JPH03249289A - Composite braid rope - Google Patents

Abstract

PURPOSE:To provide the subject rope having excellent flexural fatigue resistance and useful for running ropes, etc., by coating the surface of a braid rope prepared by braiding specific polyolefin fibers with a resin so that a prescribed volume of the rope is impregnated with the resin. CONSTITUTION:The objective braid rope is prepared by braiding fibers comprising an ultrahigh mol.wt. polyolefin (e.g. polyethylene) having a viscosity-average mol.wt, of >=500000, the surface of the braid rope being coated with a resin (e.g. an unsaturated polyester) so that at least 5% of the volume of the braid rope is impregnated with the resin from the outer periphery thereof toward the center thereof.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a composite braided rope made of ultra-high molecular weight polyolefin fibers with high strength and high modulus of elasticity, and which has excellent bending fatigue resistance, abrasion resistance and water absorption resistance. It is suitable as an excellent bare rope.

(Prior Art) High-strength, high-modulus fibers made from ultra-high molecular weight polyolefins have better weather resistance and resistance than other high-strength, high-modulus fibers such as aramid fibers, carbon fibers, and glass fibers. Because it has excellent bending fatigue resistance, abrasion resistance, and water absorption resistance, it is often used as a so-called bare rope. However, when using the above-mentioned rope as an outdoor moving rope, such as a limp rope used to tow communication cables and electric wires, etc. to prevent them from being stretched over a specified section, it is necessary to However, the water absorption resistance is insufficient, and when the water absorption resistance is particularly low, there is a problem that workers may be affected by evil spirits during rainy weather.

Therefore, various means for improving water absorption resistance have been proposed. For example, Japanese Patent Laid-Open No. 58207806 discloses that a coating layer of a hot-melt resin is provided between the middle layer and the outer layer of a rope consisting of a core thread, a middle layer, and an outer layer of a braided body. In addition, it was disclosed in Japanese Patent Application Laid-Open No. 63-1982 that the surface of a filamentous material made of long fibers with high tensile strength is coated with a soft material.
It is disclosed in Japanese Patent No. 64990. In addition, Japanese Patent Laid-Open No. 62-53495 discloses that a high-strength, low-elongation fiber string product impregnated with a polyurethane elastomer resin is coated with a thermoplastic resin.
It is disclosed in the publication No.

(Problem to be Solved by the Invention) However, in the robe described in JP-A-58-207806, since the polyester fibers and the like exist in the outermost layer in a substantially bare state, moisture is absorbed into the fibers of the outermost layer. There were other problems, such as penetrating into the inside of the yarn, resulting in an insufficient electric shock prevention function, making it impossible to observe the state of damage to the inner layer yarn, and making it heavier. In addition, in the filamentous material described in JP-A No. 63-264990, since the coating material exists only on the surface,
The bending fatigue resistance and abrasion resistance were insufficient, and moisture entered even through small scratches, resulting in an insufficient electric shock prevention function. In addition, the string-like product described in JP-A-62-53495 is impregnated with urethane resin and then coated with thermoplastic resin, which increases the number of steps and increases manufacturing costs. In addition, since the string-like product is substantially composed of aramid fiber, glass fiber, or carbon fiber, it lacks abrasion resistance and bending fatigue resistance, making it unsuitable for use as a moving rope lobe such as a reed lobe. Met.

The present invention provides a blade row 1 that is made of high-strength, high-modulus polyolefin fibers and has improved bending fatigue resistance, abrasion resistance, and water absorption resistance.

(Means for Solving the Problems) The present invention provides a braided lobe obtained by combining fibers made of ultra-high molecular weight polyolefin with a viscosity average molecular weight of 500,000 or more, wherein the surface of the braided rope is made of resin. A composite blade lobe characterized in that at least 5% of the volume of the blade lobe is coated and impregnated with the above resin from the outer periphery towards the center.

The ultra-high molecular weight polyolefin used in this invention has a viscosity average molecular weight of 500,000 or more, preferably 1,000,000 or more.
- A homopolymer of olefins or a copolymer of two or more α-olefins, which is highly crystalline. Those with a viscosity average molecular weight of less than 500,000 have an excellent elastic modulus when made into fibers through a drawing process, but cannot be used in the blade lobe of the present invention because the desired strength cannot be obtained.

Examples of the above α-olefins include ethylene, propylene, 1-butene, 4-methyl-1-pentene, ]-hexene, and -decene.

Among the ultra-high molecular weight polyolefins mentioned above, ethylene homopolymers and ethylene with small amounts of other α-
Copolymers with polyolefins are particularly preferred because they have excellent strength, cold resistance, impact resistance, self-lubricating properties, and the like.

In this invention, it is necessary that the surface of the braided rope is coated with the resin and that at least 5% of the total volume of the braided rope from the outer periphery toward the center is impregnated with the resin. If the surface of the blade lobe is not coated with a resin or if the amount of resin impregnated is less than 5%, the bending fatigue resistance, abrasion resistance and water absorption resistance will be insufficient. If the resin that coats the surface of the blade lobe and the resin that impregnates the inside are different, problems such as an increase in the number of steps and an increase in manufacturing cost will occur.

The resin impregnated into the blade lobes may be either a thermosetting resin or a thermoplastic resin.

Examples of the thermosetting resin include unsaturated polyester, vinyl ester, epoxy resin, acrylic resin, and polyurethane elastomer resin. Examples of the thermoplastic resin include polyolefin resins, polyvinyl chloride, ionomer resins, polyurethane elastomer resins, polyester elastomer resins, and polyamide resins. Among these resins, thermosetting polyurethane elastomer resins, thermoplastic polyurethane elastomer resins, and thermoplastic polyolefin resins are particularly preferred.

The above polyurethane elastomer resin is a reaction product of a polyisocyanate component and a polyol component, and various crosslinking agents and crosslinking accelerators can be added as desired. As the polyisocyanate component, 4.4''-diphenylmethane diisocyanate, 4.4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate can be used, and as the polyol component, ethylene glycol, 1,4-butylene glycol,
1,6-hexanediol, poly(ethylene adipate), poly(1,4-butylene adipate), poly(1
, 6-hexane adipate), poly-ε-caprolactone, polyoxytetramethylene glycol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, ethylene oxide/propylene oxide copolymer, tetrahydrofuran/ethylene oxide copolymer, tetrahydrofuran/propylene oxide copolymer Polymers such as poly(diethylene adipate), poly(propylene adipate), poly(hexamethylene adipate), poly(neopentylene adipate) can be used. In addition, crosslinking agents include glycol crosslinking agents such as ethylene glycol, 1,6-hexanediol, and bishydroxyethoxyglycol, amine crosslinking agents such as triethylenediamine and pentamethylene diethylene triamine, nitrogen-containing polyhydric alcohols, and isocyanate crosslinking agents. can be used. In addition, examples of crosslinking accelerators include amine crosslinking accelerators such as triethylenediamine, bis(dimethylaminoethyl)ether, N,N dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, triethylamine, stannatooctoate, dibutyl Organometallic promoters such as tin diacetate, dibutyl tin dilaurate, dibutyl tin mercaptide, dibutyl tin thiocarboxylate, dibutyl tin dimaleate, dioctyl tin mercaptide, dioctyl tin thiocarboxylate, etc. can be used.

The polyolefin resin may be a homopolymer or copolymer of at least one α-olefin such as ethylene, propylene, ■-butene, or 1-pentene, or a homopolymer or copolymer of at least one α-olefin and at least one of the above-mentioned α-olefins. Examples include copolymers with other olefinically unsaturated monomers such as vinyl acetate, acrylic acid, methacrylic acid, and glycidyl methacrylate.

If desired, resin components such as ABS, polystyrene, polystyrene-polybutadiene-polystyrene, and polystyrene-maleic anhydride may be mixed. Furthermore, if desired, known ultraviolet absorbers, thickeners, thickeners, dyes, lubricants, etc. can be added.

The above-mentioned resins can be impregnated into the blade lobes in the molten state or in the form of solutions dissolved or dispersed in organic or aqueous solvents, but it is preferred to impregnate the latter in the form of solutions, in which case , the strength retention rate of the blade lobe is improved, and resin impregnation becomes easier. Examples of organic solvents that can be used include toluene, xylene, methyl ethyl ketone, dimethylformamide, and ethyl acetate.

In order to impregnate a polyurethane elastomer resin into a blade lobe made of high strength, low elongation fibers, the blade lobe is immersed in a polyurethane elastomer solution under pressure, the solution is sufficiently impregnated between each fiber, and then heated and cured. . Further, the above-mentioned composite blade lobe may be subjected to known water-repellent finishing, flame-retardant finishing, etc.

The high-strength, high-modulus polyolefin fiber of the present invention can be obtained by dissolving ultra-high molecular weight polyethylene with a viscosity average molecular weight of 500,000 or more in a solvent such as decalin, xylene or paraffin at a temperature below its boiling point, and then dissolving the fiber in a prevention device. The polyethylene solution is extruded into air, water, or a hollow pipe equipped with a cooling device at room temperature at a temperature at which the polyethylene solution does not solidify, and then heated to such an extent that the fibers do not melt, resulting in a total stretching ratio of 10 times or more, preferably 20 times or more. It is manufactured by stretching in one or multiple stages.

(Function) By impregnating the blade lobes made of high-strength, high-modulus polyolefin fibers with resin, mutual friction and wear between the polyolefin fibers is reduced, and the bending fatigue resistance and abrasion resistance of the blade lobes are improved. , and moisture is prevented from entering the blade lobes. however,
No effect can be obtained if the amount of impregnation is less than 5% of the volume of the blade lobe.

(Example) Using high molecular weight polyethylene fibers, aramid fibers (manufactured by DuPont, Kevlar 49) and three types of resin impregnation treatment liquids, a total of six types of eight types were used: Example 1.2 and Comparative Examples 1 to 4. Hammered composite blade lobe (for high molecular weight polyethylene fiber, blade angle 30 degrees, 1600dX4X3X
8. For aramid fiber, blade angle is 30 degrees, 142
0dX4X3X8) were manufactured and their characteristics were compared. The measurement method was as follows.

Average molecular weight of high molecular weight polyethylene fiber ASTM D
After measuring the viscosity of the decalin solution at 135° C. using No. 2857 to determine the intrinsic viscosity [η], the average molecular weight (Mv) was calculated by substituting (η) into the following equation.

M Sea 3.64xlO' The test was carried out by hanging a weight 4 at the end and rotating the drive pulley 3 back and forth. However, the ratio D/d of the diameter of the roller 2 to the diameter d of the lobe 1 was set to 25. In addition, the tension of the lobe 1 (The range of variation accompanying the reciprocating rotation of the drive pulley 3) is the same as in Example 1 in order to match the ratio of the load to the lobe strength.
2 and Comparative Example 2.3 were set to 0 to 300 kg, Comparative Example 1 was set to 0 to 160 kg, and Comparative Example 4 was set to 0 to 230 kg. Also, the number of repeated bending is soo.

The rupture strength was then measured.

Abrasion resistance As shown in FIG. 2, one end of the test lobe 1 is fixed,
The above-mentioned row 11 is stretched horizontally by hanging it on a guide roller 5 and a weight 4 is attached to the other end, and a sand grinder 6 with a surface roughness of #200 is brought into contact with the horizontal part of this lobe 1 at a speed of 60 times/min. It was made to reciprocate left and right, and the breaking strength was measured after reciprocating 1000 times. However, the weight of weight 4 is the same as that in Example 1.
2 and Comparative Example 2.3 to 300 kg, Comparative Example 1 to 16
The weight of Comparative Example 4 was set to 0, and the weight of Comparative Example 4 was set to 230 kg.

Both ends of a lobe with a water absorption resistance length of 20 CII+ and weight % are sealed with the same resin as the impregnating resin, the lobe is immersed in water at a temperature of 20°C, and the weight X-x)/
Calculate the water absorption rate using X.

Resin impregnation rate Cut the resin-impregnated blade lobe vertically in the length direction at an arbitrary position, take a photograph of this cut surface with a microscope, and calculate the total cross-sectional area Y of the braided rope and the residual area after resin impregnation. The area of the impregnated portion is measured, and the resin impregnation rate is calculated using the formula (Yy)/Y.

Example 1 Ultra-high molecular weight polyethylene having a flexible polymer chain with a viscosity average molecular weight of 1.8 million was dissolved in decalin to obtain a spinning stock solution, and this spinning stock solution was extruded from a spinning device into the atmosphere through a spinneret and cooled. A gel-like fiber was formed, and the gel-like fiber was drawn at a high magnification to produce a multifilament yarn of 1600 denier and 1590 filament.

The above-mentioned eight-braided rope was braided using the above-mentioned multifilament yarn, immersed in the treatment solution shown in Table 1 below at 20°C, then heated and dried at 60°C for 5 minutes, and then heated at 120"C. It was heat cured for 2 minutes at a temperature, cooled and rolled up.

Table 1 Polyurethane elastomer prepolymer 100 parts TDI crosslinker (12% isocyanate residue) 5 parts dibutyltin dilaurate crosslinking accelerator 3 parts ethyl acetate
200 parts toluene
300 parts (However, for the polyurethane elastomer prepolymer, 1 l:
It was obtained by reacting at a molar ratio of 2 and a temperature of 100° C. for 60 minutes. ) Comparative Example 1 Polyethylene having a flexible polymer chain with a viscosity average molecular weight of 200,000 was spun in the same manner as in Example 1 to obtain a multifilament yarn of 1,600 denier and 1,590 filaments. Impregnation treatment was performed.

Comparative Example 2 Using the same braided rope as in Example 1, it was impregnated with the treatment liquid shown in Table 2 below to produce a resin-impregnated rope.

Table 2 Polyurethane elastomer prepolymer 300 parts 0I Crosslinking agent (12% isocyanate residue) 15 parts Dibutyltin dilaurate Crosslinking accelerator 9 parts Ethyl acetate
200 parts toluene
300 parts Comparative Example 3 Comparative Example 3 was prepared by using the blade lobe not impregnated with resin in Example 1 as it was.

Comparative Example 4 An impregnated rope was manufactured under the same conditions as in Example 1 using aramid fibers.

Example 2 Using the same blade lobe as in Example 1, it was immersed in the treatment solution shown in Table 3 below at 20°C, and then heated and dried at 120°C for 5 minutes.

Table 3 Modified polyethylene (ethyl acrylate/ethylene-3
5 wt%) 100 parts Toluene 500 parts The results of measuring the bending fatigue resistance, abrasion resistance, and water absorption resistance of Example 1.2 and Comparative Examples 1 to 4 are shown in Table 4 below. As is clear from Table 4, both Examples 1 and 2, which meet the requirements of the present invention, are excellent in tensile strength, bending fatigue resistance, and abrasion resistance, and have low water absorption. In contrast, comparative example 1 with a low molecular weight
Comparative Example 2, which had a low resin impregnation rate, had a high water absorption rate, and Comparative Example 3, which had no resin impregnation, had a particularly high water absorption rate. Furthermore, Comparative Example 4 using aramid fibers had low wear resistance and bending fatigue resistance.

Table 1 (Effects of the Invention) The present invention provides a blade lobe obtained by braiding high-strength, high-modulus fibers made of ultra-high molecular weight polyolefin with a viscosity average molecular weight of 500,000 or more. Since the surface is coated with resin and at least 5% of the volume of the blade lobe from the outer periphery to the center is impregnated with the same resin, the blade lobe has good bending fatigue resistance, abrasion resistance and water absorption resistance. It is suitable for use as a lead rope outdoors.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a bending fatigue resistance tester, and FIG. 2 is an explanatory diagram of an abrasion resistance tester. 1: Test rope, 2.5 guide roller, 3: Drive pulley, 4: Weight, 6: Sand grinder

Claims (1)

[Scope of Claims] [1] A braided rope obtained by braiding fibers made of ultra-high molecular weight polyolefin having a viscosity average molecular weight of 500,000 or more, the surface of the braided rope being coated with a resin, and the outer periphery of the braided rope being coated with a resin. A composite braided rope, characterized in that at least 5% of the volume of the braided rope from the center to the center is impregnated with the above-mentioned resin.