JP4940568B2 - Non-halogen flame retardant wire / cable - Google Patents

Description

  The present invention relates to a halogen-free flame retardant electric wire / cable in which a conductor is coated with an insulator or sheath made of a halogen-free flame retardant resin composition.

  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.

  As these non-halogen flame retardant resin compositions, resin compositions obtained by mixing a large amount of non-halogen flame retardants such as magnesium hydroxide with polyolefin are generally used.

  In order to improve the flame retardancy, a high amount of flame retardant is filled. However, mechanical properties and electrical properties are deteriorated, and there is a problem that a desired electric wire / cable cannot be obtained.

  For this reason, as seen in Patent Documents 1 and 2, two insulating layers are used to improve the mechanical characteristics and electrical characteristics of the inner and outer layers.

JP 2001-155554 A JP 2003-132741 A

  However, when the present inventors examined flame retardancy, for example, in order to make the outer layer more flame-retardant, even if 300 parts by weight of magnesium hydroxide is added to 100 parts by weight of polyolefin, the layer of insulator It was found that when the thickness was increased, the polyolefin fluidized during combustion, which gasified and combusted. For example, an electric wire / cable (conductor diameter: 0.64 mm) used for a backlight power source of a liquid crystal display has a problem that it cannot be made flame retardant with an insulation thickness of 0.55 mm or more.

  An object of the present invention is to provide a non-halogen flame-retardant electric wire / cable that can achieve non-halogenation even when the insulating layer is thick.

In order to achieve the above object, the present invention provides an electric wire / cable having an inner layer and an outer layer made of a resin composition on a conductor, wherein the inner layer is ethylene having an ethyl acrylate content (EA amount) of 9 to 35 wt%. comprises 50 to 150 parts by weight of flame retardant ethyl acrylate copolymer (EEA) for a single or base polymer 100 parts by weight mixed with other polyolefin resins, the outer layer amount EA of 15～35Wt% ethylene To 100 parts by weight of a base polymer obtained by mixing an ethyl acrylate copolymer (EEA) or an ethylene vinyl acetate copolymer (EVA) having a vinyl acetate content (VA amount) of 15 to 45 wt% alone or with other polyolefin resin. It comprises 150-300 parts by weight of a flame retardant for the thickness of the outer layer larger than a thickness of the inner layer lower child Is a non-halogen flame-retardant wire or cable according to claim.

Wire and cable according to the present invention, as is clear from examples described later, the inner layer thickness is 0.05 to 0.30 mm, the outer layer thickness is a 0.30 to 0.70 mm, and The ratio of the inner layer thickness to the outer layer thickness (inner layer thickness / outer layer thickness) is preferably 1/7 to 1/2.

  In the present invention, an ethylene ethyl acrylate copolymer (EEA) is used for the inner layer. As a result, when the electric wire / cable is burned, the inner layer forms a shell, and the flame disappears by inhibiting the flow caused by plasticization of the outer layer and reducing the amount of combustible gas produced.

  Embodiments of the present invention will be described below with reference to the accompanying drawings.

  First, as shown in FIGS. 1A and 1B, non-halogen flame-retardant electric wires and cables are used for, for example, a backlight power source of a liquid crystal display, and the conductor 10 (conductor diameter 0.64 mm) is used. The inner layer 11 (insulating layer thickness 0.1 mm) is extrusion-coated, and the inner layer 11 is formed by extrusion-coating the outer layer 12 (insulating layer thickness 0.45 mm).

The ethylene ethyl acrylate copolymer (EEA) used for the inner layer 11 of the present invention is used alone or mixed with another polyolefin resin. The reason why EEA is used is to form a shell of the carbonized layer at the time of combustion. The reason that the ethyl acrylate content (EA amount ) is set to 9 to 35 wt% is that the flame retardancy is reduced when the content is less than 9 wt%, This is because if the amount is too large, the mechanical properties are significantly lowered. The blend amount of EEA is preferably 50 parts by weight or more from the viewpoint of effectively forming a carbonized layer. Other polyolefin resins mixed with EEA include low density, medium density, and high density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate. Examples include copolymers, ethylene vinyl acetate copolymers, ethylene-styrene copolymers, ethylene-maleic anhydride copolymers, and maleic anhydride grafted linear low density polyethylene. These polyolefin resins may be modified with maleic acid or its derivatives. These can be used alone or in combination of two or more.

  Examples of the flame retardant include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide, and those in which nickel is dissolved. In addition, a silane coupling agent, a titanate coupling agent, a fatty acid such as stearate or calcium stearate, or a surface treated with a fatty acid metal salt may be used.

  Examples of other flame retardants include 1,3,5-triazine derivatives such as melamine, cyanuric acid, isocyanuric acid, melamine cyanurate, and melamine sulfate. More preferred is melamine cyanurate. These may be surface-treated with a nonionic surfactant or various coupling agents.

  A flame retardant may be individual or may use 2 or more types together.

  In the present invention, the amount of the flame retardant added is 50 to 150 parts by weight. If the amount added is less than 50 parts by weight, sufficient flame retardancy cannot be obtained, and if the amount added exceeds 150 parts by weight, the electrical characteristics are significantly reduced. .

  EEA and ethylene vinyl acetate copolymer (EVA) used for the outer layer 12 are used alone or mixed with other polyolefin resins. The reason for setting the EA amount to 15 to 35 wt% and the VA amount to 15 to 45 wt% is that the flame retardancy is reduced when the specified amount is small, and the mechanical properties are decreased when the specified amount is higher.

  Other polyolefin resins to be mixed include low density, medium density, and high density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer Examples thereof include a copolymer, an ethylene-styrene copolymer, an ethylene-maleic anhydride copolymer, and a maleic acid grafted linear low density polyethylene. These polyolefin resins may be modified with maleic acid or derivatives thereof. These can be used alone or in combination of two or more.

  Examples of the flame retardant include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide, and those obtained by dissolving nickel in solid solution. Further, a silane coupling agent, a titanate coupling agent, a fatty acid such as stearate or calcium stearate, or a surface treated with a fatty acid metal salt or the like may be used.

  Examples of other flame retardants include 1,3,5-triazine derivatives such as melamine, cyanuric acid, isocyanuric acid, melamine cyanurate, and melamine sulfate. More preferred is melamine cyanurate. These may be surface-treated with a nonionic surface treatment agent or various coupling agents.

  The flame retardant may be used alone or in combination of two or more.

  In the present invention, the addition amount of the metal hydroxide is 150 to 300 parts by weight. If the addition amount is less than 150 parts by weight, sufficient flame retardancy cannot be obtained. It drops significantly.

  In addition to the above-mentioned compounding agents for both the inner and outer layers, additives such as antioxidants, lubricants, softeners, plasticizers, inorganic fillers, compatibilizers, stabilizers, carbon black, and coloring agents may be added as necessary. It is possible to add.

  Furthermore, it may be crosslinked by an organic peroxide or by radiation such as an electron beam.

  In order to produce an electric wire / cable, materials blended according to the above composition were kneaded at 200 ° C. for 5 minutes using a pressure kneader having a capacity of 3 L, and pelletized using a pelletizer. The obtained pellets were extruded at 220 ° C. using a 40 mm extruder. For extrusion, the inner layer 11 and the outer layer 12 were simultaneously extruded and coated on the conductor 10 by a common method to produce an electric wire.

  Next, the difference in combustion between the non-halogen flame-retardant electric wire / cable of the present invention and the conventional electric wire / cable will be described.

  3 (a) and 3 (b) show a conventional electric wire / cable. In the figure, the electric wire / cable is produced by coating a conductor 20 with a non-halogen insulating layer 21 containing EEA, EVA and a flame retardant. The

  As shown in FIGS. 4A to 4C, when the electric wire / cable is exposed to the flame F (FIG. 4A), the non-halogen insulating layer 21 is shown in FIG. 4B. As shown in FIG. 4 (c), the combustible material of the non-halogen insulating layer 21 is melted by the flame F and flows into the flame F. Since it is gasified while being plasticized and combustion is continued, combustion cannot be prevented.

  In contrast, in the present invention, when the non-halogen flame-retardant electric wire / cable is exposed to the flame F and burns as shown in FIG. 2 (a), the outer layer 12 is as shown in FIG. 2 (b). Although the inner layer 11 is made of EEA, the inner layer 11 is made of EEA and forms a shell 11c. This shell 11c inhibits the plasticization of the outer layer 12, and the melt flows into the flame F. Thus, it is possible to prevent the generation of flammable gas and to extinguish the fire spontaneously as shown in FIG.

  For the purpose of investigating whether or not the inner layer formed a carbonized layer during combustion, the EDX (Energy Dispersive X-Ray Spectroscopy: energy analysis type X) of the inner layer remaining when the wires and cables were decomposed in a nitrogen atmosphere and an oxygen atmosphere The results of the (line spectroscopy) analysis are shown in the table below.

In nitrogen atmosphere In oxygen atmosphere C 13.1 10.8
O 46.7 44.9
Mg 35.9 38.9
Other 4.3 5.4
Total 100% by weight 100% by weight
The combustibles in the resin are C and H, and the carbon content in the oxygen atmosphere is 10.8% by weight, but in the nitrogen atmosphere, the carbon content increases to 13.1% by weight, and oxygen The content also increases from 44.9% to 46.7% by weight.

  That is, it is presumed that a carbonized layer was formed by using EEA for the inner layer.

  Next, examples of the present invention will be described together with comparative examples.

  The evaluation of the electric wire was determined by the following method.

(1) Tensile test The produced electric wire was subjected to a tensile test in accordance with JIS C 3005. The elongation was less than 150% x (failed), 150-300% was o (accepted), and the top was double circle (passed with tolerance). Tensile strength of less than 10 MPa was evaluated as x (failed), 10-13 MPa was evaluated as ◯ (accepted), and the top was double circle (accepted with tolerance).

(2) Flame retardance test The produced electric wire was subjected to a vertical combustion test (VW-1) according to UL subject 758. The determination was made with a combustion time of 1 minute or longer as x (failed), less than 1 minute as ◯ (passed), and less than 30 seconds as double circle (passed with tolerance).

(3) Heat aging test The produced wire was heated in a constant temperature bath at 136 ° C. for 168 hours, left at room temperature for about 12 hours, a tensile test was performed, and the value after heat aging relative to the initial value (residual rate) It was evaluated with. A residual elongation rate (%) of 75% or more was considered acceptable.

(4) Withstand voltage test The prepared electric wire 6m is immersed in water, the specified voltage (AC 12 kV / 30 minutes and AC 7.5 kV / 7 hours) is applied, and if there is no breakdown within the specified time, ○ (pass) ).

(5) Cold resistance test The prepared electric wire is allowed to stand in a thermostatic bath at -20 ° C for 1 hour. (Passed).

  In Tables 1 and 2, Examples 1 to 11 (Table 1), Comparative Examples 1 to 8 and Comparative Examples 10 to 13 (Table 2) show examples in which the resin compositions of the outer layer and the inner layer are changed, and are comparative examples. 9 is an insulating layer formed of the same resin composition on the outer layer and the inner layer.

  From Examples 1 to 11 in Table 1, any of those obtained by adding EEA to the inner layer 1 is good in flame retardancy (vertical combustion test).

  First, Comparative Examples 2 and 3 in which the amount of magnesium hydroxide added in the outer layer is as small as 100 parts by weight is not preferable because the flame retardancy is lowered although the tensile properties (strength and elongation) are good, and the comparison is large as 350 parts by weight. Examples 4 and 5 have good flame retardancy but poor tensile properties. On the other hand, Example 1 in which the amount of magnesium hydroxide added to the outer layer is 150 parts by weight and Example 2 in which 300 parts by weight are good both in flame retardancy and tensile properties, and the flame retardant added to the outer layer Is preferably 150 to 300 parts by weight.

  Further, the flame retardant added to the inner layer is reduced in flame retardancy in Comparative Example 12 having an addition amount of 30 parts by weight, and Comparative Example 13 having 200 parts by weight has poor tensile properties. On the other hand, both 150 parts by weight of Example 1 and 50 parts by weight of Example 2 have good flame retardancy and tensile properties (strength and elongation), and the flame retardant added to the inner layer is 50 to 150. Part by weight is preferred.

  In Examples 3 and 4, when the thickness of the outer layer is changed to 0.45 mm (Example 3) and 0.70 mm (Example 4), the flame retardance decreases when the outer layer is thickened. Is preferably thinner than 0.70 mm. Further, the thickness of the inner layer is preferably in the range of 0.05 to 0.3 mm from Examples 1 and 2.

Next, when using EEA whose inner layer EA amount is within the specified value and using EVA for the outer layer, the comparative example 1 (VA amount 12 wt%) with a small VA amount is compared with Example 1 (VA amount 17 wt%). Then, in Comparative Example 1, the flame retardancy is insufficient, whereas in Example 1, the flame retardancy is good, and Comparative Example 7 (VA amount 50 wt%) with a large amount of VA in the outer layer and Example 3 are used. , 4 (VA amount 42 wt%), Comparative Example 7 shows insufficient tensile properties , while Examples 3 and 4 show good tensile properties . Thereby, when using EVA for an outer layer, it is good to use EVA with 15 to 45 wt% of VA amount.

Similarly, when the EEA of the inner layer is within the specified value, and the EEA is used for the outer layer, the EA amount is inferior in flame retardancy in Comparative Example 6 (EA amount 9 wt%) with a small amount of EA. While many comparative examples 8 (EA amount 40 wt%) have insufficient tensile properties, Example 5 having an EA amount of 34 wt% has good tensile properties and flame retardancy . Examples 9 to 11 are examples in which EEA and EVA having an EA amount of 15 wt% are used in combination, but both have good flame retardancy. Therefore, the amount of EA when EEA is used for the outer layer is preferably 15 to 35 wt%.

Comparative Example 10 using EVA (or EEA) in which the EA amount (or VA amount) of the outer layer is within a specified value and EEA having an EA amount of 5 wt% is used for the inner layer is flame retardant, although the tensile properties are good. In Comparative Example 11 using EEA having an EA amount of 40 wt%, the flame retardancy is good, but the tensile properties are poor. In contrast, Example 1 with an EA amount of 9 wt% and Example 3 with an EA amount of 34 wt% both have good tensile characteristics and flame retardancy. For this reason, EEA having an EA amount of 9 to 35 wt% is preferably used for the inner layer.

  Further, as in Comparative Example 9, when EVA with an VA amount of 42 wt% is used for both the inner and outer layers, flame retardancy is lowered and tensile properties are poor, but EVA with an VA amount of 42 wt% is used for the outer layer and EA is used for the inner layer. Example 4 using 15% by weight of EEA and Example 3 using 34% by weight of EA have good tensile properties and flame retardancy.

In Examples 6 to 8, EVA having a VA amount of 42 wt% was used for the outer layer, and 5 wt% of maleic acid-modified EEA was added to the EVA to form an outer layer. In Example 8, maleic acid was also applied to the inner layer. In this example, 5% by weight of modified EEA is added, but both have good tensile properties and flame retardancy. On the other hand, Comparative Examples 1 and 7 in which 5 wt% of maleic acid-modified EEA was added to EVA and EEA in which the VA amount and EV amount of the inner and outer layers were outside the specified values were reduced in either tensile properties or flame retardancy. is doing.

  In Examples 1 to 11 and Comparative Examples 1 to 13, there was no difference in heat aging characteristics, and the voltage resistance and low temperature properties were both good.

It is a figure which shows one Embodiment of the electric wire and cable of this invention. In this invention, it is a figure explaining the mechanism of flame retardance. It is a figure which shows one Embodiment of the conventional electric wire and cable. It is a figure explaining the mechanism of combustion of the electric wire and cable of FIG.

Explanation of symbols

10 conductor 11 inner layer 12 outer layer

Claims (1)

In wire and cable comprising an inner layer and an outer layer of a resin composition on a conductor, wherein the inner layer of ethyl acrylate content (EA amount) of 9～35Wt% ethylene ethyl acrylate copolymer (EEA) alone or in other a flame retardant relative to the base polymer 100 parts by weight was mixed with the polyolefin resin comprises 50 to 150 parts by weight, the outer layer EA amount 15～35Wt% ethylene ethyl acrylate copolymer (EEA) or a vinyl acetate containing 150 to 300 parts by weight of a flame retardant with respect to 100 parts by weight of a base polymer obtained by mixing an ethylene vinyl acetate copolymer (EVA) having an amount (VA amount) of 15 to 45 wt% alone or with other polyolefin-based resin, The inner layer has a thickness of 0.05 to 0.30 mm, and the outer layer has a thickness of 0.30 to 0.70 mm. And non-halogen flame retardant electric wire cable, wherein a ratio of the thickness of the inner layer thickness and outer layer (inner layer thickness / thickness of the outer layer) is 1 / 7-1 / 2.

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