JPH10269859A - Cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep the airtightness and watertightness between a cable and a molding and prevent damage at a high temperature by extrusion-molding a thermoplastic resin composition mixed with a block copolymer made of polyamide as a hard segment and thermoplastic polyurethane at a specific ratio as a base, and bridging it by electron beam irradiation to form the outermost layer of the covering layers of multi-core twisted wires. SOLUTION: A flexible block copolymer of 100-10 wt.% made of polyamide as a hard segment and thermoplastic polyurethane of 0-90 wt.% are mixed as a base for the resin composition of the outermost layer 2b of multiple covering layers 2 of multi-core twisted wires 1. The inner layer 2a is preferably formed with a thermoplastic polyurethane composition, or an ethylene α olefin copolymer having a prescribed density, or an ethylene vinyl acetate copolymer as a base in view of the adhesiveness to the outermost layer 2b. The heat resistance and a rubber elastic characteristic are improved by the bridging of the covering layers 2, restoring force is generated on a cable 3, and no special sealing countermeasurement is required. The outermost layer 2b is not damaged at a high temperature of 200 deg.C or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cable used for automobiles, robots, electronic devices, and the like, and more particularly, to a cable having excellent mechanical properties and flexibility, and having a terminal portion of the cable connected to various sensors and terminals. The present invention relates to a cable suitable for being molded with a polyamide resin in order to keep the connection portion airtight or watertight after being connected to the cable.

[0002]

2. Description of the Related Art As an insulating layer of a cable used for an automobile, a robot, an electronic device or the like, a thermoplastic polyurethane composition having good mechanical properties and flexibility is employed as a covering material. When connecting a component such as a sensor or connecting an electrode terminal to such a cable, the connection portion and the vicinity thereof are hermetically or watertightly protected by a resin mold (molded body). In order to ensure airtightness and watertightness with the resin mold, it is necessary to use nylon 6, nylon 1 which is excellent in ease of molding and mechanical strength.
2. Polyamide resin such as nylon 66 is often used as a molding material.

[0003]

However, depending on the selection of the covering material and the molding material of the cable, the difference in the thermal shrinkage between the materials may cause the cable to be molded and formed in the heating and cooling process at the end processing of the cable and during use. There is a problem that a gap is formed at the interface of the body, and moisture enters through the gap. If moisture enters from the gap created at the interface, the conductors of the cable will corrode, causing problems such as deteriorating the performance of connected equipment parts.Therefore, various sealing measures must be taken to maintain airtightness and watertightness. Required. For this reason, the workability at the time of terminal processing becomes extremely complicated, and the work required a high degree of skill.

[0004] In order to solve such a problem, it is conceivable to employ a method in which the covering material of the cable is the same as or similar to the molding material. It is not practical because it has poor properties, does not satisfy various characteristics required for a cable, and is expensive. An object of the present invention is to maintain air-tightness and water-tightness at an interface between a cable and a molded body without taking special sealing measures, to prevent corrosion of a cable conductor and performance degradation of connected equipment parts, and Another object of the present invention is to provide a cable in which the outermost layer of the cable is not damaged even in a high-temperature atmosphere of 200 ° C. or higher.

[0005]

In order to achieve the above object, the present invention provides a cable having a coating layer provided on the outside of a multi-core stranded wire in which a plurality of insulated conductors are twisted. The outermost layer is a crosslinked product obtained by extruding a thermoplastic resin composition containing 100 to 10% by weight of a block copolymer containing polyamide as a hard segment and 0 to 90% by weight of a thermoplastic polyurethane as a base resin, and irradiating with an electron beam. A cable is provided that is configured.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The main object required for the cable of the present invention is to provide a cable which can be processed very easily with excellent airtightness and watertightness without impairing the cable characteristics. FIG. 1 illustrates an embodiment of the cable according to the present invention which achieves this object. In FIG. 1, reference numeral 1 denotes a multi-core stranded wire, and the multi-core stranded wire 1 is formed on a stranded wire conductor 1a obtained by twisting 20 tin-plated annealed copper wires having an outer diameter of 0.18 mmφ and finishing the outer diameter to 1 mmφ. , A plurality of (two in FIG. 1) insulated conductors provided with an insulating layer 1b made of polyethylene, polyvinyl chloride, or the like. Reference numeral 2 denotes a coating layer covering the multi-core stranded wire 1, and the coating layer 2 is composed of a plurality of layers (FIG. 1).
The inner layer 2a is made of, for example, a resin composition containing a thermoplastic polyurethane as a base resin, or an ethylene / α-olefin copolymer having a density of 0.86 to 0.90 g / cm ³ , or an ethylene / α-olefin copolymer. It is composed of a resin composition containing at least one selected from the group consisting of vinyl acetate copolymers as a base resin. The outer layer 2b is formed of a crosslinked product obtained by extruding a resin composition containing a block copolymer containing polyamide as a hard segment as a base resin and irradiating with an electron beam, or a block copolymer containing polyamide as a hard segment. It is composed of a crosslinked product obtained by extrusion-molding a resin composition comprising a base resin alone or a block copolymer containing the polyamide as a hard segment and containing 90% by weight or less of a thermoplastic polyurethane, and irradiation with an electron beam. Incidentally, reference numeral 3 in the drawing denotes a cable.

In the cable of the present invention, at least the outermost layer of the coating layer provided on the multifilamentary stranded wire is formed by a crosslinked product of a resin composition containing a block copolymer containing polyamide as a hard segment as a base resin. To
Withstands high temperature and high pressure when molding the cable end part with polyamide resin, the molded body and the outermost layer of the cable coating layer adhere well, and the cable and the molded body resulting from repeated heating and cooling during use are used. The problem of poor airtightness and poor watertightness at the interface is solved.

The outermost coating layer 2b of the cable according to the present invention
The components of the base resin constituting the above are described in detail below. (A) Block copolymer having polyamide as hard segment The block copolymer having polyamide as the hard segment used in the present invention is a thermoplastic elastomer having flexibility, and the soft segment is formed of polyether (polytetramethylene). Glycol and the like) are widely used. These are generally referred to as polyamide elastomers. As such a polyamide elastomer, for example, “Pebaks” (trade name, manufactured by Toray Industries, Inc.)
Are commercially available and can be appropriately selected and used from various grades of commercially available products. However, considering the flexibility and heat resistance of the cable, a hardness of 80 to 90 (Shore A) is preferably used. Furthermore, when blending a polyamide elastomer and a thermoplastic polyurethane described later, if the polyamide elastomer has a melting point close to the softening point of the thermoplastic polyurethane, a mixed state of the two becomes uniform at the time of kneading, and the appearance of the cable extruded is improved. Is preferable since it becomes better.

(B) Thermoplastic polyurethane The thermoplastic polyurethane used in the present invention includes polyester-based urethane resins (adipate, caprolactone-based, polycarbonate-based) and polyether-based urethane resins. For example, a polyether-based urethane resin is preferable. The hardness of thermoplastic polyurethane (type A durometer, 1 kg
f) is preferably 90 or less. Next, the mixing ratio of the block copolymer (a) having polyamide as a hard segment and the thermoplastic polyurethane (b) will be described. The proportion of (a) in the base resin is 100 to 10% by weight. When the proportion of (a) is less than 10% by weight, the adhesion between the polyamide resin molded article and the outermost layer of the cable is the same as that of (b) 100% by weight (b alone),
This is because the effect of improving the adhesiveness is not recognized. When the blending amount of (a) in the base resin exceeds 10%, the effect of sufficiently improving the adhesiveness can be obtained. Even when the outermost layer (a) alone is used as the base resin, the adhesive strength to the polyamide resin molded article can be obtained. However, when the blending ratio of (b) in the base resin is 20 to 60% by weight, the synergistic effect of the two can be obtained. Appears prominently. Therefore, the blending amount of both is (a) 80 to 40% by weight, (b) 20
More preferably, the content is set to about 60% by weight. The base resin is mainly composed of (a) and (b), but a small amount of other resin may be blended as long as the properties are not impaired.

The inner layer 2 of the coating layer of the cable according to the present invention
a is selected in consideration of the adhesion to the outermost layer 2b and the like.
One example is a thermoplastic polyurethane-based composition, and another example is an ethylene / α-olefin copolymer or ethylene / olefin having a density of 0.86 to 0.90 g / cm ^3.
It is a resin composition using any one of vinyl acetate copolymers or a mixture thereof as a base resin. Examples of the type of the thermoplastic polyurethane serving as the base resin of the thermoplastic polyurethane composition include polyester-based urethane resins (adipate-based, caprolactone-based, and polycarbonate-based).
A polyether-based urethane resin is exemplified, and a polyether-based urethane resin is preferable in terms of water resistance, mold resistance, and the like. The ethylene / α-olefin copolymer includes ethylene and propylene, 1-butene, 4-methyl-1-pentene,
A copolymer with one or more α-olefins such as hexene, 1-octene, 1-decene, and 1-dodecene, and having a density of 0.86 to 0.90 g / c in terms of crosslinkability and elasticity.
Those having m ³ are preferred. The ethylene / vinyl acetate copolymer preferably has a vinyl acetate content of 10 to 30% by weight from the viewpoint of crosslinkability and elasticity. Ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer can improve their heat resistance by crosslinking, and when molded with a resin having a high melting point such as polyamide resin, it is crosslinked. It is essential.
Further, these are suitable as the inner layer of the cable of the present invention since the rubber elasticity is greatly improved by crosslinking.

In the cable of the present invention, heat resistance and rubber elasticity can be improved by cross-linking the coating layer 2, and as a result, a resilient force is generated in the cable, and a molded article formed at the cable end is formed. Airtightness of the cable interface,
Watertightness is further improved. However, the outermost coating layer 2b
2 when the gel fraction of the resin composition is less than 10% by weight.
Melting and cracking may occur on the cable surface in a high-temperature atmosphere of 00 ° C. or more, and when it is more than 40% by weight, the adhesion to the polyamide resin tends to decrease. Therefore, the gel fraction of the outermost coating layer is 10 to 40% by weight.
It is preferable that As a method for cross-linking the coating layer, a conventionally known electron beam cross-linking method or chemical cross-linking method can be adopted, but from the viewpoint of productivity, a cross-linking method using electron beam irradiation is preferable. In the case of the electron beam crosslinking method, crosslinking is performed by irradiating the resin composition with an electron beam after extrusion molding. The degree of crosslinking can be controlled by appropriately selecting the irradiation dose, the amount and type of the crosslinking aid. As the crosslinking aid, a polyfunctional monomer (trimethylolpropane trimethacrylate, triallyl cyanurate, or the like) may be blended, and the crosslinking can be efficiently performed by blending the crosslinking assistant. In the case of the chemical crosslinking method, an organic peroxide is blended as a crosslinking agent, and crosslinking is completed by heat treatment after extrusion molding.

The resin composition used in the inner and outer layers of the coating layer of the cable in the present invention contains various additives generally used in insulated wires and cables, for example, antioxidants and metal deactivators. , A flame retardant, a dispersant, a colorant, a filler, a lubricant and the like can be appropriately compounded within a range not to impair the object of the present invention. As antioxidants, 4,
Amine antioxidants such as 4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, pentaerythrityl-tetrakis ( 3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate), octadecyl-3- (3,5-di-
(tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Phenolic antioxidants such as benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy)
-5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, and sulfur-based antioxidants such as pentaerythritol-tetrakis (3-lauryl-thiopropionate). As the metal deactivator, N, N'-bis (3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-
1,2,4-triazole, 2,2′-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

As the flame retardant, tetrabromobisphenol A (TBA), decabromodiphenyl oxide (DBDPO), octabromodiphenyl ether (O
BDPE), hexabromocyclododecane (HBC
D), bistribromophenoxyethane (BTBP)
E), halogen-based flame retardants such as tribromophenol (TBP), ethylenebistetrabromophthalimide, TBA / polycarbonate oligomer, brominated polystyrene, brominated epoxy, ethylenebispentabromodiphenyl, chlorinated paraffin, dodecachlorocyclooctane, etc. And inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, and phosphorus-based flame retardants such as phosphoric acid compounds, polyphosphoric acid compounds and red phosphorus compounds. Examples of the flame retardant aid and filler include carbon, clay, zinc oxide, tin oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silica, talc, calcium carbonate, magnesium carbonate, zinc borate and the like.

[0014]

【Example】

(Examples 1 to 14, Comparative Examples 1 to 4) Conductor (conductor diameter 1 mm)
φ tinned soft copper stranded wire Composition: 20 / 0.18mm
φ), a low-density polyethylene is extrusion-coated to form an insulating layer having an outer diameter of 1.7 mm.
The multi-core stranded wire as shown in FIG. 1 was prepared by irradiating an electron beam having an eV of 20 Mrad and twisting two insulated wires each having the insulating layer crosslinked. Then, a 40 mmφ extruder (L / D = 2)
5), the outer diameter of the coating resin composition shown in Table 1 or Table 2 was 5.0 mm under the condition of a die temperature of 180 ° C.
It was extruded and covered to make a cable of φ. Example 1
With respect to No. 11 and Comparative Examples 1 to 4, after the extrusion coating, the coating layer was further cross-linked by irradiating an electron beam at an acceleration voltage of 750 keV and a dose of 12 Mrad. For Examples 12 to 14, Table 2 was obtained on a multi-core stranded wire prepared under the same conditions as in Example 1.
Extrusion coating of the inner layer resin shown in the above, the coating layer is crosslinked by electron beam irradiation, and the outer layer resin composition shown in Table 2 is extrusion-coated on each of them so that the outer diameter becomes 5.0 mmφ,
Electron beam irradiation was performed to obtain a cable having two coating layers.

Various characteristics of the obtained cables were evaluated by the following test methods. (1) Airtightness of terminal As shown in FIG.
b was removed to expose the conductor 1a, and the electrode terminal 5 was connected to the end. Next, the connection portion and the vicinity thereof were covered with a resin molded body 4 by molding with a polyamide resin (nylon 12). About this cable,
A heat cycle test of 10 cycles was performed with one hour at -40 ° C. × 1 hour. After that, compressed air of 2 atm is injected from the terminal opposite to the resin molded body side,
It was immersed in water to check for airtightness by checking whether there was any leakage from the resin molded body side by the presence or absence of air bubbles. The test was carried out on 5 samples, and when all passed, it was evaluated as ○, and when any of the samples failed, it was evaluated as x.

(2) Observation of Adhesive Surface As an evaluation of adhesiveness, the resin molded body was disassembled, and the presence or absence of the coating layer resin composition on the surface of the polyamide resin molded body in contact with the coating layer of the cable was examined. ◎ indicates that the peeling of the polyamide resin molded article and the cable is not possible because of strong adhesive strength, and ○ indicates that an aggregate of the coating resin composition exists at the bonding interface between the polyamide resin and the coating layer,
In all other cases, it was marked as x. (3) Heat resistance The cable is wound around its own diameter (5.0 mmφ) for 6 turns or more, left at 200 ° C. for 30 minutes, taken out, and cooled to room temperature. Thereafter, the presence or absence of melting and cracks on the surface of the wound cable was observed. All samples were evaluated as ○, and any sample was evaluated as unacceptable. (4) Gel Fraction About 0.5 g of the outermost layer of the cable was firstly shaved and extracted with xylene at 110 ° C. for 24 hours. The insoluble matter was taken out and dried sufficiently to volatilize xylene. Thereafter, the mixture is further extracted with dimethylformamide at 110 ° C. for 24 hours, and then sufficiently dried to evaporate dimethylformamide. The weight after drying was measured, and the weight after extraction and drying with respect to the weight of the original product before xylene extraction was expressed as a percentage, and was defined as a gel fraction.

The following components were used as the components shown in Tables 1 to 3. (01) Polyamide elastomer hardness 75A manufactured by ATOCHEM Product name Pebax 2533SAOO Hardness Shore A75 Specific gravity 1.01 Melt index 6 g / 10 min [235 ° C 1 kg
f] Melting point 148 ° C (02) Polyamide elastomer hardness 83A manufactured by ATOCHEM Corporation Pebax 3533SAOO Hardness Shore A83 Specific gravity 1.01 Melt index 7g / 10min [235 ° C 1kg
f] Melting point 152 ° C (03) Polyamide elastomer hardness 90A manufactured by ATOCHEM Corporation Pebax 4033SAOO Hardness Shore A90 Specific gravity 1.01 Melt index 7g / 10min [235 ° C 1kg
f] Melting point 168 ° C. (04) (10) Ether-based thermoplastic polyurethane hardness 85A manufactured by Nippon Miractran Co., Ltd. E-385PNAT hardness Shore A85 Specific gravity 1.11

(05) PTBP ^* pentaerythrityl-tetrakis (3- (3,5-di-t)
-Butyl-4-hydroxyphenyl) propionate) Ciba Geigy Co., Ltd. Product name Irganox 1010 (06) TMPTM ^* Trimethylolpropane trimethacrylate Shin-Nakamura Chemical Co., Ltd. Product name Ogmont T200 (07) Ethylene bispentabromobiphenyl albemarle Product name Cytex 8010 (08) Ethylene / vinyl acetate copolymer Product name Evaflex V527-4 manufactured by Mitsui / Dupont Polychemical Co., Ltd. Vinyl acetate content 17% by weight Melt flow rate 0.8 g / 10 min. Density 0.94 g / cm ³ (09) ethylene-alpha-olefin copolymer Dow Chemical Co., trade name engage CL8003 alpha-olefin (octene) content 18 wt% melt flow rate 1 g / 10min. density 0. 89 g cm ³

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

Each of the embodiments is excellent in terminal airtightness, adhesion and heat resistance. On the other hand, Comparative Example 1 was inferior in airtightness and adhesion because the outermost layer of the coating was only a thermoplastic polyurethane resin, and Comparative Examples 2, 3, and 4 all contained a block copolymer containing polyamide as a hard segment. , The airtightness and adhesion are inferior.

[0023]

The cable of the present invention is obtained by extrusion molding and then crosslinking by electron beam irradiation.
(B) When the end portion of the cable is molded with a polyamide resin by using 0 to 90% by weight of a thermoplastic polyurethane resin as a base resin, the cable and the molded body can be formed without taking special sealing measures. Airtightness of the interface of
Watertightness is maintained, preventing corrosion of the conductor of the insulated wire inside the cable and deterioration of the performance of connected equipment parts, heat resistance,
This has the effect of providing a cable with excellent airtightness and watertightness, and can provide a cable that can be used for a long period of time for automobiles, robots, electronic devices, and the like.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of the cable of the present invention.

FIG. 2 is an explanatory view showing a state where an electrode terminal is fixed to a terminal of the cable of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multi-core stranded wire 2 Coating layer 3 Cable 4 Resin molding 5 Electrode terminal

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI (C08L 77/00 75:04) (72) Inventor Ryoji Ohno 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric Co., Ltd. (72) Inventor Masahiro Tanaka 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric Co., Ltd.

Claims (4)

[Claims] 1. A cable in which a coating layer is provided on the outside of a multi-core stranded wire in which a plurality of insulated conductors are twisted, wherein at least the outermost layer of the coating layer has a block copolymer containing polyamide as a hard segment. A cable comprising a crosslinked body obtained by extruding a thermoplastic resin composition containing a base resin containing 0 to 90% by weight of a thermoplastic polyurethane and 0 to 90% by weight of a thermoplastic polyurethane, and irradiating with an electron beam. 2. The cable according to claim 1, wherein the gel fraction of the outermost layer is 10 to 40% by weight. 3. The cable according to claim 1, wherein a resin composition containing a thermoplastic polyurethane as a base resin is used for the inner layer of the coating layer. 4. The inner layer of the coating layer has a density of 0.86 to 0.9.
0 g / cm ³ ethylene / α-olefin copolymer,
The cable according to claim 1 or 2, wherein a resin composition having any one of an ethylene-vinyl acetate copolymer or a mixture thereof as a base resin is used.