JPH0699876B2 - High strength rope - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a high-strength rope having high strength and high elastic modulus and excellent in wear resistance.

<Prior art and problems> As fibers for ropes, natural fibers such as hemp,
Synthetic fibers such as polyethylene, polypropylene and nylon have been used. These fibers have a single yarn strength of 10 g / d
In order to make a high-strength rope, it was necessary to increase the diameter of the rope or use steel wire.

If the rope diameter becomes thick, there is a problem that it will be difficult to handle or it will be heavy, and if a steel wire enters, it will cause insulation failure in addition to weight, and it cannot be used in the field of using electricity, and it will rust. There was a problem.

Recently developed aromatic polyamide fiber is light weight, 20g /
Although it has a strength exceeding d, it has a difference in the physical properties of the rope when it is dry and wet due to water absorption, has poor wear resistance during use, has a short life, and is of a wet spinning type that uses sulfuric acid and expensive solvents. Therefore, there is a problem that it is economically expensive and it is impossible to obtain a thick fiber having a thickness of more than 15 μm.

<Purpose of the present invention> The purpose of the present invention is to have light weight, high strength, high elastic modulus, no difference in physical properties when dry and wet, and also excellent in abrasion resistance. The purpose of the present invention is to provide a high-strength rope made of elastic fiber.

<Means for Solving Problems> That is, the present invention is the invention described below.

Shows anisotropy when melted, and is (1) aromatic consisting of 20 to 80 mol% of p-hydroxybenzoic acid residue, 10 to 40 mol% of aromatic dicarboxylic acid residue, and 10 to 40 mol% of aromatic diol residue. Polyester, or (2) P-hydroxybenzoic acid residue 20-80 mol% and 2-
Characterized by using fibers having a strength of 23.3 g / d or more and an elastic modulus of 840 g / d or more obtained by melt spinning an aromatic polyester composed of 80 to 20 mol% of hydroxynaphthalene-6-carboxylic acid residue High strength rope.

What is the polyester that exhibits anisotropy when melted in the present invention?
This means that when the polyester sample powder is placed on a heating sample table between two polarizing plates that are orthogonal to each other by 90 ° and the temperature is raised, it has the property of transmitting light in a fluid temperature range. .

Many of such aromatic polyesters are known to consist of aromatic dicarboxylic acids, aromatic diols and / or aromatic hydroxycarboxylic acids and derivatives thereof, but in the present invention, the constituent monomer units are (1 ) 20-80 mol% of p-hydroxybenzoic acid residue, 10-40 mol% of aromatic dicarboxylic acid residue, and 10-40 mol% of aromatic diol residue
Or (2) p-hydroxybenzoaromatic acid residue 20 to 80 mol% and 2-hydroxynaphthalene-6-carboxylic acid residue 80 to 20 mol% are used.

Aromatic dicarboxylic acids include terephthalic acid, isoflutaic acid, 4,4-dicarboxydiphenyl, 2,6-dicarboxynaphthalene, 1,2-bis (4-carboxyphenoxy)
Examples thereof include ethane and the like, as well as the alkyl, aryl, alkoxy, and substitution products of these halogen groups.

Aromatic diols include hydroquinone, resorcin,
4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylethane, 2,2-
Bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, etc. These alkyl, aryl,
Examples thereof include the alkoxy and halogen groups.

If the residue from p-hydroxybenzoic acid is less than 20 mol%, the abrasion resistance of the rope will be poor, and if it exceeds 80 mol%, melt spinning cannot be performed stably. This is 20-80 mol%
The presence of the p-hydroxybenzoic acid residue in (1) is considered to be one of the reasons why it becomes a highly crystalline fiber.

Using these starting materials, the polycondensation reaction is carried out as it is or by esterification with a derivative or the like to reach the polyester of the present invention.

As the polycondensation reaction, known bulk polymerization, solution polymerization, suspension polymerization method or the like can be adopted, and at 150 to 360 ° C., atmospheric pressure or
Polymerization catalyst such as Sb, Ti, Ge compounds under reduced pressure of 10 to 0.1 torr,
A stabilizer such as a phosphorus-based compound or a filler such as TiO ₂ , CaCO ₃ , or talc may be added as the case may be.

The obtained polymer is used as it is, or in the form of powder, which is heat-treated in an inert gas or under reduced pressure to prepare a spinning sample. Alternatively, it can be granulated once with an extruder and used.

A known device can be used for the melt spinning in the present invention. The spinning temperature is 280 to 420 ° C, preferably 30
It is 0 to 400 ° C. If the temperature is lower than this range, a load is applied to the apparatus, the homogeneity of the melt is not sufficient, and conversely, if the temperature is high, a decomposition reaction or the like occurs and stable spinning cannot be performed.

The melt-spun fibers are either left as they are, or after the oil agent or treatment agent is attached, they are wound or drawn off. The obtained fiber can be used as it is, but may be appropriately subjected to an operation of drawing, heat treatment, or a combination thereof.

Since the aromatic polyester fiber used in the present invention is obtained by melt spinning, it is possible to control the diameter and cross-sectional shape of the single fiber according to the application and physical properties by changing the spinneret, discharge conditions, winding conditions and the like. it can.

For example, regarding the cross-sectional shape By using a spinneret having such a spinneret cross section, it is possible to obtain a spinneret having a large surface area, a side groove, or a flat shape.

The strength of single fiber of aromatic polyester fiber is 23,3 g /
The elastic modulus is 840 g / d or more in order to prevent creep deformation and the like.

In the rope of the present invention, it is desirable that at least 50 vol% or more, preferably 70 vol% or more of the fibers forming the rope are composed of the aromatic polyester fiber.

Depending on the use and purpose, other fibers may be mixed in an amount of 50% vol% or less.

Examples of the rope structure include twisted ropes such as three striking, four striking, six striking, and loose striking, braided ropes, or ropes with a special structure such as rock yarn and longline. In order to make the best use of the high strength and high elastic modulus of the single fiber, it is preferable to select a fiber having a small number of twists.

When twisting or knitting, it is effective to attach a sizing agent, an oil agent, a surface treatment agent to the filament, or to apply a polymer coating in some cases. These processes may be performed after making the rope once.

Such surface treatment is effective for the deterioration of physical properties due to friction and wear between the fibers that make up the rope, the wear due to contact with other materials such as the rope and the metal of the fibers during the manufacture and use of the rope, and weather resistance. Have.

<Operations and Effects of the Present Invention> The rope made according to the present invention is lightweight, has high strength and high elastic modulus, and is excellent in non-water absorption, electrical insulation, and abrasion resistance. And compared to conventional ropes, it is finer, stronger, and more flexible, making it easier to handle.

Such high-strength ropes include light bulbs, buoys, boat moorings, towings, stanchions for antennas, rangers, mountaineering ropes, cargo handling ropes, marine exploration, hydrous acid, anchors, fishing ropes, undersea cables, lifting ropes. It can be used in the coating field such as.

<Examples> Examples and comparative examples are shown below in order to explain the present invention in more detail, but these are merely illustrative.
It is not limited to these.

The tensile test of the fiber in the example uses Instron universal testing machine No1180, sample interval 20mm, pulling speed 0.5mm / mi
It was measured by n.

The strength of the rope was measured according to JIS-L-2705.

The abrasion resistance test of the rope was performed by applying a tension of 80 kg to the rope and reciprocating the grindstone in a range of 20 cm in length to measure the number of breaks, and when it did not break, measuring the rope strength. Then, in order to see the difference between dryness and humidity, the rope was immersed in water at 25 ° C for 15 hours, and water was applied during the measurement to create a wet condition.

The optical anisotropy was measured by placing the sample on a heating stage and heating it at 25 ° C./min under polarized light for visual observation.

Example 1 p-acetetoxybenzoic acid 7.20 kg (40 mol), terephthalic acid 2.49 kg (15 mol), isophthalic acid 0.83 kg (5 mol), 4,4'-diacetoxydiphenyl 5.45 kg (20.2 mol) are comb-shaped. The mixture was charged in a polymerization tank having a stirring blade, heated under stirring in a nitrogen gas atmosphere, and polymerized at 330 ° C. for 3 hours. During this period, acetic acid produced was removed, polymerization was carried out with vigorous stirring, and then gradually cooled, and the polymer was taken out of the system at 200 ° C. The polymer yield is 10.88 kg, which is the theoretical yield of 97.
It was 8%.

This is crushed with a hammer mill from Hosokawa Micron Co., 2.5m
The particles were m or less. This was treated in a rotary kiln under a nitrogen atmosphere at 280 ° C. for 5 hours. Optical anisotropy was observed for this polyester at 850 ° C or higher.

Using this polyester, melt spinning was performed by a 25 mm diameter screw type extruder. The nozzle used has a hole diameter of 0.08 m
Spinning was carried out at 365 ° C. with m and 650 holes.

A pale yellow transparent fiber was obtained, which was treated in nitrogen at 320 ° C. for 3 hours. The obtained fiber has a cross section close to a perfect circle,
The strength was 2.8d, the strength was 80.4g / d, the elongation was 2.7%, and the elastic modulus was 1150g / d.

Using this fiber, polyethylene terephthalate 8φ for the core
The cord was placed and a six-strand rope was formed. The rope diameter was 9φ.

Table 1 shows the physical properties of the obtained rope.

Example 2 In the same manner as in Example 1, a polymer was synthesized from 60 mol% of p-acetoxybenzoic acid and 40 mol% of 2-acetoxy-6-naphthalenecarboxylic acid.

Optical anisotropy was observed at 310 ° C or higher, melt spinning at 325 ° C and heat treatment at 300 ° C for 12 hours, 2.3d, strength 23.3g
/ d, the elongation was 2.8%, and the elastic modulus was 840 g / d.

Using this fiber, a rope was prepared in the same manner as in Example 1,
The physical properties are shown in Table 1.

Comparative Example 1 Using poly-p-phenylene terephthalamide fiber, a rope was prepared in the same manner as in Example 1 and evaluated. This fiber is 1.
52d, 1.000 filament, strength 23.2g / d, elongation 3.6%, elastic modulus 682g / d. The results are shown in Table 1.

Comparative Example 2 In the same manner as in Example 1, a polyester was synthesized from 2,5-diacetoxybiphenyl and terephthalic acid. (A p-hydroxybenzoic acid residue is not contained.) This polyester shows optical anisotropy at 340 ° C or higher. It was spun at 360 ° C. The other conditions were the same as in Example 1. When heat treatment was also performed under the same conditions, 2.4d, strength 20.3g / d, elongation 3.3.
%, And the elastic modulus was 640 g / d. Table 1 shows the results of evaluation of physical properties by making ropes from this.

Claims (1)

[Claims] 1. Anisotropy when melted, (1) 20-80 mol% of p-hydroxybenzoic acid residue, 10-40 mol% of aromatic dicarboxylic acid residue, and 10-40 mol of aromatic diol residue. % Of aromatic polyester, or (2) 20-80 mol% of P-hydroxybenzoic acid residue and 2-
Characterized by using fibers having a strength of 23.3 g / d or more and an elastic modulus of 840 g / d or more obtained by melt spinning an aromatic polyester composed of 80 to 20 mol% of hydroxynaphthalene-6-carboxylic acid residue High strength rope.