JPS61114406A - Noncombustible insulated wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to ultraviolet irradiation! ) l A flame-retardant insulated wire with excellent adhesion to hardening paints.

[Prior Art] When coloring thermosetting or thermoflexible polymer materials,
There are two methods: one is to knead coloring agents such as pigments directly into the material during compounding, and the other is to apply paint after molding.

In the former case, it is necessary to prepare as many inbound bottles as the number of colors required, which poses problems in terms of manufacturing and storage.

In the latter case, it is necessary to prepare only one type of natural-colored compound, which is extremely advantageous in terms of cost, and has recently become rapidly popular.

There are various methods for applying this paint, but among them, the ultraviolet irradiation curing method is attracting attention due to its increased production speed, energy savings, safety, and equipment costs, and will be used in more and more applications in the future. It is considered that

However, the adhesion of ultraviolet ray curable paints to substrates varies greatly depending on the substrate material. For example, polyvinyl chloride,
It shows good adhesion to so-called polar polymers such as nylon, urethane, and ABS resin, but it shows good adhesion to so-called polar polymers such as nylon, urethane, and ABS resin.
] Adhesion to non-polar or less polar polymers such as pyrene and ethylene-propylene rubber is poor, and there is a problem that the paint may peel off over time.

In particular, in the case of flame retardant compositions, the brominated flame retardant decoupled diphenyl ether and the chlorinated dodecachlorodobylhydrodimethinodibenzosic (cooctene) (commercially available from Hooker Chemical under the trade name Dechlorane Plus) are used. )
is added, but this further promotes a decrease in adhesion.

As a solution to this problem, the substrate surface can be treated by (1) chemical treatment, (a) solvent treatment, (3) coupling treatment, (4) Nanatsuma or polymer coding, solid surface active treatment, (6) steam treatment, (7) Depending on the material and shape, the appropriate 1.73 type is selected from surface grafting, etc. However, even with such treatment, the adhesion of the paint is not necessarily sufficient, and the lifespan may be slightly extended. Therefore, long-term stabilization cannot be achieved.

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned problems, and it has flame retardancy and also significantly improves the adhesion to the surface of an ultraviolet curable paint. The purpose of this invention is to provide flame-retardant insulated wires with high heat resistance.

[Means for Solving the Problems] The flame retardant insulated wire of the present invention contains 10 to 40 parts of a halogen flame retardant having a halogen content of 60% or more based on 100 parts by weight of the ethylene polymer. A coating layer of a resin composition containing 10 to 30 parts by weight of antimony trioxide and 0.5 to 10 parts by weight of low molecular weight polyolefin polyol is provided on the outer periphery of the conductor. The invention is characterized in that it is constructed by providing a coating layer of.

In the present invention, the ethylene polymers include polyethylene, ethylene-vinyl acetate copolymer, copolymer of ethylene and acrylic acid or its ester, ethylene-propylene copolymer, and ethylene-propylene-diene monomer copolymer. etc. can be mentioned. Furthermore, examples include ethylene-α olefin copolymers, ethylene-butylene copolymers, halogenated polyolefins, and those on which vinyl chloride monomers are grafted. These materials can be used alone or in combination.

The halogen-based organic flame retardant must contain 60% or more of halogen-containing M. If the halogen content ω is less than 60% by weight, the amount of ω required to impart flame retardance is too high.
6), which reduces mechanical strength and causes agglomeration on the surface, reducing printability.

In addition, the halogen-based right mM fuel is ethylene-based boria 10
It is necessary to add in the range of 10 to 40 parts by weight relative to 0 parts by weight. If it is less than 10 parts by weight, flame retardancy will be insufficient, and if it exceeds 40 parts by weight, mechanical strength will decrease and printing will occur. It leads to a decline in sexuality.

Such flame retardants include methylene-bis-tetrabromophthalimide (Br: 68%), ethylene-bis-tetrabromophthalimide (Br: 67%), propylene-bis-tetrabromophthalimide (Br: 66%),
Butylene-bis-tetrabromophthalimide (Sr:6
5%), decabromodinol ether (Br: 83%
), Dechlorane Plus (manufactured by Hooker Chemical Co.) (
C1:65%), etc., and can be used alone or in combination.

'E Antimony trioxide and halogenated mH flame retardant improve the flame retardance through a mutual action, and it is necessary to add it in the range of 10 to 30 parts by weight per 100 parts by weight of the ethylene polymer.

If it is less than 10 parts by weight, sufficient M furnace strength cannot be imparted, and if it exceeds 30 parts by weight, the mechanical strength will be reduced.

The low molecular weight polyolefin polyol is a resin having a molecular group having four water groups at the end of the molecule in the range of 1,000 to s, ooo, and is commercially available from Mitsubishi Kasei Corporation under the trade name Polytail. There are two basic resins: one that is wax-like solid at room temperature (Polysol H) and one that is liquid (Polytail HΔ), and Polytail I-IE is a modified resin.

This resin is thought to be used for the purpose of improving printability, and is used at a concentration of 0.5 parts by weight per 100 parts by weight of ethylene borea.
It is necessary to add in the range of ~10 parts by weight; if it is less than 0.5 parts by weight and 1 part by weight, the printability cannot be improved, and if it exceeds 10 parts by weight, the mechanical strength will decrease.

A resin composition containing the above various components is extruded and coated on the outer periphery of the conductor. This coating layer may be crosslinked or non-crosslinked. In the case of crosslinking, the most common crosslinking method is heating crosslinking by adding n peroxides.
-butylperoxy-isopropyl)benzene.

Furthermore, antioxidants, hypothetical auxiliaries, fillers, and the like may be added.

The surface of the insulator thus formed is colored by applying an ultraviolet ray curable paint containing a coloring agent.

Examples of UV curable paints include acrylic urethane oligomers, acrylic varnish oligomers, acrylic-[boxyoligomers, and mixtures of thiol compounds and compounds with carbon-carbon double bonds (ReP9311 product from W.R. Brace & Company). (commercially available), and if necessary, reactive octamants such as ethyl-hexyl acrylate, styrene, and vinylpyrrolidone, and photosensitizers such as benzophenone, benzoin isopropyl ether, and anthraquinone may be added. It's okay.

[Example] After mixing C in a Panbury mixer according to the formulations shown in Table 1, a 2 mm2 conductor was coated with a thickness of 1 mm by an extruder.
．． Extrusion coating was performed to a thickness of 1 mm, and heat crosslinking was performed. Then RC
Apply a thin layer of black paint based on P9311, and apply a UV curing device with a light emitting length of 250 mm to 125 mm/S.
Curing was achieved by passing through at CC speed.

Thus, the evaluation results for the 17 wires are shown in the lower column of Table 1.

The flame retardancy evaluation was conducted based on UL standard 5UB758, and the adhesion of the paint was measured using a NEMA abrasion tester. A 4sφ chrome-plated iron rod was moved back and forth over the sample at a load of 300q to cause abrasion. Evaluation was based on the number of times. 100
If it is more than twice, it is sufficient for practical use.

As is clear from Table 1, Examples 1 to 4, which fall within the wood range, are well-balanced in each characteristic.

Comparative Example 1 uses a flame retardant with an antimony trioxide content below the specified value of the present invention, and Comparative Example 2 uses a flame retardant with a halogen content below the specified value of the present invention. Passed. Comparative Example 3 does not contain a low molecular weight polyolefin polyol and has poor adhesion.

Comparative Example 4 contains a flame retardant in an amount exceeding the specified value of the present invention, and has poor tensile strength and adhesiveness. Comparative Example 5 contains a low molecular weight polyolefin polyol in an amount greater than the specified value of the present invention, and has poor tensile strength.

[Effects of the Invention] As explained above, according to the present invention, an insulated wire having excellent adhesion to colored paint and flame retardancy can be obtained.

Claims (1)

[Claims] (1) Add 1 part of halogen-based organic flame retardant with a halogen content of 60% by weight or more to 100 parts by weight of ethylene-based polymer.
0 to 40 parts by weight, 10 to 30 parts by weight of antimony trioxide, and 0.5 to 1 part of low molecular weight polyolefin polyol.
1. A flame-retardant insulated wire, characterized in that a coating layer of a resin composition containing 0 parts by weight is provided on the outer periphery of a conductor, and a layer of an ultraviolet ray curable paint is formed on the outer periphery.