KR101582853B1 - Flame-retardant resin composition for abs sensor cable sheath for vehicle and abs sensor cable for vehicle comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition for an automotive ABS sensor cable sheath and an automotive ABS sensor cable made therefrom. In one embodiment, the thermoplastic resin composition for automobile ABS sensor cable sheath comprises (A) 100 parts by weight of a polyurethane elastomer, (B) 0.5 to 10 parts by weight of a crosslinking auxiliary and (C) 0.1 to 10 parts by weight of a stabilizer, Wherein the polyurethane elastomer (A) comprises a polyurethane elastomer having a glass transition temperature (Tg) of -35 占 폚 or less and the crosslinking aid (B) is a triallyl isocyanurate (TAIC), a triallyl cyanurate (TAC), a trimethylopropane trimethacrylate And TMPTA (Trimethylolpropane Triacrylate).

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition for an automobile ABS sensor cable sheath, and an automobile ABS sensor cable including the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a thermoplastic resin composition for an automotive ABS sensor cable sheath and an automotive ABS sensor cable made therefrom. More particularly, the present invention relates to a thermoplastic resin composition for a cable sheath of an automobile ABS (Anti-Lock Breaking System) sensor which is excellent in adhesion with an insulated electric wire including a sheath including a polyurethane elastomer and excellent in flame retardancy and heat resistance, To an automotive ABS sensor cable.

In the case of a vehicle (automobile) equipped with a general braking device, when the vehicle suddenly stops, the rotation of the vehicle wheel stops, the slip of the wheel occurs, the direction stability of the vehicle body is lost, Steering does not work even when the handle is operated during braking. ABS (Anti-Lock Breaking System) has been developed to ensure the stability and controllability of braking of such a vehicle. When the ABS is installed in the vehicle, the locking and unlocking of the wheel is repeated electronically several tens of times per second, The braking distance can be further shortened by maximizing the friction between the ground and the tire wheel.

Such an ABS includes a brake control module for controlling the brake, an ABS sensor (wheel speed sensor) for detecting the rotation speed or speed of the wheel and sending it to the ECU, a brake switch for sensing the braking force of the brake, And an ABS warning lamp informing the driver if any abnormality is found. The ABS sensor cable (hereinafter referred to as sensor cable) is the cable that transmits signals to the brake control module through this ABS sensor.

These sensor cables are repeatedly braked, operated, suddenly braked, and operated during operation of the vehicle due to the characteristics of the ABS system, and the risk of disconnection is very high due to the stress caused by the bending and vibration of the road surface due to the characteristics of the vehicle. This is used in an environment where water is adhered to the cable sheath or water is frozen. In addition, when the brake is operated, it is also exposed to a high temperature environment. That is, shortening the life of the ABS sensor cable shortens the service life of the automobile braking system, reduces the operating effect, and causes malfunctions. Therefore, the ABS sensor cable for automobiles is considered to be important in bending resistance and heat resistance. In recent years, in accordance with the weight reduction and high performance of automobile parts, ABS sensor cable for automobiles satisfying light weight, thinning, high internal resistance, And a cable using the same.

Meanwhile, the ABS sensor cable has an inner sheath formed on the outer side of one or more insulated wires including a conductor line in the center thereof, and an outer sheath formed on the outer side of the inner sheath. On the other hand, ethylene vinyl acetate or a thermoplastic polyurethane resin is mainly used as the material of the inner sheath. In the case of the ethylene vinyl acetate, since the flame retardancy and the low temperature flexibility are low, it is not suitable for use as an ABS sensor cable for automobile in a low temperature environment. In the case of the thermoplastic polyurethane resin, as the hardness increases, the hard segment increases and the urethane air increases. The urethane group has a C = O bond and has a polarity, and the bonding force between the sheath and the insulated wire is improved by the attractive force Van der Waals force between the molecules. When the urethane groups are increased, hydrogen bonds are generated to pull hydrogen (H) present around oxygen (O), thereby improving the adhesive strength and tensile strength. On the other hand, the lower the hardness of the thermoplastic polyurethane resin is, the more the soft segment becomes, and the soft part having a low glass transition temperature is present in the rubber phase at room temperature, and thus the bending resistance at low temperature is excellent.

An object of the present invention is to provide a thermoplastic resin composition for a sensor cable sheath which is capable of forming a small diameter.

Another object of the present invention is to provide a thermoplastic resin composition for a sensor cable sheath which is excellent in heat resistance, cold resistance, flame retardancy, flexibility and low temperature bending property.

Another object of the present invention is to provide a thermoplastic resin composition for a sensor cable sheath having excellent adhesion between an insulated wire and a sheath.

Another object of the present invention is to provide a sensor cable including the sheath.

It is still another object of the present invention to provide a method of manufacturing the sensor cable.

One aspect of the present invention relates to a thermoplastic resin composition for a sensor cable sheath. In one embodiment, the thermoplastic resin composition for sensor cable sheath comprises (A) 100 parts by weight of a polyurethane elastomer, (B) 0.5 to 10 parts by weight of a crosslinking auxiliary and (C) 0.1 to 10 parts by weight of a stabilizer, Wherein the elastomer (A) comprises a polyurethane elastomer having a glass transition temperature (Tg) of -35 占 폚 or less and the crosslinking auxiliary (B) is a triallyl isocyanurate (TAIC), a triallyl cyanurate (TAC), a trimethylopropane trimethacrylate (TMPTMA) Trimethylolpropane triacrylate).

In one embodiment, the polyurethane elastomer (A) has a Shore hardness (A) of 70 to 95.

The stabilizer (C) may include at least one of a phenol-based, phosphorus-based, amine-based, and sulfur-based antioxidant.

(D) 0.1 to 10 parts by weight of a crosslinking accelerator and (E) 0.1 to 5 parts by weight of a lubricant based on 100 parts by weight of the polyurethane elastomer (A).

The crosslinking accelerator (D) may include at least one of ZnO and MgO, and the lubricant (E) may include at least one of calcium, zinc and amide.

The thermoplastic resin composition for sensor cable sheath further comprises at least one of a polyester-based, polycarbonate-based, polyether-based and polystyrene-based resin having a glass transition temperature (Tg) of -35 캜 or less.

Another aspect of the present invention relates to a sensor cable including the sheath. In one embodiment, the sensor cable comprises an inner conductor wire; An insulated electric wire surrounding the internal conductor line; A first sheath surrounding the insulated electric wire; And a second sheath surrounding the first sheath, wherein the first sheath includes the thermoplastic resin composition for the sensor cable sheath described above.

Another aspect of the present invention is to provide a method of manufacturing the sensor cable. In one embodiment, the method of manufacturing the sensor cable includes: kneading the thermoplastic resin composition for sensor cable sheath described above; Forming a first sheath by extruding the kneaded composition outside an insulated wire including a conductor therein; Extruding a second sheath outside the first sheath to produce an intermediate formed body; And irradiating the intermediate formed body with electron beam irradiation.

The sensor cable including the sheath made of the thermoplastic resin composition of the present invention is more cured and lightweight than the conventional ABS sensor cable for automobiles and has excellent heat resistance, cold resistance, flame retardancy, flexibility and low temperature flexibility, And the adhesion between the sheaths is excellent.

1 shows a sensor cable according to one embodiment of the present invention.
2 is a cross-sectional photograph of a sensor cable according to one embodiment of the present invention.
Fig. 3 shows a bending test method for the examples and comparative examples according to the present invention.
Fig. 4 shows the adhesion test method for Examples and Comparative Examples of the present invention.
5 shows a method of inserting a grommet into a conventional sensor cable.
FIG. 6 is a photograph comparing the jumping phenomenon of the sensor cable sheath when the grommet is inserted according to the embodiment of the present invention and the comparative example.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be exemplary, self-explanatory, allowing for equivalent explanations of the present invention.

One aspect of the present invention relates to a thermoplastic resin composition for a sensor cable sheath. In one embodiment, the thermoplastic resin composition for a sensor cable sheath may comprise (A) a polyurethane elastomer, (B) a crosslinking aid, and (C) a stabilizer. (A) 100 parts by weight of a polyurethane elastomer, (B) 0.5 to 10 parts by weight of a crosslinking auxiliary and (C) 0.1 to 10 parts by weight of a stabilizer, wherein the polyurethane elastomer (A) has a glass transition temperature ) Is -35 占 폚 or lower and the crosslinking auxiliary (B) may include at least one of TAIC (Triallyl Isocyanurate), TAC (Triallyl cyanurate), TMPTMA (Trimethylopropane Trimethacrylate) and TMPTA (Trimethylolpropane Triacrylate).

Hereinafter, the thermoplastic resin composition for a sensor cable sheath according to the present invention will be described in detail.

(A) a polyurethane elastomer

The polyurethane elastomer (A) may be included in the present invention for the purpose of imparting excellent flexibility, durability, flexibility, low temperature flexibility and flame retardancy.

In one embodiment, the polyurethane elastomer (A) comprises a hard segment having an aromatic or aliphatic chain linked by a urethane bond and a soft segment comprising at least one of polyester, polycarbonate, polyether and polystyrene. . ≪ / RTI >

The hard part can be prepared by a conventional method. For example, polyol monomers such as diols such as aromatic or aliphatic diisocyanate monomers and monomers that extend chains can be polymerized.

Polyurethane elastomer used in existing sensor cables is made of high-hardness polyurethane elastomer with a glass transition temperature (Tg) of -35 ℃ or higher and high room temperature properties. In the present invention, the polyurethane elastomer (A) may have a glass transition temperature (Tg) of -35 캜 or lower. In a specific example, the polyurethane elastomer (A) may have a glass transition temperature (Tg) of -35 ° C to -55 ° C. When the glass transition temperature is higher than -35 占 폚, the low-temperature characteristics of the present invention are lowered and can not be easily used in a low-temperature environment.

In one embodiment, the Shore hardness (A) of the polyurethane elastomer (A) may be 70 to 95. Preferably 75 to 90, can be used. The balance of the adhesive force, tensile strength, hardness, density, low-temperature characteristics, flexibility and the like of the sheath of the present invention can be excellent in the hardness range.

(B) Crosslinking auxiliary

The crosslinking assistant (B) may be added for the purpose of increasing the crosslinking efficiency during the crosslinking step of the present invention, uniform crosslinking, and improving adhesion and adhesion between the sheath and the insulated electric wire of the present invention.

As the crosslinking auxiliary (B) in the present invention, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylopropane trimethacrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA) can be used. These may be used alone or in combination of two or more. Preferably, one or more of TMPTMA and TAIC can be used.

When the crosslinking aid (B) is used, the crosslinking efficiency is excellent and the crosslinking is uniform. After the crosslinking, the adhesion between the sheath of the present invention and the insulated electric wire to be described later can be further improved.

In one embodiment, the crosslinking auxiliary (B) may be contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the polyurethane elastomer (A). Preferably 1 to 5 parts by weight. More preferably 1 to 3.5 parts by weight. In the above range, the crosslinking efficiency is excellent, and the cross-linked sheath of the present invention can have excellent adhesion and adhesiveness. When the crosslinking aid (B) is contained in an amount of less than 0.5 parts by weight, the crosslinking degree is lowered, and when it exceeds 10 parts by weight, durability and abrasion resistance may be lowered.

(C) Stabilizer

The stabilizer (C) is an antioxidant and may be included for the purpose of preventing decomposition of raw materials during processing of the composition of the present invention, improving heat resistance, and preventing aging of electric wires and cables.

In the present invention, the stabilizer (C) may be selected from phenol-based, phosphorus-based, amine-based and sulfur-based antioxidants.

Examples of the phenolic antioxidants include sterically hindered phenolic stabilizers such as alkylated monophenols, polyphenols or alkylation products of dienes and polyphenols, but are not limited thereto. Do not. For example, 2,6-di-tetra-butyl-4-methylphenol, octadecyl-3- (3,5-di- -Bis (4'-hydroxy-3'-t-butylphenyl) butanoic acid) glycol ester and tetrabis (methylene-3- ) Methane and 1,2-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamoyl) hydrazine ), But the present invention is not limited thereto.

As the phosphorus antioxidant, phosphorus ester compounds, aromatic phosphine compounds, and the like may be used, but the present invention is not limited thereto.

As the amine antioxidant, N, N'-di-2-naphthyl-p-phenylenediamine and the like can be used, but the present invention is not limited thereto.

Examples of the sulfur-containing antioxidant include diaryl 3,3-thiodipropionate, diamylmethyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thioiodipropionate, pentaerythritol-tetrakis- (beta -lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) 8,10-tetraoxaspiro [5,5] undecane, and the like, but the present invention is not limited thereto.

In one embodiment, the stabilizer (C) may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyurethane elastomer (A). Preferably 0.5 to 5 parts by weight. More preferably 0.5 to 3.5 parts by weight. Within this range, the effect of preventing aging, deterioration and decomposition of the polymer can be greatly increased. When the stabilizer (C) is contained in an amount of less than 0.1 part by weight, the oxidation preventing effect is insignificant and the heat resistance is decreased. When the stabilizer (C) is contained in an amount exceeding 10 parts by weight, the physical properties and mechanical strength of the present invention may be lowered.

In another embodiment, the stabilizer (C) may comprise a phenolic antioxidant and a phosphorus antioxidant in a weight ratio of 1: 0.1 to 1: 2. When the content is in the above range, the synergistic effect between the components is excellent, so that the composition of the present invention is excellent in compatibility with the composition of the present invention, and thus the effect of aging, deterioration and prevention of decomposition of the polymer can be greatly increased.

In another embodiment of the present invention, the thermoplastic resin composition for sensor cable sheath may further comprise (D) a crosslinking accelerator and (E) a lubricant.

(D) Crosslinking accelerator

The crosslinking accelerator (D) may be included for the purpose of promoting crosslinking of the present invention. As the crosslinking accelerator, ZnO and MgO may be used. These may be included singly or in combination. In one embodiment, the surface area of the crosslinking accelerator may be from 40 m 2 / g to 150 m 2 / g. In the above range, the crosslinking promoting property and workability can be excellent.

In one embodiment, the crosslinking accelerator (D) may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyurethane elastomer (A). Preferably 0.5 to 5 parts by weight. Within the above range, the crosslinking efficiency can be excellent without impairing the physical properties of the present invention.

(E) Lubricant

The lubricant (E) may be included for the purpose of improving the fluidity and processability of the composition of the present invention. As the lubricant (E) in the present invention, a conventional lubricant may be used. For example, calcium-based, zinc-based and amide-based lubricants. These may be used singly or in combination of two or more, but are not limited thereto.

In one embodiment, the lubricant (E) may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyurethane elastomer (A). Preferably 0.1 to 3 parts by weight. Within the above range, the workability can be excellent without impairing the physical properties of the present invention.

In addition, the composition of the present invention may further comprise (F) a polyolefin resin having a glass transition temperature (Tg) of -35 캜 or lower. For example, it may include a polyolefin resin (F) having a glass transition temperature (Tg) of -35 ° C to -55 ° C.

In one embodiment, the polyolefin resin (F) may further comprise a polyester-based, polycarbonate-based, polyether-based or polystyrene-based resin. These may be used singly or in combination of two or more, but are not limited thereto. When the resin of the above kind is included, it is excellent in compatibility with the composition and synergistic effect, and can be excellent in properties such as heat resistance, flame retardancy, flexibility and low temperature bending property.

In one embodiment, 5 to 50 parts by weight of the polyolefin resin may be added to 100 parts by weight of the polyurethane elastomer (A). Preferably 30 to 50 parts by weight. When it is included in the above range, the compatibility and synergistic effect with the composition of the present invention are excellent, and the physical properties such as heat resistance, flame retardancy, bending property and low temperature bending property can be excellent.

Another aspect of the present invention relates to a method of manufacturing the sensor cable. In an embodiment, the sensor cable manufacturing method may include the steps of (a) manufacturing an insulated wire, (b) kneading the composition, (c) forming a first sheath, (d) have.

More specifically, the step of kneading the thermoplastic resin composition for sensor cable sheath described above; Forming a first sheath by extruding the kneaded composition outside an insulated wire including a conductor therein; Extruding a second sheath outside the first sheath to produce an intermediate formed body; And irradiating the intermediate formed body with electron beam irradiation.

Hereinafter, the method of manufacturing the sensor cable according to the present invention will be described step by step.

(a) Insulated wire manufacturing step

The insulated electric wire is formed to include a conductor therein. The conductor may be a conventional conductive metal material. For example, at least one of tin, copper, and alloys thereof, but is not limited thereto.

The insulated electric wire (or inner insulator) may be manufactured by including a conventional component. In one embodiment, a composition comprising a polyolefin resin, an inorganic filler, an antioxidant, and a crosslinking aid is kneaded using a biaxial mixer, the strand is cut with water to obtain a pellet, Extruded and coated on the outside of the conductor using a single-screw extruder, and then irradiated with an electron beam to be crosslinked to produce an insulated wire.

As the polyolefin resin, ethylene vinyl acetate (EVA), ethylene methacrylate (EMA), polyethylene (PE), and polypropylene (PP) can be used. These may be used singly or in combination of two or more, but are not limited thereto.

(b) Kneading step

The above step is a step of kneading the thermoplastic resin composition for sensor cable sheath described above. The kneading can be carried out in a conventional manner. In one embodiment, the composition may be melt-kneaded at a temperature of 120 ° C to 200 ° C using a twin screw extruder, hot cut to produce a pellet.

In another embodiment, the composition can be processed in the form of pellets by processing it at a temperature of 120 ° C to 200 ° C using a twin-screw mixer or kneader and underwater cutting the strand.

(c) Sheps  Forming step

In this step, the kneaded composition is extruded to the outside of the insulated electric wire to form a first sheath. At this time, the insulated electric wire may be in a twisted form including one or more. In one embodiment, the kneaded composition may be coated on the outside of one or more twisted twisted insulation wires using a single screw extruder for wire extrusion and cooled to form the first sheath.

(d) Intermediate molding  Manufacturing stage

In this step, a second sheath is formed on the outside of the formed first sheath to produce an intermediate formed body.

In one embodiment, the second sheath may be formed by kneading a composition comprising a polyurethane elastomer and then extruding the composition out of the first sheath using a single-screw extruder for wire extrusion. In one embodiment, the second sheath may be of the same kind as the aforementioned polyurethane elastomer (A). When the polyurethane elastomer (A) is used, excellent external surface and flexibility as well as adhesive strength, tensile strength, hardness, density and low temperature characteristics to the first sheath can be obtained, and the appearance of the present invention can be excellent.

In an embodiment, the extruder may be manufactured by using a tandem extruder in which a wire extruder is located immediately after extrusion and cooling of the first sheath, and a second sheath is directly injected outside the first sheath.

(e) Bridging step

The above step is an electron beam cross-linking step of the intermediate formed body. The electron beam cross-linking can be performed using a conventional electron beam accelerator. In one embodiment, electron beam irradiation can be carried out under conditions of 1 to 2 MeV and 11 to 20 Mrad. When the electron beam is crosslinked in the above range, it can be crosslinked at room temperature, can be crosslinked in a short time reaction, and the action of impurities due to the compounding agent or other decomposition is reduced.

(Hydrogen) existing in the insulated wire at the interface between the first sheath and the insulated wire formed by the composition of the present invention and the urethane groups of the urethane group of the first sheath, The bonding causes hydrogen bonding while arranging, and the sheath and the cable can be reduced in diameter, and the adhesion and heat resistance of the sheath can be further improved.

Another aspect of the present invention relates to a sensor cable manufactured by the sensor cable manufacturing method.

FIG. 1 shows a sensor cable 100 according to one embodiment of the present invention, and FIG. 2 is a cross-sectional photograph of a sensor cable according to one embodiment of the present invention. Referring to FIGS. 1 and 2, in one embodiment, the sensor cable 100 includes inner conductor lines 10a and 10b; Insulated wires (20a, 20b) surrounding the inner conductor wires (10a, 10b); A first sheath 30 surrounding the insulated wires 20a and 20b; And a second sheath 40 surrounding the first sheath 30. The first sheath 30 may be made of the thermoplastic resin composition for sensor cable sheath described above.

1, the conductor wires 10a and 10b are formed at the center of the insulated wires 20a and 20b, and the insulated wires 20a and 20b are twisted by one or more strands, Lt; / RTI >

The sensor cable 100 has an excellent adhesion between the insulated wires 20a and 20b and the first sheath 30 and prevents the sheath 30 or 40 from jamming when inserting the sensor cable 100 into the grommet. The phenomenon can be prevented.

In one embodiment, the adhesion between the twisted insulated wires 20a and 20b and the first sheath 30 may be between 30N and 60N.

In one embodiment, the outer diameter of the sensor cable 100 may be 4.0 to 5.0 mm. Preferably from 4.2 to 4.5 mm. Since the sensor cable 100 of the present invention is excellent in tensile strength, bending property and flame retardancy, it is possible to prevent the occurrence of disconnection due to stress in the vibration and braking operation of the vehicle, It is possible to minimize the increase in the volume of the wire even when the dose increases due to the high functioning. In addition, since the heat resistance is excellent, it is possible to prevent the occurrence of fire of a cable in the event of a fire in a vehicle, and it is excellent in low-temperature characteristics such as low-temperature bending property and can be excellent in the effect of preventing disconnection due to vehicle vibration generated at low temperature of -35 占 폚.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example  1 to 4 and Comparative Example  1 to 7

Specific components of the composition for a sensor cable sheath used in Examples and Comparative Examples of the present invention are as follows.

1st Sheps

(A1) a polyurethane elastomer having a polyether-based soft part and having a hardness of Shore A 95 and a glass transition temperature of -30 ° C.

(A2) polyether-based soft segment and having a hardness Shore A of 85 and a glass transition temperature of -35 占 폚.

(A3) polyurethane elastomer having a hardness Shore A of 75 and a glass transition temperature of -47 占 폚.

(A4) Ethylene vinyl acetate having a vinyl acetate content of 28% by weight, a melting point (Tm) of 75 占 폚 and a Brittleness temperature of -76 占 폚 was used.

(B) Crosslinking aid: TMPTMA was used.

(C) Antioxidant

(C1) Irganox 1010 was used as a phenol antioxidant.

(C2) Irganox 168 was used as a phosphorus antioxidant.

(D) a crosslinking accelerator: ZnO was used.

(E) Lubricant: Amide-based lubricant and calcium (Ca) lubricant were used.

(F) Flame retardant: Mg (OH) ₂ was used.

Insulated wire manufacturing

80 parts by weight of ethylene vinyl acetate (EVA) having a vinyl acetate content of 28% by weight and a melting point (Tm) of 75 DEG C and a melting point (Tm) of 125 DEG C and a melt index of 2.0 g / 10min (ASTM D1238, 230 DEG C, 2.16kg dimension) of high density polyethylene (HDPE), 20 parts by weight, the surface of silane-Mg (OH) ₂ 60 parts by weight of the coated average particle diameter 1㎛, the surface of the silane Al (OH-average particle diameter of the coated 1㎛) ₃ 40 parts by weight of an antioxidant, 0.5 parts by weight of Iganox 1010, 1.5 parts by weight of Iganox 168 and 1024 parts by weight of MD and 1.5 parts by weight of TMPTMA as a crosslinking assistant were melt-mixed using a twin screw mixer, The pellets produced by water-cooling cutting were extruded to a thickness of 0.46 mm on the outside of a tin-copper alloy conductor having a cross-sectional area of 0.25 mm 2 by using a wire single-screw extruder and irradiated under the conditions of 1 MeV and 11 Mrad using an electron beam accelerator, Insulated wires were manufactured.

1st Sheps  Produce

The compositions of the composition ratios shown in Table 1 were melted and kneaded at 120 ° C to 200 ° C using a twin screw extruder and the strand was hot-cut (Comparative Examples 1 to 4), and the mixture was kneaded in a twin-screw mixer or kneader Processed at 120 ° C to 200 ° C, and water-cooled (Examples 1 to 4 and Comparative Examples 5 to 7) to prepare pellets.

Two twisted pairs of the insulated wires thus produced were twisted to a pitch of 10 mm or less to form a twisted pair, and the first sheath composition was coated on the outside with a single shear extruder for wire extrusion as shown in Table 1 so as to have an outer diameter of 3.65 mm , The second sheath was extruded by using a single screw extruder for wire extrusion so as to have an outer diameter of 4.3 mm and irradiated under the condition of 1 to 2 MeV and 11 to 20 Mrad using an electron beam accelerator, A sensor cable of the same type as that of FIG. At this time, the second sheath used a polyurethane elastomer having a polyether-based soft part and having a hardness Shore A of 75 and a glass transition temperature (Tg) of -47 ° C.

In the case of Comparative Example 6, a sensor cable was manufactured in the same manner as in Example 1 except that no crosslinking was performed.

Example Comparative Example One 2 3 4 One 2 3 4 5 6 7 (A1) - - - - 100 - - 100 - - - (A2) - - - - - 100 - - 100 - - (A3) 100 100 100 100 - - 100 - - 100 - (A4) - - - - - - - - - - 100 (B) 2.5 2 2.5 1.5 2.5 2.5 0.1 2.5 2.5 12 One (C1) 0.5 0.5 0.5 0.5 0.5 5 0.5 - 0.1 0.5 0.5 (C2) - One One - - 7 - - - - 0.2 (D) 2 2 2 2 2 2 2 - 2 2 - (E) 0.2 0.2 0.2 0.2 - 0.2 0.2 - 0.2 0.2 0.2 (F) - - - - - - - - - - 5

(Unit: parts by weight)

The properties of the above Examples 1 to 4 and Comparative Examples 1 to 7 were evaluated according to the following evaluation criteria and are shown in Table 2 below.

(1) Extrusion workability: When the first sheath containing the components of Examples 1 to 4 and Comparative Examples 1 to 7 was extruded, whether or not there was a problem was evaluated.

(2) Flexibility: The examples 1 to 4 and the comparative examples 1 to 7 were mounted as shown in Fig. 3, loaded under a load of 1 kgf, and tested under the conditions of a bending angle of 90 degrees and a speed of 30 turns / min, The cable turns 90 degrees to the left and the right until it becomes disconnection. The number of times is measured and the number of times is measured. When the number of times is more than 50,000 times, the sensor cable internal conductor is not broken. Respectively.

(3) Cold resistance: Each of Examples 1 to 4 and Comparative Examples 1 to 7 was taken in an appropriate length, placed in a low-temperature bath at -45 ± 2 ° C, held for 3 hours, And the surface was irradiated to observe whether or not there was crack. Then, when there was no crack for 1 minute at 1,000 V, crack occurred on the surface after the low temperature bending, or X Respectively.

(4) Low-temperature Flexibility: The above Examples 1 to 4 and Comparative Examples 1 to 7 were each taken in an appropriate length, placed in a low-temperature bath at -35 占 폚, bent more than two million times by the travel distance (65 mm) , And when the cable conductor was disconnected, it was judged as X.

(5) Abrasion resistance: The above Examples 1 to 4 and Comparative Examples 1 to 7 were taken at a length of about 900 mm and fixed, and a load of 450 gf was applied to the abrasive tape of 150 G specified in KS L 6002 (abrasive cloth) , The tape was moved at a speed of 1500 mm / min to determine the length of the tape until the conductor and the tape were in contact with each other.

(6) Adhesion (1): Three test samples each having a length of 100 mm were prepared for each of Examples 1 to 4 and Comparative Examples 1 to 7 above. An insulator having a length of 25 mm (A to B section in Fig. 4) was cut from one end of the conductor inside the sample, and then carefully peeled off. Then, the test sample was cut at the point C in FIG. 4 so that the length was 75 mm, and the 35 mm section between B and C was not influenced by the outside. As shown in FIG. 4, a test fixture including a metal plate having a circular hole having a diameter similar to that of the conductor of the sample was prepared, and a tensile tester at a speed of 250 mm / mn was used to conduct friction between the test apparatus itself and the test sample So that the test sample can be pulled out. The test specimen was pulled to the test fixture as shown in FIG. 4, and the applied force (F) was recorded while pulling the test specimen at a speed of 250 mm / min while causing no friction between the test apparatus and the conductor. If a flexure occurs in a 35 mm length of insulation (between B and C) while sliding, prepare a new test sample with a length of 25 mm and repeat this test procedure. At this time, when the applied force F was within the range of 30 N to 60 N,

Adhesion (2): Fig. 5 shows a typical grommet insertion method of a sensor cable. Referring to FIG. 5, when the sensor cable is inserted into the grommet, the sheath is pushed when the degree of tightness is low, and the length deviation occurs. When the degree of tightness is excessively high, sheathing with the insulator is prevented. The sensor cables of Examples 1 to 4 and Comparative Examples 1 to 7 were subjected to a grommet insertion test as shown in FIG. 5, and when the sheath outside the insulated wire was pushed to 1 mm or less, The results are shown in Table 2 and FIG.

(7) Flame Retardancy (1): The above Examples 1 to 4 and Comparative Examples 1 to 7 were taken to have a length of about 300 mm and supported horizontally. Flames were irradiated until the front end of the flame source was burned to the bottom of the center of the sample within 10 seconds And the digestion time of the sample was examined within 30 seconds to see if it was digested within 15 seconds.

Flame resistance (2): Examples 1 to 4 and Comparative Examples 1 to 7 were taken to have a length of about 300 mm, supported horizontally, and the flame was gently removed until the front end of the flame source was burned to the bottom of the center of the sample within 30 seconds It was observed whether the digestion time of the post-test sample was 15 seconds or less.

Example Comparative Example One 2 3 4 One 2 3 4 5 6 7 Extrusion workability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Flexibility ○ ○ ○ ○ ○ ○ ○ ○ ○ X ○ Cold resistance ○ ○ ○ ○ X ○ ○ X ○ ○ X Low temperature flexibility ○ ○ ○ ○ X X ○ X ○ X X Abrasion resistance ○ ○ ○ ○ X X ○ X X X X Adhesion (1) ○ ○ ○ ○ ○ X X ○ X X ○ Adhesion (2) ○ ○ ○ ○ ○ X X ○ X X ○ Flammability (1) ○ ○ ○ ○ ○ ○ X X X X X Flammability (2) ○ ○ ○ ○ ○ ○ X X X X X

Referring to Table 2, it was found that the properties of Comparative Examples 1 to 7, which were outside the content range of the present invention or contained some components, were lower than those of Examples 1 to 4.

Fig. 6 is a photograph showing a comparison of the bowing phenomenon of the sensor cable sheath when the grommet is inserted in Example 1 of the present invention (Fig. 6 (b)) and Comparative Example 3 of the present invention (Fig. 6 (a)). Referring to FIG. 6, in the case of Comparative Example 3 using a polyurethane elastomer having a Tg value higher than -35 ° C, it was found that the room temperature property and the adhesion between the sheath and the insulated wire were lowered, I could.

Referring to Table 2, in Comparative Example 6 in which a polyurethane elastomer having a Tg value lower than -35 占 폚 was applied, the adhesiveness, low-temperature bending property and flame retardancy were lowered than in Examples 1 to 4, .

Further, in the case of the sensor cable including the sheath of Comparative Example 7 to which ethylene vinyl acetate was applied, it was found that the adhesion was satisfactory due to the increase in polarity, but the flame retardancy, low temperature bending resistance and abrasion resistance were lower than those of Examples 1 to 4 there was.

10a, 10b: inner conductor wire 20a, 20b: insulated wire
30: first sheath 40: second sheath
100: Sensor cable

Claims (8)

(A) 100 parts by weight of a polyurethane elastomer, (B) 2.5 to 10 parts by weight of a crosslinking auxiliary, (C) 0.5 to 5 parts by weight of a stabilizer, (D) 0.1 to 10 parts by weight of a crosslinking accelerator, By weight,
The polyurethane elastomer (A) has a glass transition temperature (Tg) of -55 ° C to -35 ° C, a Shore hardness (A) of 70 to 95,
The crosslinking auxiliary (B) includes at least one of TAIC (Triallyl Isocyanurate), TAC (Triallyl cyanurate), TMPTMA (Trimethylopropane Trimethacrylate) and TMPTA (Trimethylolpropane Triacrylate)
Wherein the crosslinking accelerator (D) comprises at least one of ZnO and MgO, and the lubricant (E) comprises at least one of a calcium-based, zinc-based and amide-based thermoplastic resin composition.
delete The thermoplastic resin composition for a sensor cable sheath according to claim 1, wherein the stabilizer (C) comprises at least one of a phenol-based, phosphorus-based, amine-based and sulfur-based antioxidant.
delete delete The thermoplastic resin composition for a sensor cable sheath according to claim 1, wherein the thermoplastic resin composition for sensor cable sheath further comprises at least one of a polyester-based, polycarbonate-based, polyether-based and polystyrene-based resin having a glass transition temperature (Tg) Wherein the thermoplastic resin composition is a thermoplastic resin composition for a sensor cable sheath.
Internal conductor wire;
An insulated electric wire surrounding the internal conductor line;
A first sheath surrounding the insulated electric wire; And
And a second sheath surrounding the first sheath,
Wherein the first sheath comprises the thermoplastic resin composition for a sensor cable sheath according to any one of claims 1, 3 and 6.
Kneading the thermoplastic resin composition for a sensor cable sheath according to any one of claims 1, 3, and 6;
Forming a first sheath by extruding the kneaded composition outside an insulated wire including a conductor therein;
Extruding a second sheath outside the first sheath to produce an intermediate formed body; And
And irradiating the intermediate molded body with electron beam irradiation.

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