JP2007254536A - Phosphorus-free, highly flame-retardant, highly strong non-halogen resin composition and insulated electric wire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly flame-retardant, highly strong, phosphorus-free type non-halogen resin composition, and to provide an insulated electric wire. <P>SOLUTION: This highly flame-retardant, highly strong, phosphorus-free type non-halogen resin composition comprising 100 pts.wt. of a polyester-based resin and 5 to 100 pts.wt. of a 1,3,5-triazine derivative is characterized by using a resin mixture comprising 60 to 95 wt.% of polybutylene terephthalate and 5 to 40 wt.% of a polybutylene terephthalate-polyether block copolymer as the polyester-based resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a phosphorus-free high flame-retardant high-strength non-halogen resin composition and an insulated wire excellent in flame retardancy, particularly in a vertical flame-retardant level.

  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 a non-halogen flame retardant such as magnesium hydroxide is mixed with polyolefin is generally used as an electric wire insulator.

JP-A-8-48812 Japanese Patent No. 2681051

  However, an electric wire flame-retarded with a non-halogen flame retardant such as magnesium hydroxide is mixed with a very large amount of a non-halogen flame retardant in order to pass a vertical flame test such as VW-1 in the UL standard. Therefore, there is a problem that the mechanical strength is greatly reduced. On the other hand, there are methods 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. There is a tendency to refrain from using it recently because concerns are pointed out.

For these reasons, development of a phosphorus-free and halogen-free flame retardant wire excellent in flame retardancy has been required.
Then, the objective of this invention is providing the highly flame-retardant and high intensity | strength phosphorus-free type halogen-free resin composition and an insulated wire.

  In order to achieve the above object, the invention according to claim 1 is a composition obtained by mixing 5 to 100 parts by weight of a 1,3,5 triazine derivative with 100 parts by weight of a polyester resin. A phosphorus-free, highly flame-retardant, high-strength non-halogen resin composition characterized by being a mixed resin of 60-95% by weight of polybutylene terephthalate and 5-40% by weight of a polybutylene terephthalate-polyether block copolymer.

  In the invention of claim 2, the polybutylene terephthalate-polyether block copolymer is

The phosphorus-free high flame-retardant high-strength non-halogen resin composition according to claim 1.

  In the invention of claim 3, the polybutylene terephthalate-polyether block copolymer is

The phosphorus-free high flame-retardant high-strength non-halogen resin composition according to claim 1.

  A fourth aspect of the present invention is a phosphorus-free, highly flame-retardant, high-strength non-halogen insulated electric wire comprising a conductor coated with the composition according to any one of the first to third aspects.

  ADVANTAGE OF THE INVENTION According to this invention, the phosphorus-free high flame-retardant high intensity | strength non-halogen resin composition and insulated wire which have high flame retardance of a VW-1 level can be obtained.

  Hereinafter, a preferred embodiment of the present invention will be described in detail.

  The present invention relates to a composition in which 5 to 100 parts by weight of a 1,3,5 triazine derivative is mixed with 100 parts by weight of a polyester resin, and the polyester resin has a polybutylene terephthalate content of 60 to 95% by weight, A mixed resin of 5 to 40% by weight of butylene terephthalate-polyether block copolymer is used.

  The polybutylene terephthalate (hereinafter referred to as PBT) used in the present invention is preferably not reinforced with glass fiber or graphite. This is because the reinforced grade has no elongation.

  The PBT-polyether block copolymer is a thermoplastic elastomer in which the hard segment (crystalline phase) is PBT as shown in Chemical Formula 1 and the soft segment (amorphous phase) is made of polyether as shown in Chemical Formula 2. is there.

  The PBT-polyether block copolymer has an advantage that, as an engineering plastic, elongation is hardly lowered even when a relatively large amount of a filler such as a flame retardant is mixed.

  The reason why the PBT is defined as 60 to 95% by weight and the PBT-polyether block copolymer is defined as 5 to 40% by weight is that when the PBT is less than 60% by weight, the wear resistance is decreased. This is because the elongation is greatly reduced by mixing the triazine derivative.

  Examples of the 1,3,5-triazine derivative used in the present invention include 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. The reason why these amounts are limited to 5 to 100 parts by weight is that if the amount is less than 5 parts by weight, the flame retardancy is not effective, and if the amount exceeds 100 parts by weight, the elongation and wear resistance are remarkably lowered.

In the present invention, a metal hydroxide such as magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₃ ), hydrotalcite, calcium aluminate hydrate, calcium hydroxide, hydroxide Barium etc. can be added. Examples of magnesium hydroxide include synthetic magnesium hydroxide, natural magnesium hydroxide obtained by pulverizing natural ore, and a solid solution with other elements such as Ni.

  Moreover, the surface of these metal hydroxides may be used after being surface-treated by a known technique using vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, fatty acid, fatty acid metal salt, or the like.

  The composition of the present invention can be crosslinked, for example, by irradiation with an electron beam or γ-ray, or chemically crosslinked using peroxide.

  In addition, metal oxide compounds such as magnesium oxide, antimony oxide, aluminum oxide, silicone compounds such as silicone gum, silicone powder, silicone oil, silicone graft polyolefin, polyorganosiloxane and acrylic rubber composite rubber, zinc borate, boric acid Boric acid compounds such as calcium, barium borate, and barium metaborate, or nitrogen-based flame retardants such as guanidine sulfamate may be added.

  Furthermore, an intumescent flame retardant, which is a flame retardant composed of a mixture of a foaming component and a solidifying component, for example, a nitrogen-based foaming agent as a foaming component, has a high decomposition temperature such as a tetrazole compound (300 ° C. The above may be used as appropriate.

  These resin compositions include antioxidants, lubricants, surfactants, softeners, plasticizers, inorganic fillers, compatibilizers, stabilizers, crosslinking agents, UV absorbers, and light stabilizers as necessary. Colorant additives can be added.

  Examples and comparative examples of the present invention are shown in Table 1.

  The electric wire 10 according to the present invention was produced in the following manner.

As shown in FIG. 1, a 1.25 mm ² copper stranded wire conductor 11 was coated with the resin composition shown in Table 1 at 220 to 250 ° C. using a 40 mm extruder as the insulator 12. The thickness of the insulator 12 was 0.3 mm.

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

(1) Tensile properties:
The core wire is extracted from the produced electric wire, and is pulled at a speed of 200 mm / min using a shopper type tensile tester according to JISC3005, and the tensile strength and elongation are evaluated. .

(2) Flame retardancy:
The manufactured electric wire was subjected to a VW-1 combustion test according to ULsubject758. The flame spread time after removing the flame for 15 seconds was measured. Of the five tests, the one with the maximum fire spread time was taken as the measured value, the fire extinguished in less than 60 seconds passed, and the fire spread for 60 seconds or longer was rejected.

(3) Abrasion resistance:
Using a UL abrasion tester (90 ° sharp edge, 3 blades), the number of reciprocations when the load was 200 g was evaluated, and the target was 100 times or more.

  As can be seen from Table 1, Examples 1 to 5 of the present invention are all excellent in tensile properties, flame retardancy, and wear resistance.

  On the other hand, Comparative Example 1 having a PBT less than the specified value has insufficient tensile strength and wear resistance, and Comparative Example 2 having a PBT value exceeding the specified value does not reach the target. Further, Comparative Example 3 with less melamine cyanurate failed in flame retardancy, and Comparative Example 4 with more melamine cyanurate failed in tensile strength, elongation, and abrasion resistance.

It is a figure which shows the structure of the insulated wire using the composition in this invention.

Explanation of symbols

10 Electric wire 11 Conductor 12 Insulator

Claims (4)

  In a composition in which 5 to 100 parts by weight of a 1,3,5 triazine derivative is mixed with 100 parts by weight of a polyester resin, the polyester resin contains 60 to 95% by weight of polybutylene terephthalate, polybutylene terephthalate-poly A phosphorus-free high flame-retardant high-strength non-halogen resin composition, which is a mixed resin of 5 to 40% by weight of an ether block copolymer. Polybutylene terephthalate-polyether block copolymer is

The phosphorus-free high flame-retardant high-strength non-halogen resin composition according to claim 1. Polybutylene terephthalate-polyether block copolymer is

The phosphorus-free high flame-retardant high-strength non-halogen resin composition according to claim 1.   A non-phosphorus-free flame-retardant high-strength non-halogen insulated wire, comprising a conductor coated with the composition according to claim 1.

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