JPH01239182A - Compounded ribbon-like article - Google Patents

Abstract

PURPOSE:To obtain a compound ribbon-like article having excellent flexing resistance, wear resistance, corrosion resistance, insulating properties and lightweight properties, by coating high-strength cords having low elongation, using a high-strength aromatic polyester yarn having high modulus of elasticity, with a thermoplastic resin. CONSTITUTION:High-strength yarn having low elongation comprising an aromatic polyester compound capable of forming an anisotropic melt is made into ribbon-like articles and further the ribbon-like articles are coated with a thermoplastic resin (preferably one having 400-15,000kg/cm<2> stiffness modulus).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coated composite string-like article of high strength and low elongation cord using aromatic polyester fibers having high strength and high modulus of elasticity. The company supplies coated composite string-like products that have superior bending resistance, abrasion resistance, corrosion resistance, insulation properties, and lightness compared to other metal wires.

[Conventional technology]

Conventional wires are made by aligning thin metal wires, so when used in related parts such as automobiles, there have been problems with bending resistance, corrosion resistance, insulation, light weight, etc. On the other hand, in recent years, fibers made of various polymer compounds with high strength and low elongation have been developed, and fibers made of various polymer compounds with high strength and low elongation have been developed. It began to be used as a substitute for wire and other products. These fibers are mainly aramid fibers, high molecular weight polyethylene fibers, carbon fibers, and glass fibers.

In particular, aramid fibers are attracting attention because of their good balance between performance and cost.

[Problem to be solved by the invention]

However, the above-mentioned high-strength, low-elongation fibers can be used to produce multifilament untwisted yarns, pre-twisted single yarns, aligned yarns, twisted yarns, braids made of multiple of these yarns, or string-like products such as cords and lobes made of multiple of these yarns. However, it had the disadvantage of poor bending fatigue resistance and abrasion resistance.

Therefore, by first impregnating such a string-like article with a polyurethane elastomer resin and then covering it with a thermoplastic resin, the high-strength, low-elongation fibers can be directly fused with each other or with a support such as a roller. Attempts have been made to avoid this and improve bending fatigue resistance and wear resistance. (JP-A-62-53495, JP-A-62-78276) However, the poor bending fatigue resistance and abrasion resistance of high-strength, low-elongation fibers themselves have not yet been improved; It has been desired to develop high-strength, low-elongation fibers with improved properties and abrasion resistance.

[Means to solve the problem]

In the present invention, high-strength, low-elongation fibers (hereinafter referred to as aromatic polyester fibers) made of an aromatic polyester compound capable of forming an anisotropic melt are made into string-like products, and the string-like products are made of thermoplastic resin. It is a composite string-like product obtained by coating with.

That is, the present invention uses aromatic polyester fibers, which have significantly improved bending fatigue resistance and abrasion resistance than conventional aramid fibers, for string-like products, thereby increasing the bending fatigue resistance and wear resistance of the resulting composite string-like products. It is based on the discovery that wear resistance can be significantly improved.

The aromatic polyester compound capable of forming an anisotropic melt referred to in the present invention is a polymer compound whose main components are aromatic diol, aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid, etc. It exhibits optical anisotropy. Such characteristics can be easily recognized by heating a sample placed on a hot stage in a nitrogen atmosphere and observing the transmitted light.

Preferred examples of aromatic polyester compounds capable of forming anisotropic melts for use in the present invention are those consisting of the repeating component combinations shown below.

OOO o 0 0 The fact that aromatic polyester fibers having higher strength and lower elongation than conventional polyester fibers for clothing can be obtained from the above aromatic polyester compound by melt spinning method is disclosed in Japanese Patent Application Laid-Open No. 54-7.
No. 7691, JP-A-50-43223, JP-A-58-
No. 191219 and the like.

It is disclosed in Japanese Patent Publication No. 55-20008 that strength and thermal stability can be further improved by heat-treating the atoms after rough spinning in an inert gas atmosphere such as nitrogen.

The effects of the present invention are most clearly exhibited in the following [I]
, (the portion consisting of repeating structural units of III is 80 mol%
The above polymers are particularly aromatic polyester compounds having a component strength of 5 to 45 mol % [■].

In addition, as the third component, for example, one of the structural units listed below.
The content may be 20 mol% or less.

oo o.

-+ O-@/-O+ (J +, ±0 millet O+ A method for spinning fibers from this compound is described in Japanese Patent Application No. 31166/1983.
Details are given in issue 8.

The string-like product of the present invention can be used in combination with high strength and low elongation fibers other than aromatic polyester fibers, and examples of these fibers include aramid fibers, carbon fibers, glass fibers, etc. .

The form of the string-like product can be the same as the shape used for conventional wires and aramid fibers.
It is preferable to use a pre-twisted single yarn, a drawn yarn made of a plurality of these yarns, a twisted yarn, a braided cord, or a cord or rope made of a plurality of these yarns.

Further, in order to improve the shape retention and abrasion resistance of the string-like article, it is also good to wrap the string-like article with fibers made of thermoplastic resin. There are no particular restrictions on the fibers made of this thermoplastic resin, but it is preferable that the fibers have low friction, heat resistance, high strength, and flexibility because they do not interfere with the basic performance of aromatic polyester fibers. family polyester fiber, aramid fiber.

Examples include polyethylene terephthalate fiber, nylon fiber, polyvinyl alcohol fiber, and acrylic fiber.

Methods of wrapping these fibers around the string-like core include arranging them in filament form around the core, wrapping them in a bag net or braided net around the core yarn, and wrapping the fibers around the core yarn to cover them. This can be done by

In the case of a string-like product, wear between the filaments of aromatic polyester fibers can be prevented by using a wax-based finishing oil to lower the coefficient of friction between the fibers.

Furthermore, as disclosed in JP-A No. 62-78276, after applying 0.05 to 10% by weight of a reactive brimer containing a reactive epoxy group or incyanate group to a string-like article, a polyurethane elastomer resin is applied. By adhering 0.5 to 20% by weight and heating and curing, each fiber may be covered with a polyurethane elastomer resin to reduce interfiber friction.

It is necessary to coat the string-like article with a thermoplastic resin to avoid abrasion caused by the aromatic polyester fibers of the string-like article coming into direct contact with objects. Thermoplastic resins that can be used for this coating include polyurethane elastomers, ionomer resins, polyamide resins, and the like. Examples of the polyurethane elastomer resins include Kurami A7L (manufactured by Kuraray Co., Ltd.), Elastolan (manufactured by Nippon Elastolan Co., Ltd.), Pandesox (manufactured by Inu Nippon Ink Chemical Co., Ltd.), and examples of the polyester elastomer resins include Hytrel (manufactured by Toshiba Co., Ltd.). Ionomer resins include Surlyn (manufactured by DuPont) and Mitsui DuPont Polychemicals, etc. Polyamide resins include Nylon 12, which has a small flexural modulus. UBE Nylon 12 (manufactured by Ube Industries, Ltd.) and the like can be used.These resins preferably have a bending modulus of 400 to 15,000 ky/d.4
If it is less than 0.0 kglc1, it may adhere to other objects depending on the use as a composite string-like product, and if it is less than 1.
If it exceeds 5000 kQ/d, the composite string-like product becomes too hard and its bending fatigue resistance deteriorates.

A general extrusion molding machine for covering electric wires can be used to coat the string-like article with these thermoplastic resins.

According to the present invention, by coating a string-like article made of aromatic polyester fiber with high strength and low elongation with a thermoplastic resin,
It has now become possible to provide a composite string-like product that has significantly improved bending fatigue resistance and abrasion resistance compared to conventional composite string-like products made of metal wires and polyamide fibers.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these Examples.

The bending fatigue resistance test described in the examples refers to the bending fatigue resistance test using the testing machine shown in Figure 1.
)) to the string diameter (d) is 25, the tensile force is 2 to 4 kg, and the rotation speed of the reversing pulley is 300 times/min.
After 10,000 reciprocations, the breaking strength was measured. In addition, the abrasion resistance test involves aligning 10 composite string-like products, twisting them 1.5 times between the reversing pulley and the free roller at the other end, and installing them in a figure-8 shape.
Twisting abrasion test in which a load of kg is applied and a reciprocating pulley is used to twist a composite string at a speed of 76 times per minute, and the number of times until breakage is measured, and one end of one composite string is fixed. Then apply a load of 1/10 Q/d to the other end, and make a diameter of 10
G! A grinder abrasion test was conducted in which a round whetstone of No. 1 was rotated at a contact angle of 100 degrees, a contact length of 9C+m, and a rotational speed of 100 times/min, and the number of rotations until cutting was measured.

Example 1 An aromatic polyester polymer containing the structural units CI) and (II) in a 70/30 mole % ratio was used for melt spinning. The physical properties of this polymer were y7 inh = 6.0 dl/g MP = 278°C. Here, ηinh is the intrinsic viscosity, which is 60 to 0.1% by weight when the sample is dissolved in pentafluorobenol.
(80°C) and 60°C in a constant temperature bath using an Utsbelohde viscometer, and calculated using the following formula.

r) inh = In(77tel)/e[ηr
el: relative viscosity, C: concentration of the measured solution] and MP:
It is the melting point and the endothermic peak temperature measured by IJO8.

The conditions for melt spinning are 320 with a 300-hole spinneret.
Discharged from the spinning head at ℃, 151 at a winding speed of 800 m
A filament of 5 dr/300 f was obtained.

This spinning yarn is wound on a perforated bobbin at a winding density of 0. s 7 g/
Wrap with cc, 1 hour at 260℃, 270℃ to 280℃
Heat treatment was performed from 280° C. to 285° C. for 5 I￥f for 3 hours. The mechanical performance of the obtained heat treatment system is as follows: yarn denier (1) l(): 1500clr strength (L
ET): 25.5 y/d elongation (DB) 73
．． 6% Initial modulus (IM): 590 Q/d.

Bunacol EX-313 (manufactured by Nagase Kasei Kogyo Co., Ltd.), which is an aqueous dispersion of a jepoxy compound, was applied to this heat treatment system and dried so that the pure amount of the compound was 1% by weight.
00 times/M of twisting to create a string-like product with a screw diameter of 35;
Nylon 12 resin ([JBE Nylon 12, product number 3035
JL11, a flexural modulus of elasticity of 7000 kg/clt, manufactured by Ube Industries Co., Ltd., was coated at 200°C to obtain a composite string-like product having a coating with a thickness of 0.2 mm.A composite string-like product made in this way. Table 1 shows the test results of bending fatigue resistance and wear resistance.

Example 2 The following structural unit is CI)/(II)/[ll1) = 6
The physical properties of this polymer were: 77 inh = 4.9 dVg MP = 298°C. This polymer was spun in the same manner as in Example 1, except that the spinning discharge temperature was 355°C.

The obtained spun yarn was heat treated in the same manner as in Example 1. The mechanical properties of the obtained heat treatment system are DB=150
5dr DT = 18.1 g/d L)E = 3.296 IM = s76a/d.

Bunacol EX-313 (manufactured by Nagase Kasei Kogyo Co., Ltd.), which is a dispersion aqueous solution of a jepoxy compound, was attached to this heat treatment system and dried so that the pure amount of the compound attached was 1% by weight.
The yarn was twisted at a rate of 00 times/M to obtain a string-like product. This string-shaped product was molded using thermoplastic polyurethane elastomer resin (Clamicron U,
Product number 9180, hardness JIS Δ80°, bending modulus ro
(manufactured by Kuraray Co., Ltd.) at 190°C to a thickness of 0.
A composite string-like article with a 2 mm coating was obtained.

Table 1 shows the test results of the bending fatigue resistance and abrasion resistance of this composite string-like article.

Comparative Example 1 Kevlar B (manufactured by DuPont), which is an aramid fiber with high strength and low elongation, was mixed with Bunacol EX-313 (manufactured by Nagase Kasei Kogyo Co., Ltd.), which is an aqueous dispersion of a jepoxy compound, and the pure amount of the compound attached was 1% by weight. After adhering and drying, 100
The yarn was twisted again and made into a string-like product. The mechanical properties of Kevlar B were as follows: D li = 1518 dr l) T = 22.2 g/d DE = 3.6% 1M = 571 g/d.

This string-like product was coated in the same manner as in Example 1 to a thickness of 0.2
A composite string-like article with a coating of mm was obtained. Table 1 shows the test results of the bending fatigue resistance and abrasion resistance of this composite string-like article.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of a testing machine for a bending fatigue resistance test. In the figure, 1 is a string-like object to be tested, 2 is a free roller, 3 is a reversing pulley, and 4 is a spring.

Claims (1)

[Claims] (1) A composite string-like article made by coating a string-like article of high-strength, low-elongation fibers made of an aromatic polyester compound capable of forming an anisotropic melt with a thermoplastic resin.