JPH06158568A - Rope, string or net made of high strength polyethylene fiber coated with synthetic resin - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide ropes, strings and nets coated with synthetic resin that are lightweight, yet have excellent strength, creep resistance, weather resistance and abrasion resistance, and that allow arbitrary coloring. . [Structure] A rope, string or net comprising a filament or a twisted yarn of a molecular orientation molded body of an ultra high molecular weight ethylene polymer having an intrinsic viscosity [η] of at least 5 dl / g and having a surface coated with a synthetic resin. As the synthetic resin,
A resin selected from the group consisting of a polyolefin resin or a modified product thereof, an acrylic resin or a copolymer modified product thereof, a polyurethane resin or an epoxy resin is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rope, string or net made of high-strength polyethylene fiber coated with a synthetic resin, and more specifically, a filament composed of a molecular oriented body of an ultra high molecular weight ethylene polymer. Or a rope, string or net by coating a twisted thread with a synthetic resin, or by first forming a filament or twisted thread into a rope, a string or a net, and then coating the surface with an adhesive resin Obtained, colorability, weather resistance,
It relates to ropes, cords or nets with excellent wear resistance and fatigue characteristics.

[0002]

2. Description of the Related Art Molecularly oriented products (multifilaments) of ultra-high molecular weight ethylene polymers are particularly excellent in mechanical strength. Taking advantage of these characteristics, twisted filaments and reinforcing fibers are used. Fiber, string, rope, net,
Although it is used as a net, etc., this ultra high molecular weight ethylene polymer has poor coloring properties and cannot be colored in any desired color for the purpose of improving the appearance of the product. In some cases, the properties, wear resistance, and fatigue characteristics were not always sufficient. In recognition of such prior art, the present inventors have developed a cord in which the surface of a filament or a base yarn made of a molecular orientation molded product of an ultrahigh molecular weight ethylene polymer is coated with a synthetic resin, and Japanese Patent Application No. -2
A patent application was filed as No. 64160 (referred to as a prior invention).
The present inventors have obtained the knowledge that this technology can be effectively applied to other than the above code in the process of re-trying the invention of the earlier application and continuing the research, and based on this knowledge, the present invention completed.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to coat the surface of ropes, cords or nets or the surface of internal fibers with a synthetic resin so as to have excellent coloring properties, and to further improve weather resistance, wear resistance and abrasion resistance. Rope with improved fatigue characteristics,
To provide a string or net.

[0004]

The present invention has been proposed in order to achieve the above-mentioned object, and it is synthesized on the surface of a filament or a twisted yarn composed of a molecular oriented body of an ultra high molecular weight ethylene polymer. It is characterized in that after coating with a resin, it is made into a rope, a string or a net, or after filaments or twisted yarns are made into a rope, a string or a net and then coated with a synthetic resin.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The filament or twisted yarn according to the present invention has an ultrahigh molecular weight ethylene having an intrinsic viscosity [η] of at least 5 dl / g, preferably 7 to 30 dl / g measured in a solvent of decalin at 135 ° C. It is composed of a molecular orientation molded body of a polymer, the molecular orientation body itself, or a simple alignment of the molecular orientation body, or
Any of those twisted with a small number of twists (what is called a sweet twist) may be used. The thickness of the filament or the twisted yarn made of this molecular oriented material can be set in various ranges depending on the application, but is usually 0.5 mm to 2
It is preferably about mm.

Further, according to the present invention, the ultra-high molecular weight ethylene-based polymer contains ethylene and α-olefin containing an average of 0.1 to 20 α-olefins having 3 or more carbon atoms per 1000 carbon atoms. Copolymers of α-
The olefin is butene-1,4-methylpentene-1,
It is possible to use ethylene and α-olefin copolymers which are one or more selected from the group consisting of hexene-1, octene-1 and decene-1.

The ultra high molecular weight ethylene polymer is not limited to ultra high molecular weight polyethylene, but also ethylene having the above-mentioned intrinsic viscosity and an α-olefin having 3 or more carbon atoms, preferably 4 to 10 carbon atoms, such as propylene. , Butene-1, pentene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, decene-1
And a copolymer with one or more of the above, selected from the group consisting of ethylene and butene-1,4-methylpentene-1, hexene-1, octene-1 and decene-1. The above-mentioned copolymer with one or two or more α-olefins has high strength and is excellent in creep resistance, and is preferably used for the purpose of the present invention. Further, the ultra high molecular weight ethylene polymer is ethylene and α
When it is a copolymer with an olefin, it is desirable that the α-olefin comonomer is contained in an average of 0.1 to 20, preferably 0.5 to 10 per 1000 carbon atoms. When the content of the α-olefin comonomer in the copolymer is within the above range, α
The olefin component forms an intermolecular entangled structure effective for achieving high breaking energy, and this structure provides excellent mechanical properties such as high strength and low elongation.

Ultrahigh molecular weight ethylene / α-in the present invention
The quantification of the α-olefin component in the olefin copolymer is
An infrared spectrophotometer (manufactured by JASCO Corporation) was used.
That is, the absorbance at 1378 cm -1, which represents the bending vibration of the methyl group of the α-olefin incorporated in the ethylene chain, was measured, and from this, it was previously measured by a ¹³ C nuclear magnetic resonance apparatus.
It was calculated from the value measured by converting it into the number of methyl branches per 1000 carbon atoms with an inspection line prepared using the model compound.

If the intrinsic viscosity [η] of the ultra-high molecular weight ethylene polymer is less than 5 dl / g, a molecularly oriented molded product having sufficient strength cannot be obtained even if the stretching ratio is increased, and conversely [η] ] Of 30 dl / g or more has a very high melt viscosity under high concentration, melt fracture occurs during extrusion, and melt spinnability is poor, so that a suitable multifilament cannot be obtained.

The ultra high molecular weight ethylene polymer of the present invention is
Presence of a catalyst comprising ethylene, or ethylene and the α-olefin comonomer, a transition metal compound of Group IVb, Vb, VIb, VIII of the Periodic Table and a metal hydride or organometal of Group I to III of the Periodic Table. Below, for example, it can be obtained by slurry polymerization in an organic solvent.

The ultrahigh molecular weight ethylene polymer thus obtained is blended with a diluent for enabling melt molding, or is mixed with a paraffin wax which is solid at room temperature, melt-extruded, and then stretched. By
For example, a molecular orientation molded product such as a fiber is used.

As the diluent, a solvent for the ultra high molecular weight ethylene polymer or various waxes having dispersibility in the ultra high molecular weight ethylene polymer are used.

The solvent is preferably a solvent having a boiling point not lower than the melting point of the polymer, more preferably not lower than the melting point + 20 ° C.

Specific examples of such a solvent include n-nonane, n-decane, n-undecane, n-dodecane and n-
Aliphatic hydrocarbon solvents such as tetradecane, n-octadecane or liquid paraffin, kerosene, xylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, benzylbenzene, dodecylbenzene, bicyclohexyl, decalin, methyl Aromatic hydrocarbon solvents such as naphthalene and ethylnaphthalene or hydrogenated derivatives thereof, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,2,3-trichloropropane, dichlorobenzene, 1,2 Examples thereof include halogenated hydrocarbon solvents such as 1,4-trichlorobenzene and bromobenzene, and mineral oils such as paraffin-based process oil, naphthene-based process oil and aromatic-based process oil.

As the wax, an aliphatic hydrocarbon compound or its derivative is used.

The aliphatic hydrocarbon compound is mainly a saturated aliphatic hydrocarbon compound and usually has a molecular weight of 2
000 or less, preferably 1000 or less, more preferably 800 or less, which is called paraffin wax. Specific examples of these aliphatic hydrocarbon compounds include n-alkanes having 22 or more carbon atoms such as docosane, tricosane, tetracosane, and triacontane, or mixtures with lower n-alkanes containing these as the main components, and separation and purification from petroleum. So-called paraffin wax, low molecular weight polymer obtained by copolymerizing ethylene or ethylene or other α-olefin, polyethylene wax for medium / low pressure method, polyethylene wax for high pressure method, ethylene copolymer wax or medium / low pressure method Examples thereof include waxes obtained by reducing the molecular weight of polyethylene such as polyethylene and high-pressure polyethylene by thermal degradation, oxides of these waxes, oxidized waxes such as maleic acid-modified waxes, and maleic acid-modified waxes.

The aliphatic hydrocarbon compound derivative is, for example, one or more, preferably 1 or 2, and particularly preferably 1 at the terminal or inside of the aliphatic hydrocarbon group (alkyl group, alkenyl group). A compound having a functional group such as a carboxyl group, a hydroxyl group, a carbamoyl group, an ester group, a mercapto group and a carbonyl group, having 8 or more carbon atoms, preferably 12 to 50 carbon atoms, or a molecular weight of 130 to 2000, preferably 200 to 8
00 fatty acid, fatty alcohol, fatty acid amide, fatty acid ester, aliphatic mercaptan, aliphatic aldehyde,
Examples thereof include aliphatic ketones. Specifically, capric acid as a fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, lauryl alcohol as an aliphatic alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, caprinamide as a fatty acid amide, laurinamide, Examples of palmitic amide, stearyl amide, and stearyl acetic acid ester as the fatty acid ester can be given.

The ratio of the ultra high molecular weight ethylene polymer to the diluent varies depending on the kind thereof, but generally it is 3:97 to 80:20, and particularly 15:85 to 60:40. Good to use in ratio. When the amount of the diluent is lower than the above range, the melt viscosity becomes too high, which makes melt-kneading and melt-molding difficult, and the surface roughness of the molded product is remarkable, and stretch breakage easily occurs. On the other hand, when the amount of the diluent is more than the above range, the melt-kneading becomes difficult and the stretchability of the molded product becomes poor.

Melt kneading is generally 150 to 300.
It is desirable to carry out at a temperature of 170 ° C., especially 170 to 270 ° C. At a temperature lower than the above range, the melt viscosity becomes too high, which makes melt molding difficult. The molecular weight of the ultra-high molecular weight ethylene polymer decreases, and it becomes difficult to obtain a molded product having a high elastic modulus and high strength. The composition is Henschel mixer, V
You may do it by dry blending with a type blender,
It may be performed by melt mixing using a single-screw or multi-screw extruder.

Melt molding is generally carried out by melt extrusion molding. For example, a filament for stretching can be obtained by melt extrusion through a spinneret, and a tape for stretching can be obtained by extrusion through a flat die or a ring die. At this time, a draft, that is, stretching in a molten state, can be added to the melt extruded from the spinneret. Extrusion speed VO of the molten resin in the die / orifice and winding speed V of the unstretched material that has been cooled and solidified
The ratio with and can be defined as the draft ratio by the following formula. Draft ratio = V / VO Although such a draft ratio changes depending on the temperature of the mixture, the molecular weight of the ultrahigh molecular weight ethylene polymer, etc., it can be usually 3 or more, preferably 6 or more.

Next, the unstretched molded product of the ultrahigh molecular weight ethylene polymer thus obtained is stretched. The stretching operation can be performed in one stage or in multiple stages of two or more stages. The draw ratio depends on the desired molecular orientation and the accompanying effect of improving the melting temperature, but it is generally satisfactory if the draw operation is carried out so that the draw ratio is 5 to 80 times, especially 10 to 50 times. You get the results you need. Generally, multi-stage drawing of two or more stages is advantageous, and in the first stage, it is 8
The stretching operation is performed while extracting the diluent in the extrusion-molded product at a relatively low temperature of 0 to 120 ° C., and at the second and subsequent stages, the temperature is 120 to 160 ° C. and higher than the stretching temperature of the first stage. It is advisable to continue the stretching operation of the shaped body at temperature.

The molecular orientation molded body thus obtained can be heat-treated, if desired, under restraint conditions. This heat treatment is generally carried out at a temperature of 140 to 180 ° C., especially 150 to 175 ° C., for 1 to 20 minutes, especially 3 to 1
It can be done for 0 minutes. The heat treatment further promotes the crystallization of the oriented crystal part, which brings about the shift of the crystal melting temperature to the high temperature side, the improvement of the strength and the elastic modulus, and the improvement of the creep resistance at high temperature.

The process of molecular orientation in the molded body can be known by X-ray diffraction method, birefringence method, fluorescence polarization method and the like. In the case of the drawn filament of the ultra-high molecular weight ethylene polymer of the present invention, the degree of orientation according to the full width at half maximum as described in detail in, for example, Yukichi Kure, Kouichiro Kubo: Industrial Chemistry Journal, Vol. 39, p. formula (In the formula, H ° is the half-value width (°) of the intensity distribution curve along the Debye ring of the strongest paratropic plane on the equator.) The degree of orientation (F) defined by 0.90 or more, particularly 0.95 or more. It is desirable from the viewpoint of mechanical properties that the molecules are oriented so that

The ultra-high molecular weight ethylene-based polymer of the present invention may be used as it is, or by simply aligning or twisting the molecularly-oriented product of the ultra-high-molecular-weight ethylene-based polymer. It is possible to obtain filaments or twisted yarns of polymer molecular orientation. When a primer, which will be described later, is applied to these molecularly oriented materials, the adhesiveness and handleability are further improved. Also,
The sweet twisted yarn can be obtained, for example, by preliminarily twisting the multifilament around 100 times / minute with a ring twisting machine.

In the present invention, the surfaces of the filaments or twisted yarns of these molecularly oriented molded products are coated with synthetic resin in advance and then made into ropes, cords or nets, or the filaments or twisted yarns are made into ropes, cords or nets. rear,
Coat with synthetic resin. The resin to be coated may be any as long as it can adhere to the molecular oriented body of the ultra high molecular weight ethylene polymer of the present invention, but it withstands outdoor long-term use, rubbing, bending fatigue resistance, etc. Those having excellent durability characteristics are preferable. As the synthetic resin satisfying such required characteristics, for example, a resin selected from the group consisting of a polyolefin resin or a modified product thereof, an acrylic resin or a copolymerization modified product thereof, a polyurethane resin, or an epoxy resin is preferable. The thickness of the coated synthetic resin layer can be set in various ranges depending on the use, but normally 0.1 to 0.5 mm is suitable.

The filament or twisted yarn is a rope,
Stringing or netting can be performed by a method known per se, but generally suitable rope forms are three striking, six striking as a twisted structure, and eight striking as a knitted structure ( Eight ropes), 12 hits (towel ropes) and double braids (tuff ropes) are exemplified. As the net, a net having a knotted portion, a knotless net, or the like can be arbitrarily processed.

To these synthetic resins, various compounding agents known per se can be added within a range not impairing the object of the invention. The compounding agent may be any compounding agent known in the prior art of the present application, and examples thereof include a colorant, a stabilizer, a plasticizer, a lubricant and a filler.

Inorganic pigments, organic pigments, and organic dyes are known as colorants, and suitable examples include titanium oxide, cadmium compounds, carbon black, azo compounds, cyanine dyes, polycyclic pigments, and the like. can do. The amount of the colorant compounded is usually 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the resin.

The method of adding these colorants to the synthetic resin may be any of the methods known before the present application. In particular, a paste prepared by kneading the colorant with a plasticizer is used in the resin. And a method of blending a masterbatch in which a colorant and a resin are kneaded at a high concentration in the resin.

In the present invention, the resin composition thus obtained is dissolved in, for example, various good solvents at room temperature or in the form of a water emulsion, and the rope made of the high-strength polyethylene fiber, The object is obtained by impregnating and coating a string or net-like material, or by a roll transfer coating method or the like.

In the present invention, the surface of the filament or twisted yarn is previously corona-treated in order to improve the adhesion between the filament or the twisted yarn made of molecularly oriented body of ultra high molecular weight ethylene polymer and the coating resin. ,
Plasma treatment, graft modification treatment, flame treatment and the like can be performed.

As an example of suitable applications of the rope, cord and net provided by the present invention, the rope is used for marine construction, ship mooring, land construction, etc.
As a string, use such as fishing line, kite cord, string for paraglider, and as a net, on land,
On the net for various competitions such as golf courses, at sea,
It can be suitably used as a net for marine products. Needless to say, it can be suitably used for other applications such as ropes, cords and nets that require weather resistance, wear resistance and fatigue resistance.

[0033]

According to the present invention, the surface of a rope, a string or a net made of filaments or twisted yarns made of a molecular orientation product of an ultra high molecular weight ethylene polymer is coated with a synthetic resin to produce an ultra high molecular weight ethylene. While maintaining the excellent physical properties originally possessed by filaments or twisted yarns composed of a molecularly oriented polymer of a polymer, not only the colorability is improved, but also the weather resistance, abrasion resistance and fatigue characteristics are further improved.

[0034]

EXAMPLES The present invention will be described below with reference to examples. Reference Example 1 <Polymerization of Ultra High Molecular Weight Ethylene / Butene-1 Copolymer> Slurry polymerization of ultra high molecular weight ethylene / butene-1 copolymer was carried out using a Ziegler catalyst and 1 liter of n-decane as a polymerization solvent. It was A mixed monomer gas with a molar ratio of ethylene and butene-1 of 97.2: 2.8 was continuously fed to the reactor so that the pressure was kept constant at 5 kg / cm ² . The polymerization was completed in 2 hours at a reaction temperature of 70 ° C. The yield of the ultra-high molecular weight ethylene-butene-1 copolymer powder obtained was 160 g, and the intrinsic viscosity [η] (decalin: 135 ° C) was 8.2d.
1 / g, butene-1 content by infrared spectrophotometer was 1.5 per 1000 carbon atoms.

<Preparation of Stretched Oriented Product of Ultra High Molecular Weight Ethylene / Butene-1 Copolymer> 20 parts by weight of ultra high molecular weight ethylene / butene-1 copolymer powder obtained by the above-mentioned polymerization and paraffin wax (melting point = 69 A mixture of 80 parts by weight at 80 ° C. and a molecular weight of 490) was melt-spun under the following conditions. The mixture 100
To the parts by weight, 0.1 part by weight of 3,5-di-tert-butyl-4-hydroxytoluene was added as a process stabilizer. Then, the mixture was melt-kneaded at a preset temperature of 190 ° C. using a screw type extruder (screw diameter = 25 mm, L / D = 25, manufactured by Thermoplastics Co., Ltd.). Continued,
The mixed melt was melt-spun with a spinning die having an orifice diameter of 2 mm attached to the extruder. The extruded melt was taken with a draft ratio of 36 times with an air gap of 180 cm, cooled in air and solidified to obtain an unstretched fiber. Further, the unstretched fiber was stretched under the following conditions.

Two-stage stretching was performed using three godet rolls. At this time, the heat medium in the first drawing tank was n-decane, the temperature was 110 ° C, the heat medium in the second drawing tank was triethylene glycol, and the temperature was 145 ° C. The effective length of each tank was 50 cm. At the time of drawing, the rotational speed of the first godet roll was set to 0.5 m / min and the rotational speed of the third godet roll was changed to obtain an oriented fiber having a desired draw ratio. The rotation speed of the second godet roll was appropriately selected within a range in which stable stretching was possible. Almost all the paraffin wax mixed in the initial stage was extracted into n-decane during stretching. After that, the oriented fiber was washed with water, dried under reduced pressure at room temperature for a whole day and night, and subjected to measurement of various physical properties. The stretching ratio was calculated from the rotation speed ratio of the first godet roll and the third godet roll.

<Measurement of Tensile Properties> Modulus of elasticity and tensile strength were measured at room temperature (23 ° C.) using a Shimadzu DCS-50M type tensile tester. At this time, the sample length between the clamps is
100 mm, tensile speed 100 mm / min (100% / min strain rate)
Met. The elastic modulus was calculated using the initial elastic modulus and the slope of the tangent line. The fiber cross-sectional area required for the calculation was calculated from the weight with a density of 0.960 g / cc.

<Tensile elastic modulus and strength retention rate after heat history> The heat history test was conducted in a gear oven (perfect oven:
It was performed by leaving it in the Tabayi Seisakusho).
The sample had a length of about 3 m, and was folded back on a stainless steel frame provided with a plurality of pulleys at both ends to fix both ends of the sample. At this time, fix both ends of the sample so that the sample does not sag,
The sample was not actively tensioned. The tensile properties after thermal history were measured based on the description of the measurement of the tensile properties described above.

<Measurement of creep resistance> The creep resistance was measured by using a stress strain measuring device TMA / SS10 (manufactured by Seiko Denshi Kogyo Co., Ltd.), sample length 1 cm, ambient temperature 70 ° C.
The load was applied under accelerated conditions of a weight corresponding to 30% of the breaking load at room temperature. The following two values were obtained in order to quantitatively evaluate the creep amount. That is, the value of creep elongation (%) CR90 at 90 seconds after applying a load to the sample and the average creep speed (sec at 90 seconds to 180 seconds)
-1) The value of ε.

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

The original crystal melting peak of the ultra-high molecular weight ethylene-butene-1 copolymer drawn filament (Sample-1) was 126.7 ° C., and the ratio of Tp to the total crystal melting peak area was 33.8%. Creep resistance is CR90 = 3.1%,
ε = 3.03 × 10 −5 sec −1. Furthermore, the elastic modulus retention rate after heat history at 170 ° C for 5 minutes is 102.2%, and the strength retention rate is 10%.
At 2.5%, no performance deterioration due to thermal history was observed. The work required to break the drawn filament is 10.3 kgm
/ g, the density was 0.973 g / cm3, the dielectric constant was 2.2, the dielectric loss tangent was 0.024%, and the impulse voltage breakdown value was 180 kV / mm. The reduction rates of the knot strength and the loop strength of the multifilament with respect to the linear strength were 38% and 36%, respectively.

Reference Example 2 <Polymerization of Ultra High Molecular Weight Polyethylene> Slurry polymerization of ultra high molecular weight polyethylene was carried out using 1 liter of n-decane as a polymerization solvent using a Ziegler type catalyst. Prior to polymerization, the reactor was filled with a mixed gas of ethylene gas and hydrogen gas at a pressure of 5 kg / cm ² (of which the hydrogen gas partial pressure was 0.2 kg / cm ² ), and thereafter only ethylene gas was used as the polymerization pressure. 5kg / c
It was supplied so as to keep m ² . The polymerization was completed in 2 hours at a reaction temperature of 70 ° C. The yield of ultra high molecular weight polyethylene obtained is
Intrinsic viscosity [η] at 170 g (decalin: 135 ° C) is 7.42
It was d 1 / g.

<Preparation of Stretched Aligned Product of Ultra High Molecular Weight Polyethylene> Ultra high molecular weight polyethylene (homopolymer) powder (intrinsic viscosity [η] = 7.42 dl / g, decalin, 135 ° C.): 20
Parts by weight and paraffin wax (melting point = 69 ° C., molecular weight = 49
0): 80 parts by weight of the mixture was melt-spun by the method of Reference Example 1 and stretched to obtain a stretched and oriented fiber (Sample-2). Table 2 shows the tensile properties of the multifilament obtained by bundling a plurality of the obtained stretched and oriented fibers.

The original crystal melting peak of the ultrahigh molecular weight polyethylene drawn filament (Sample-2) was 135.1 ° C., and the ratio of Tp 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 was 1% or less. Creep resistance is CR90 =
It was 11.9% and ε = 1.07 × 10 −3 sec −1. Also 170 ℃,
After a thermal history of 5 minutes, the elastic modulus retention was 80.4% and the strength retention was 78.2%. Furthermore, the work required for fracture of Sample-2 is 10.2 kgm / g, the density is 0.985 g / cm3, the dielectric constant is 2.3, the dielectric loss tangent is 0.030%, and the impulse voltage breakdown value is 182 kV / mm. Met. The reduction rates of the knot strength and the loop strength of the multifilament with respect to the linear strength were 54% and 52%, respectively.

Example 1 A knotless net was prepared by using four stretched oriented products of the ultrahigh molecular weight ethylene-butene-1 copolymer obtained in Reference Example 1, which were aligned. The obtained net had a diameter of about 1 mm and a mesh size of 50 mm. This net contains 0.5% by weight of carbon black based on the solid content of weather resistant polyurethane (manufactured by Nippon Polyurethane Co., Ltd., “Nipolan 519”).
9 ") and diluted with a solvent to obtain a solid content concentration of 10% by weight.
Was impregnated with the above and then air-dried to obtain a coated net having a resin adhesion amount of 18% by weight. The obtained net had an initial strength of 104 kg, weather resistance; a sunshine weatherometer (63 ° C. with rain), and a strength of 60 kg after 2000 hours. Abrasion resistance: Using the rubbing tester shown in FIG. 1, set # 1000 sandpaper on a non-rotating wear element having a diameter of 3 cm, 100 cycles / minute (3 cm reciprocation),
When the cycle until fracture was evaluated under the condition of a load of 25 g, it was fractured at 5000 cycles.

Example 2 A braid was prepared by using 15 stretched oriented materials of the ultrahigh molecular weight ethylene-butene-1 copolymer obtained in Reference Example 1, which were prepared by aligning 15 pieces. The same cord was used as in Example 1 to obtain a coated cord having a resin adhesion amount of 15% by weight. Initial strength: 27 kg Weather resistance: 16 kg (Sunshine Weatherometer 2
After 000 hours) Abrasion resistance; When the cycle until breakage was evaluated under the same conditions as in Example 1, breakage occurred at 3200 cycles.

Example 3 The stretched and oriented product of the ultra-high molecular weight ethylene-butene-1 copolymer obtained in Reference Example 1 was twisted with 8 strands of 100 aligned and twisted with 12 strands to form a rope. It was made. This rope was treated in the same manner as in Example 1 to obtain a coated rope having a resin adhesion amount of 5% by weight. Initial strength: 16 tons Weather resistance: 13 tons (Sunshine Weatherometer 2
After 000 hours) Abrasion resistance; # 200 hardness 5 using the apparatus shown in FIG.
6 wearers with a diameter of 30 cm with a 5 degree grinder
It was 12 tons when the strength after 500 cycles of abrasion was evaluated at 60 cycles / min (30 cm reciprocation) by rotating at 0 cycles / min, applying a load of 1 t.

Comparative Example 1 The net used in Example 1 was evaluated without resin coating. Initial strength: 104 kg Weather resistance: 20 kg (Sunshine Weatherometer 2
After 000 hours) Abrasion resistance; When the cycle until breakage was evaluated by the same method as in Example 1, it was found to break after 150 cycles.

Comparative Example 2 The braid used in Example 2 was evaluated without resin coating. Initial strength: 27 kg Weather resistance: 8 kg (Sunshine Weatherometer 20
After 00 hours) Abrasion resistance; When the cycle until breakage was evaluated by the same method as in Example 1, it was found to break at 80 cycles.

Comparative Example 3 The rope used in Example 3 was evaluated without resin coating. Initial strength: 16 tons Weather resistance: 8 tons (Sunshine weatherometer 20
After 00 hours) Abrasion resistance: In the same manner as in Example 3, the strength after 500 cycles of abrasion was evaluated and found to be 3 tons.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for testing the wear resistance until breakage of a string-like object in Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention.

FIG. 2 is a schematic view of an apparatus for testing the strength of a rope-shaped article after a certain number of cycles in Example 3 and Comparative Example 3 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D02G 3/44 D06M 15/19 // D06M 101: 18

Claims (5)

[Claims] 1. An intrinsic viscosity [η] of at least 5 dl / g
A rope, string or net which is composed of a filament or twisted yarn of a molecular orientation molded body of an ultra high molecular weight ethylene polymer which is, and whose surface is coated with a synthetic resin. 2. The ultra-high molecular weight ethylene polymer is a copolymer of ethylene and α-olefin, which contains 0.1 to 20 α-olefins having 3 or more carbon atoms per 1000 carbon atoms on average. The rope, cord or net according to claim 1. 3. The rope according to claim 1, wherein the synthetic resin is selected from the group consisting of a polyolefin resin or a modified product thereof, an acrylic resin or a copolymer modified product thereof, a polyurethane resin or an epoxy resin. String or net. 4. The α-olefin is one or more selected from the group consisting of butene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1. Item 2. The rope, cord or net according to item 2. 5. The α-olefin content is 1000 carbon atoms.
The rope, cord or net according to claim 2, which has an average of 0.5 to 10 pieces per piece.