JP5692619B2 - Phosphorus-free non-halogen flame-retardant insulated wires and phosphorus-free non-halogen flame-retardant insulated cables - Google Patents

Description

  The present invention is a phosphorus-free non-halogen flame retardant insulated wire and phosphorus-free wire having high flame resistance that passes overseas flame retardant standards (EN, DIN, BS), excellent mechanical properties, and smooth extrusion appearance. This relates to a non-halogen flame retardant insulated cable.

  In recent years, non-halogen flame retardant electric wires and cables that do not use polyvinyl chloride or halogen-based flame retardants and have a low environmental load are rapidly spreading as so-called eco electric wires and cables.

  In these non-halogen flame-retardant electric wires and cables, a resin composition in which a large amount of non-halogen flame retardant such as magnesium hydroxide is mixed with polyolefin is generally used as an electric wire insulator.

  Using non-halogen flame retardants such as magnesium hydroxide and passing overseas flame retardant standards (EN, DIN, BS), a large amount of non-halogen flame retardants to achieve high flame retardant in vertical combustion test Therefore, there is a problem that mechanical properties such as tensile strength and elongation are significantly lowered.

  In order to solve such problems, there is a technique of using, as a base polymer, a high-strength and flexible polyolefin having a narrow molecular weight distribution polymerized by a metallocene catalyst (for example, JP 2009-19190 A).

JP 2009-19190 A

  With such a method, there is an excellent advantage that even if a large amount of non-halogen flame retardant is mixed into the base polymer, the mechanical properties are not easily impaired, but there is no room for improvement.

  In other words, in order to reduce the production cost, it is desirable to increase the extrusion speed of the resin composition. However, a polymer having a narrow molecular weight distribution, such as a polyolefin polymerized by a metallocene catalyst, is melted during extrusion. Fracture tends to occur significantly, and the extrusion appearance may be impaired.

  On the other hand, there is a method to reduce the amount of non-halogen flame retardants by adding a flame retardant aid such as red phosphorus, but red phosphorus generates harmful phosphine during combustion, and generates phosphoric acid during disposal to contaminate groundwater veins. Since concerns have been pointed out, recently there has been a tendency to refrain from use, and the development of phosphorus-free non-halogen flame retardant wires and cables with excellent flame retardancy has been required.

  Accordingly, the present invention provides a phosphorus-free non-halogen flame retardant insulated wire having high flame resistance that passes overseas flame retardant standards (EN, DIN, BS), excellent mechanical properties, and smooth extrusion appearance. An object is to provide a phosphorus-free non-halogen flame retardant insulated cable.

In order to achieve the above object, the invention of claim 1 is characterized in that the copolymer of ethylene and α-olefin polymerized by a metallocene catalyst on the outer periphery of the conductor is 50 wt% or more, and the amount of vinyl acetate is 40% or more. -An electric wire provided with an insulating layer formed by coating a phosphorus-free non-halogen flame retardant resin composition comprising a base polymer containing 5 wt% or more and 30 wt% or less of a vinyl acetate copolymer, which is added to 100 parts by weight of the base polymer On the other hand, the metal hydroxide is contained in an amount of 100 parts by weight or more and 250 parts by weight or less, the mineral oil is contained in an amount of 1 part by weight or more and 20 parts by weight or less, the insulating layer is crosslinked, and the elongation is 350 in a tensile test based on JIS C3005. %, The insulating layer has a surface roughness Ra value of 1.5 μm or less, and passes a vertical combustion test according to EN60332-1-2. This is a phosphorus-free non-halogen flame retardant insulated wire.

In the invention of claim 2, the outer periphery of the insulated wire provided with an insulating layer on the outer periphery of the conductor has a copolymer of ethylene and α-olefin polymerized by a metallocene catalyst at 50 wt% or more, and the amount of vinyl acetate is Phosphorus-free non-halogen flame retardant insulation having a sheath layer coated with a phosphorus-free non-halogen flame retardant resin composition comprising a base polymer containing 40% or more of ethylene / vinyl acetate copolymer of 5 wt% to 30 wt% A cable, comprising 100 parts by weight to 250 parts by weight of a metal hydroxide and 1 part by weight to 20 parts by weight of mineral oil with respect to 100 parts by weight of the base polymer, and the sheath layer is crosslinked, In the tensile test based on JIS C3005, it has an elongation property of 350% or more, the surface roughness Ra value of the sheath layer is 1.5 μm or less, and EN This is a phosphorus-free non-halogen flame retardant insulated cable that passes the vertical combustion test in accordance with 60332-1-2.

  According to the present invention, a phosphorus-free non-halogen flame-retardant insulated electric wire having high flame resistance that passes overseas flame retardant standards (EN, DIN, BS), excellent mechanical characteristics, and smooth extrusion appearance, and A phosphorus-free non-halogen flame retardant insulated cable can be obtained.

1 is a cross-sectional view of a phosphorus-free non-halogen flame retardant insulated wire according to an embodiment of the present invention. 1 is a cross-sectional view of a phosphorus-free non-halogen flame retardant insulated cable according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a phosphorus-free non-halogen flame retardant resin comprising a base polymer containing an ethylene / vinyl acetate copolymer whose main component is a copolymer of ethylene and α-olefin polymerized by a metallocene catalyst on the outer periphery of a conductor. An electric wire having an insulating layer coated with a composition, comprising 100 parts by weight or more and 250 parts by weight or less of mineral oil and 1 part by weight or more and 20 parts by weight or less of 100 parts by weight of the base polymer. It is a phosphorus-free non-halogen flame retardant insulated wire having a surface roughness Ra value of 1.5 μm or less and passing a vertical combustion test in accordance with EN60332-1-2. In addition, the main component here means the component which occupies 50 wt% or more with respect to a polymer.

  The present invention is based on a copolymer of ethylene and α-olefin polymerized with a metallocene catalyst as a main component, a base polymer containing an ethylene / vinyl acetate copolymer, and a vertical combustion test according to EN60332-1-2. Even if it is highly filled with a flame retardant to pass the above, it has succeeded in producing a phosphorus-free non-halogen flame retardant insulated wire having a smooth appearance.

  FIG. 1 is a cross-sectional explanatory view of an embodiment of the present invention, and shows a structural example of a phosphorus-free non-halogen flame retardant insulated electric wire.

  The phosphorus-free non-halogen flame retardant insulated electric wire 11 has a structure in which an insulating layer 2 is provided on the outer periphery of the conductor 1, and each material can be made of, for example, copper or a copper alloy. This is not particularly limited as long as it is present, and the insulating layer 2 is a phosphorus-free non-halogen flame retardant resin composition described below.

  FIG. 2 is a cross-sectional view showing a preferred embodiment of the phosphorus-free non-halogen flame retardant insulated cable according to the present invention.

  As shown in FIG. 2, the phosphorus-free non-halogen flame retardant insulated cable 10 of the present embodiment is an outer periphery of a core configured by twisting two parallel phosphorus-free non-halogen flame retardant insulated wires 11 together with an intervening 3 Further, a cable sheath 4 made of a phosphorus-free non-halogen flame retardant resin composition described below is coated. The interposition 3 is made of polypropylene, for example.

  The resin composition of the phosphorus-free non-halogen flame retardant resin composition that has an insulating layer surface roughness Ra value of 1.5 μm or less and passes the vertical combustion test in accordance with EN60332-1-2 is not particularly limited. An example is shown below.

  The base polymer of the phosphorus-free non-halogen flame retardant resin composition includes a copolymer of ethylene polymerized by a metallocene catalyst and an α-olefin having 3 to 8 carbon atoms, and a melt flow rate of 50 g / min or more. In addition, it is preferable to use a polymer composed of an ethylene / vinyl acetate copolymer having a vinyl acetate content of 40% or more.

  Examples of the copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms include ethylene / propylene / copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and ethylene / octene copolymer.

  Examples of the α-olefin having 3 to 8 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Of these, 1-butene and 1-octene are more preferable.

  In the present invention, a base polymer obtained by blending a copolymer of ethylene and an α-olefin and an ethylene / vinyl acetate copolymer is used. The blend ratio is a copolymer of ethylene and an α-olefin. Is preferably the main component in the entire base polymer, and the ethylene / vinyl acetate copolymer is preferably 5 wt% or more and 30 wt% or less with respect to the entire base polymer.

  In the present invention, it is preferable that a copolymer of ethylene and α-olefin is a main component in the entire base polymer, and the ethylene / vinyl acetate copolymer is 5 wt% or more and 30 wt% or less with respect to the entire base polymer. However, as long as the effects of the present invention are exhibited, the resin composition may be blended with another polymer. For example, it can be blended with polyethylene (for example, LLDPE), ethylene copolymer (EVA, EEA, etc.), EP rubber.

  In the present invention, a metal hydroxide is added to the base polymer. The reason for adding the metal hydroxide is to impart further flame retardancy to the base polymer.

  As the metal hydroxide, for example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like can be used. These flame retardants include silane cups such as vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, and aminosilane. It is desirable to use a ring agent, a fatty acid such as stearic acid and oleic acid, titanate, and the like after surface treatment by a known method.

  The total mixing amount of the metal hydroxide is 100 parts by weight or more and 250 parts by weight or less with respect to 100 parts by weight of the base polymer. A more preferable range is 150 parts by weight or more and 200 parts by weight or less.

  The present invention adds mineral oil to the base polymer. The reason for adding and using mineral oil is to further reduce the load on the extruder during extrusion and to smooth the appearance of extrusion.

  The mineral oil used in the present invention is, for example, a rubber process oil, and one or more selected from paraffinic oil, naphthenic oil, and aroma oil can be used in combination. In particular, paraffinic oil having high compatibility with the ethylene / α-olefin copolymer is preferable.

  The total amount of mineral oil blended is from 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the base polymer.

  Depending on the application of phosphorus-free non-halogen flame retardant insulated wires and phosphorus-free non-halogen flame retardant insulated cables, the wires and cables obtained above may be irradiated with an electron beam or ultraviolet light, or organic peroxides. It is also possible to use after crosslinking with a known method.

  In the present invention, in addition to the above-described components, a crosslinking aid, a flame retardant aid, an antioxidant, a lubricant, a stabilizer, a filler, a colorant, silicone, and the like may be added.

  Moreover, since the phosphorus-free non-halogen flame retardant insulated cable 10 of this embodiment forms the sheath 4 with the same resin composition as the insulating layer 2 of the phosphorus-free non-halogen flame retardant insulated wire 11, the phosphorus-free non-halogen-containing cable 10 The flame retardant insulated cable 10 also has the same effects as the phosphorus-free non-halogen flame retardant insulated wire 11.

  The phosphorus-free non-halogen flame retardant insulated cable 10 shown in FIG. 2 has both the insulating layer 2 and the sheath 4 made of the phosphorus-free non-halogen flame retardant resin composition. The fuel insulated cable 10 may be configured such that only the sheath 4 is made of the above resin composition.

  The phosphorus-free non-halogen flame retardant resin composition constituting the insulating layer 2 and the sheath 4 can be applied to, for example, a protective layer of a flat cable in addition to circular electric wires and cables.

  Next, embodiments of the present invention will be described based on examples, but the embodiments of the present invention are not limited to these examples.

(Examples 1-6)
Using a 40 mm extruder (L / D = 24) which was put into an 8-inch open roll maintained at 100 to 130 ° C. and kneaded and held at 100 ° C. after kneading, the components listed in Table 1 had a conductor diameter of 0. . Extrusion coating was carried out at a thickness of 1.0 mm on a copper wire in which seven single wires of 26 mm were twisted. Subsequently, this was put into a 12-atmosphere steam vulcanizing can for 3 minutes and crosslinked to produce a non-halogen flame-retardant electric wire (sample).

  The evaluation method of each sample was performed as follows.

(1) Flame retardancy The sample was subjected to a vertical combustion test in accordance with EN60332-1-2, and the flame retardance in the vertical direction was evaluated. The criteria for evaluation were those that self-extinguished within 1 minute (passed), and those that exceeded 1 minute were rejected (x).

(2) Tensile properties A tube obtained by extracting the conductor from the sample was subjected to a tensile test according to JIS C3005. The tensile speed was 200 mm / min. The targets for tensile strength and elongation were 10 MPa or more and 350% or more, respectively.

(3) Extrusion appearance When the sample was extruded while being slightly pulled down at an extrusion speed of 40 m / min, the state of the sample surface was measured using a surface roughness meter. If the Ra value was 1.5 μm or less, it was acceptable (◯). When it exceeded, it was set as the rejection (x).

  As shown in Table 1, it can be seen that Examples 1 to 6, which are the present invention, all passed the vertical combustion test, and the tensile properties and extrusion appearance are also good.

DESCRIPTION OF SYMBOLS 1 Conductor 2 Insulation layer 3 Interposition 4 Sheath 10 Phosphorus-free non-halogen flame-retardant insulated cable 11 Phosphorus-free non-halogen flame-retardant insulated wire

Claims (2)

A copolymer of ethylene and α-olefin polymerized by a metallocene catalyst on the outer periphery of the conductor is 50 wt% or more, and an ethylene / vinyl acetate copolymer having a vinyl acetate content of 40% or more is contained in an amount of 5 wt% to 30 wt% . An electric wire provided with an insulating layer formed by coating a phosphorus-free non-halogen flame retardant resin composition comprising a base polymer, wherein 100 parts by weight or more and 250 parts by weight or less of a metal hydroxide with respect to 100 parts by weight of the base polymer The mineral oil is contained in an amount of 1 part by weight or more and 20 parts by weight or less, the insulating layer is crosslinked, and has an elongation characteristic of 350% or more in a tensile test in accordance with JIS C3005. A phosphorus-free non-halogen flame-retardant insulated electric wire having a Ra value of 1.5 μm or less and passing a vertical combustion test in accordance with EN60332-1-2. A copolymer of ethylene and α-olefin polymerized with a metallocene catalyst on the outer periphery of an insulated wire having an insulating layer on the outer periphery of the conductor is 50 wt% or more, and an ethylene / vinyl acetate copolymer having a vinyl acetate content of 40% or more. A phosphorus-free non-halogen flame retardant insulated cable comprising a sheath layer formed by coating a phosphorus-free non-halogen flame retardant resin composition comprising a base polymer containing 5 wt% or more and 30 wt% or less of a polymer, the base polymer 100 100 parts by weight or more and 250 parts by weight or less of metal hydroxide and 1 part by weight or more and 20 parts by weight or less of mineral oil with respect to parts by weight, and the sheath layer is crosslinked and stretched in a tensile test according to JIS C3005. Vertical combustion with an elongation characteristic of 350% or more, a surface roughness Ra value of the sheath layer of 1.5 μm or less, and in accordance with EN60332-1-2 Phosphorus-free non-halogen flame retardant insulated cable characterized by passing the test.

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