atoms.
The above α-olefin is contained in an amount of 0.1 to 20, preferably 0.5 to 10, and more preferably 1 to 7 per 1000 carbon atoms of the polymer.

The molecularly oriented molded product obtained from such an ultra-high molecular weight ethylene/α-olefin copolymer has particularly good impact resistance and creep resistance compared to the molecularly oriented molded product obtained from ultra-high molecular weight polyethylene. .

This ultra-high molecular weight ethylene/α-olefin copolymer is
It is lightweight and has high strength, and has excellent abrasion resistance, impact resistance, and creep resistance, as well as excellent weather resistance and 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 5 dj/g or more, preferably in the range of 7 to 30 dj/Ir. 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/c13 preferably 0.960~0,985g
/c13.

Here, the density was measured by the density piping method according to a conventional method (ASTM D 1505). The density pipe 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 (1kHz, 23°C)
is 1.4 to 3.0, preferably 1.8 to 2.4, and the positive electric tangent (1kHz, 80'C) is 0.05 to o, oos
%, preferably 0.040 to 0.010. Here, the dielectric constant and the positive electric dissipation tangent were measured according to ASTM D 150 using a film-like sample in which fibers and tape-like oriented molecules were closely aligned 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 copolymer of the present invention is a drawn filament, which can be determined by linear diffraction method, birefringence method, fluorescence polarization method, etc.
Vol., p. 992 (1939), the degree of orientation according to the half-width, that is, the formula % (where Ho is the half-value of the intensity distribution curve along the Debye ring of the strongest paratropic plane on the equator; The degree of orientation (F) defined by the width (°) 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 11
0-250kv/III preferably 150-220
kv/in. The impulse voltage breakdown value was measured using a sample similar to that used for the dielectric constant.
) with the JIS type electrode, the negative polarity impulse is 2kV.
The pressure was increased while adding in steps of /3 times, and the measurement was performed.

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 the molecularly oriented molded products of these 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.
/g or more, preferably 10 kg-11/(1 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 K (ε, 5ec-') after 90 seconds to 180 seconds is 4 x 10-'5ec
-' or less, especially 5 x 10-5 sec -' 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 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 (T11) of the copolymer. The heat of fusion based on (Tp) is 15% or more, preferably 20% or more, particularly 30% or more.

The original crystalline melting temperature (Ti) of the ultra-high molecular weight ethylene/α-olefin copolymer is determined by completely melting the molded body, cooling it, relaxing the molecular orientation in the molded body, and raising the temperature again. It can be determined in a second run in a so-called differential scanning calorimeter.

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 (
Tp) is generally within the temperature range TIm+20°C to TI+50
℃, especially in the region of Tn+20℃ to TIl+100℃, and this peak (Tp) often appears as multiple peaks within the above temperature range, that is, this crystal melting peak (TEI) are the high temperature side melting peak ('rp 1 ) in the temperature range TI+35°C to Tm+100°C and the temperature range To++20°C to T
It often appears as two separate peaks, the low-temperature side melting peak ('rp2) at m+35°C, and depending on the manufacturing conditions of the molecularly oriented molded product, Tp and Tp2 may further consist of a plurality of peaks.

These high crystal melting peaks (Tp, T112) are
It is believed that this significantly improves the heat resistance of molecularly oriented molded articles of ultra-high molecular weight ethylene/α-olefin copolymers, and also contributes to strength retention or elastic modulus retention after high-temperature thermal history.

Moreover, the total amount of heat of fusion based on the high temperature side melting peak ('rp1) in the temperature range T11+35℃~'rn+xoo℃ is as follows:
It is desirable that the content be 1.5% or more, particularly 3.0% or more, based on the total heat of fusion.

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

Differential scanning calorimeter is DSCn type (manufactured by PerkinElmer)
was used. The sample size is approximately 3cm x 4rxxr x 4cm
The orientation direction was restrained by wrapping the sample around an aluminum plate having a thickness of 0.2 mm.The sample, which was then wrapped around the aluminum plate, was sealed in an aluminum pan and used as a sample for measurement. Also, the empty aluminum pan that is usually placed in the reference holder contains
The same aluminum plate used for the sample was enclosed to maintain heat balance. First, the sample was held at 30°C for about 1 minute, and then
Raise the temperature to 250 °C at a temperature increase rate of °C/min, complete the melting point measurement at the first temperature increase, continue to hold the temperature at 250 °C for 10 minutes, then decrease the temperature at a rate of 20 °C/min. The temperature was lowered, 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, the straight line (
Draw a perpendicular line to a point 20°C higher than the original crystalline melting temperature (Tm) of the ultra-high molecular weight ethylene copolymer, which is determined as the main melting peak during the second temperature rise, and the area on the low temperature side surrounded by these. is based on the crystalline melting (T11) inherent to the ultra-high molecular weight ethylene copolymer, and the high temperature side part is based on the crystalline melting (T11) that exhibits the function of the molded article of the present invention.
Tp), and the heat of fusion of each crystal is
Calculated from these areas. Also, Tpl and TE1
The heat of fusion based on the melting of Ti-
The part surrounded by the perpendicular line from 1-20°C and the perpendicular line from T1+/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 TE11. .

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.

Regarding the molecular orientation of ultra-high molecular weight polyolefin, the method for obtaining the above-mentioned ultra-high molecular weight polyolefin molecularly oriented molded product having high elasticity and high tensile strength includes, for example,
JP-A-56-15408, JP-A-58-5228
No. publicity, JP-A-59-130313, JP-A-59
Stretchability of the ultra-high molecular weight polyolefin is achieved by making the ultra-high molecular weight polyolefin into a dilute solution, or by adding a low molecular weight compound such as paraffin wax to the ultra-high molecular weight polyolefin, as described in detail in Publication No. 187614, etc. An example of a method of improving the drawing ratio and stretching it to a high magnification can be exemplified.

To ultra-high molecular weight ethylene and α-olefin
1 Notice-2 Next, the present invention will be explained below in order of raw materials, manufacturing method, and purpose so that it can be easily understood.

1-Kazuo 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 in an organic solvent using a Ziegler catalyst. can get.

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 the amount stated above per 1000 carbon atoms of the resulting copolymer. In addition, ultra-high molecular weight ethylene, α-
The olefin copolymer should have a molecular weight corresponding to the aforementioned 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 (+lI-'), 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 calculated in advance from the 13C nucleus. Ultra-high molecular weight ethylene α-
The amount of α-olefin in the olefin copolymer is determined.

1. In the present invention, when producing a molecularly oriented body from the ultra-high molecular weight ethylene/α-olefin copolymer, a diluent is added to 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-)-dichlorobenzene, and bromobenzene, and mineral oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil.

Further, as the waxes used as diluents, specifically, aliphatic hydrocarbon compounds or derivatives thereof are 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 or low molecular weight polymer obtained by copolymerizing ethylene with other α-olefins, medium/low pressure polyethylene wax, 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 getons, 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, 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
: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.

Melting crosstalk is generally 150~300℃, especially 170~2
It is carried out at a temperature of 70°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. death,
It becomes difficult to obtain a molded article having excellent high elastic modulus and high strength. In addition, the blending may be done by dry blending using a Henschel mixer, ■ type blender, etc.
Alternatively, 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 within the die orifice. The ratio of the winding speed V of the cooled and solidified undrawn material can be defined as a draft ratio by the following formula.

Draft ratio = ■/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.

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.

The core member of the course rope for swimming pools of the present invention is composed of an ultra-high molecular weight polyolefin molecularly oriented molded product, and this core member is made of stretched filaments of three strokes, four strokes,
It can be constructed by twisting or braiding a six-strand, eight-strand, loose-strand, etc., and in the present invention, the core member may be a braided rope or a multifilament of ultra-high molecular weight polyolefin. It can also be constructed by aligning bundled ultra-high molecular weight polyolefin multifilaments with gold threads, or by coating with a resin that is compatible with the resin of the coating resin.

Moreover, the breaking energy of the core portion 1 of the pool course rope of the present invention, which is made into a rope by braiding, is 3 kg·117 g or more, preferably 4 kg·rx/a or more.

Another feature of the molecularly oriented molded product of the present invention is that the strength utilization rate is less reduced (decreased) when unevenly assembled.

Good 1 The resin used in the coating resin layer forming the double layer* of the pool course robe according to the present invention is specifically a resin that has excellent chemical resistance and flexibility, and is heat resistant.・
Weather-resistant polyolefin resins, polyester elastomer resins, ionomer resins, etc. are used, and they are especially heat-resistant and weather-resistant! I-shaped low density polyethylene (L-LDPR) is preferably used.

The thickness of the coating resin layer in the pool course rope according to the present invention varies depending on the diameter of the rope, but is usually 0.5 to 0.5 -
5-1 Preferably 1 to 3 ffil.

Specifically, resin coating means such as extrusion coating and coating are used to coat the outer periphery of the filament assembly made of a molecularly oriented molded body of ultra-high molecular weight polyolefin as a core member with the above resin. Among these, in the case of extrusion coating, after coating the outer periphery of the core member with molten resin using a cross-head die, the core member is introduced into a sizing die, and then rapidly cooled with cooling water. Extrusion coating is preferably used because it can be coated.

The course robe for swimming pools according to the present invention uses a filament assembly made of lightweight and high-strength molecularly oriented molded polyolefin for the core member, and the outer periphery of the core member has excellent chemical resistance. Since it is coated with a highly flexible resin, it is lightweight, has high strength, has excellent chemical resistance, water resistance, and scratch resistance, and is easy to handle.

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

Fire” Figure 1”.

Polymerization of ultra-high molecular weight ethylene/butene-1 copolymer> An ultra-high molecular weight ethylene/butene-1 copolymer was slurry polymerized using a Ziegler catalyst and n-decane 1j as a polymerization solvent. A monomer gas mixture with a molar ratio of ethylene and butene-1 of 97.2:2.35 was continuously supplied to the rear eaves so as to maintain a constant pressure of 55 kg/-.The reaction temperature was 70. The process was completed in 2 hours at ℃.

The yield of the obtained ultra-high molecular weight ethylene-butene-1 copolymer powder was 160 tons, and the intrinsic viscosity [η] (decalin: 13
5° C.) was 8.2 dJ/l, 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 (
A mixture of 80 parts by weight (melting point = 69°C, molecular weight = 490) was melt-spun under the following conditions.

3.5- as a process stabilizer to 100 parts by weight of the mixture.
6 Next, the mixture was mixed with 0.1 part by weight of dimethyl-tert-butyl-4-hydroxytoluene in a screw extruder (screw diameter = 25 fl, L/D = 25.
(manufactured by Thermoglastics), set temperature 190
Melt kneading was performed at ℃. Subsequently, the melt was melt-spun using a spinning die with an orifice diameter of 2 mm attached to the extruder. The extrusion melt was drawn off with an air gap of 180 aa at a draft ratio of 36 times, cooled and solidified in air,
It was made into an undrawn fiber. 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 cm.

During stretching, the rotational speed of the first godet roll is set to 0.
By changing the rotation speed of the third godet roll to 5 m/ff1 inch, 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 was extracted into n-decane during stretching. Thereafter, the oriented fibers were washed with water, dried under reduced pressure at room temperature overnight, and then subjected to measurement of various physical properties. Note that 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 DC8-50M tensile tester manufactured by Shimadzu Corporation.

At this time, the sample length between the clamps was 100 cm, and the tensile rate was 100 ffil+/min (100%/min strain rate).1 The elastic modulus was calculated using the slope of the tangent at the initial elastic modulus.

The fiber cross-sectional area required for the calculation was calculated from the weight, assuming a density of 0.960 g/cc.

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

The sample had a length of about 3 m, and a plurality of pulleys were installed at both ends of a stainless steel frame, which was folded back to secure 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 the thermal history were measured based on the description of the measurement of the tensile properties described above.

Measurement of creep resistance characteristics〉 Creep resistance was measured using a thermal stress strain measuring device TMA/331.
0 (manufactured by Seiko Electronic Industries, Ltd.), sample length ICs,
The test was carried out under accelerated conditions at an ambient temperature of 70° C. and a weight equivalent to 30% of the breaking load at room temperature. The following two values were determined to quantitatively evaluate the amount of creep. In other words, the creep elongation (%) after 90 seconds after applying a load to the sample
) The value of CR9° and the value of the average creep rate (sec-1) ε after 180 seconds have elapsed from this time of 90 seconds.

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.
It was 8%. Also, creep resistance is CR9o=3.1%
, ε=3,03X10-"sec", and 1
Elastic modulus retention after heat history at 70°C for 5 minutes is 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.
3 kg·m/IH, density was 0.973 t/-, dielectric constant was 2.2, dielectric loss tangent was 0.024%, and impulse voltage breakdown value was 180 KV/fi.

Using the above-mentioned drawn filament (sample-1), 1.0
An 8-strand braid of OOdx4x8 was obtained as a core member. The diameter of the obtained core member was 3 steel.

With a pack tension of 2 kg applied to the obtained core member, the core member was made of linear low-density polyethylene (L-LDPE, MFR 11 g/10 min, density 0.925 g/cj) subjected to heat-resistant and weather-resistant treatment. ), the core member was coated by extrusion through a die heated to 160°C, and then the core member was
The sample was introduced into a sizing die, and further into a water tank for cooling.

In order to improve the heat resistance and weather resistance of linear low-density polyethylene, heat-resistant and weather-resistant treatments include adding ordinary sterically hindered phenol stabilizers, organic phosphite stabilizers, and organic thioether stabilizers to the linear low-density polyethylene. A stabilizer or the like may be added.

The outer diameter of the resin-coated rope obtained by cooling was 4.8-, and the amount of coated resin was 14 g/m.

The resulting resin-coated rope was measured for breaking strength, durability, and chemical resistance. Note that durability and chemical resistance were tested using the following method.

[Durability test] 5-TYPE with a safety factor of -5 as a durability evaluation method
Conduct a repeated bending fatigue test and measure the number of bends at break. (D/d=20...Repetitive bending fatigue test using a sheave 20 times the rope diameter) [Chemical resistance test @] The rope was immersed in a commercially available bleach (product name "Haiter", manufactured by Kao Corporation). Change in tensile strength of rope after soaking at room temperature (
Strength retention rate) is measured.

The results are shown in Tables 2 and 3.

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 IJ as a polymerization solvent.

At this time, 125 ml of octene-1 was added as a comonomer.
Before starting the polymerization, 4ONml of hydrogen was added all at once to adjust the molecular weight, and the polymerization was started. 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 g, and its intrinsic viscosity [η] (decalin,
(135°C) was 10.66 dJ/+r, and the octene-1 comonomer content was 0.5 per 1000 carbon atoms as determined by an infrared spectrophotometer.

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

The original crystal melting peak of the ultra-high molecular weight ethylene/octene-1 copolymer drawn filament (Sample-2) was 132.
Tll and Tp for total crystal melting peak area at 1°C
The proportions of l were 97.7% and 5.0%, respectively. The creep resistance of sample-2 is CR90=2, 0%,
ε=9.50xlOsec. Also, 170℃,
After 5 minutes of heat history, the elastic modulus retention rate was 108.2% and the strength retention rate was 102.1%. Furthermore, the amount of work required to fracture sample-2 is 10.1 kir·m/ir,
The density was 0.971+r/-, the dielectric constant was 2.2, the dielectric loss tangent was 0.031%, and the impulse voltage breakdown value was 185 KV/peng.

The above-mentioned drawn filament (sample-2) was formed into a rope by the method described in Example 1, and then extrusion coated to obtain the robe of the present invention.

The outer diameter of the resin-coated lobe obtained by cooling was 4.8 m+, and the amount of resin coated was 14 tr/m.

The resulting resin-coated rope was measured for breaking strength, durability, and chemical resistance.

The results are shown in Tables 5 and 6.

11-"Σ fi-co-poor 11"-Ultra high molecular weight polyethylene (homopolymer) powder (intrinsic viscosity [η] = 7.42 dj/l, Decalin, 135
°C) = 20 parts by weight and paraffin wax (melting point = 69
C, molecular weight = 490): A mixture of 80 parts by weight was melt-spun and drawn by the method of Example 1 to obtain draw-oriented fibers. Table 7 shows the tensile properties of a multifilament obtained by bundling a plurality of the obtained stretched and oriented fibers.

Ultra-high molecular weight polyethylene drawn filament (Sample-3)
The original crystal melting peak was 135.1°C, and the ratio of Tρ to the total crystal melting peak area was 8.8%. Similarly, the high temperature side peak Tpi with respect to the total crystal melting peak area
The proportion was less than 1%. Creep resistance is CR9o=
11.9%, ε = 1, 07 x 10'SeC'', and after heat history at 170°C for 5 minutes, the elastic modulus retention was 80.4% and the strength retention was 78.2%. there were.

Furthermore, the amount of work required to break sample-3 is 10.2 kg□
m/l, the density was 0.985 g/d, the dielectric constant was 2.3, the dielectric loss tangent was 0.030%, and the impulse voltage breakdown value was 182 K V / tm.

A rope of the present invention was obtained by the method described in Example 1 using Sample-3.

The outer diameter of the resin-coated rope obtained by cooling was 4.8 am, and the amount of resin coated was 14 f/m.

The resulting resin-coated rope was measured for breaking strength, durability, and chemical resistance.

The results are shown in Tables 8 and 9.

In Example 1, instead of the 8-strand braid made of ultra-high molecular weight polyethylene drawn filaments with a diameter of 3 cm, a braid made of Kevlar fiber (aramid fiber) with a diameter of 3 cm was used. A resin-coated robe was obtained in the same manner as in Example 1, except that an eight-strand braid was used as the core member.

The outer diameter of the resulting resin-coated lobe was 4.8B, and the amount of resin coated was 16 t/m.

The resulting resin-coated lobe was measured for breaking strength, durability, and chemical resistance in the same manner as in Example 1.

The results are shown in Tables 10 and 11.

In Example 1, the 8-braided rope itself made of stretched ultra-high molecular weight polyethylene filaments used as the core member was used as a rope, and the durability and durability were evaluated in the same manner as in Example 1. Chemical properties were measured.

The results are shown in Tables 12 and 13.

iU≦≧

Claims (2)

[Claims] (1) A course rope for a swimming pool, characterized in that the core member is a filament assembly made of a molecularly oriented molded product of ultra-high molecular weight polyolefin, and the outer periphery of the core member is coated with a resin. (2) The course rope for a swimming pool according to claim 1, wherein the ultra-high molecular weight polyolefin is ultra-high molecular weight polyethylene, ultra-high molecular weight polypropylene, or ultra-high molecular weight ethylene-α-olefin copolymer. .