JP2616114B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame retardant having flame retardancy, good heat aging resistance, excellent electrical insulation, and relatively good mechanical properties. The present invention relates to a conductive resin composition.

[Prior art] All materials conventionally used as insulators and sheaths of electric wires and cables, including polyolefins, which are widely used because of their excellent electrical insulation properties, are all flammable and fire. When an outbreak occurs, fires often spread along the wiring system of electric wires and cables, and the demand for flame-retardant electric wires and cables has increased rapidly.

In recent years, the demand for flame retardancy has increased, especially for electric wires and cables, and the ULVW-1 vertical combustion test, IEEE Standard 383, IEC
There is an increasing demand for highly flame-retardant materials having a vertical tray combustion test level such as standard 332.

As a method for making a polyolefin flame-retardant, the following method is generally employed.

(1) A method in which a compound containing a hagen molecule in a molecule such as hexabromobenzene and an antimony trioxide or a zirconium salt are used in combination.

(2) A method of blending a hydrated compound such as aluminum hydroxide and magnesium carbonate.

(3) A method of blending a flame-retardant polymer such as chlorinated polyethylene in combination with antimony trioxide or a zirconium salt.

Each of these methods has advantages and disadvantages, and the most appropriate method is selected and applied according to the purpose of flame retardation.

[Problems to be Solved by the Invention] However, in each of the above-described methods, when the amount of the flame retardant mixed is increased in order to enhance the flame retardant effect, the electrical characteristics and mechanical properties of the obtained polyolefin-based composition are increased. In addition to deteriorating the characteristics, various problems are caused.

That is, when the content of the halogen-containing compound is increased, a large amount of halogen-based gas is generated, and this gas is often toxic such as hydrogen chloride, and generates a large amount of smoke containing such a toxic gas. The outlook worsens, hinders evacuation and extinguishing activities in the event of a fire, or the toxic gas may have a negative effect on the human body, causing a secondary disaster. It may react and become hydrohalic acid, corroding equipment and the like.

In addition, since inorganic flame retardants have a small flame retardant effect, in order to impart a high degree of flame retardancy suitable for each of the above combustion tests,
It is necessary to add a large amount of an inorganic flame retardant, and as a result, there is a problem that the tensile properties, water resistance, etc. of the resulting insulator or sheath are reduced.

An object of the present invention is to solve the above-mentioned problems of the prior art, and to have flame retardancy, good heat aging resistance, excellent electrical insulation, and relatively good mechanical properties. An object of the present invention is to provide a novel flame-retardant resin composition.

[Means for Solving the Problems] The gist of the present invention is as follows. And 10 to 100 parts by weight of talc and 0.1 to 10.0 parts by weight of a P-phenylenediamine-based antioxidant, and secondly, 20 to 50 parts by weight of chlorinated polyethylene and ethylene-based copolymer. For 100 parts by weight of a composition obtained by blending 80 to 50 parts by weight of a polymer, 5 to 50 parts by weight of talc, 5 to 50 parts by weight of calcined clay and P
-It is obtained by blending 0.1 to 10.0 parts by weight of a phenylenediamine-based antioxidant and crosslinking.

As the ethylene-based copolymer used in the present invention, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), ethylene·
There are a propylene copolymer and an ethylene / hexene copolymer.

In the present invention, the reason for blending the chlorinated polyethylene is to impart flame retardancy, and the reason for limiting the mixing ratio with the copolymer is that the ratio of the chlorinated polyethylene is limited.
If it is less than 20%, sufficient flame retardancy cannot be obtained, and if it is more than 50%, heat resistance will decrease.

In addition, talc and calcined clay were selected as fillers because they improve electrical insulation and heat resistance without reducing mechanical properties and flame retardancy.

In addition, the amount of these fillers was limited because talc or the total amount of talc and calcined clay was less than 10 parts by weight, there was almost no effect on the improvement of heat resistance and electrical insulation. If there is too much, further performance improvement can not be expected,
This is because the mechanical properties are rather deteriorated.

It is not preferable that the amount of the P-phenylenediamine-based antioxidant is limited because less than 0.1 part by weight has no effect as an antioxidant, and more than 10.0 parts by weight causes crosslinking inhibition and blooming. Because.

The P-femiresinamine-based antioxidants used in the present invention include N, N'-diphenyl-P-phenylenediamine, N-isopropyl-N'-phenyl-P-phenylenediamine, N, N'-di-2. -Naphthyl-P-phenylenediamine, N-cyclohexyl-N'-phenyl-P
-Phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -P-
Phenylenediamine, N, N'-bis (1-methylheptyl) -P-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -P-phenylenediamine, N, N'-
Bis (1-ethyl-3-methylpentyl) -P-phenylenediamine, N- (1,3-dimethylbutyl) -N'-
Phenyl-P-phenylenediamine, diallyl-P-phenylenediamine mixture, phenyl, hexyl-P-
Phenylenediamine, phenyl, octyl-P-phenylenediamine and the like.

It is to be noted that an appropriate amount of commonly used compounding agents such as a plasticizer, a lubricant, an ultraviolet absorber, a coloring agent, an antistatic agent and other antioxidants may be added to the above composition.

The composition of the present invention comprises the above components, an open roll,
After kneading with a Banbury mixer etc. into pellets,
For example, it is easily supplied to an extruder, extruded and coated on a metal conductor, heated with superheated steam, cross-linked, and processed into a predetermined product.

In the present invention, the P-phenylenediamine-based antioxidant is used because, when the present composition is crosslinked, consumption of free radicals generated by decomposition of an organic peroxide (eg, dicumyl peroxide) used as a crosslinker is reduced. This is because a flame-retardant composition having little heat resistance and excellent heat resistance can be obtained.

[Examples] Specific examples are described below using Examples according to the present invention and Comparative Examples using calcium carbonate as a filler, and Comparative Examples using phenolic and quinoline-based antioxidants as antioxidants. explain.

According to the respective composition shown in Table 1, chlorinated polyethylene and a copolymer mainly composed of ethylene were melt-wound with an open roll for mixing at 120 ° C. so as to be uniform. A fuel, an antioxidant, a filler and the like were added and kneaded uniformly. Next, press molding at 120 ° C, thickness 1mm
Was prepared and crosslinked with superheated steam at 13 kg / cm ² for 3 minutes, and the properties of each sheet were evaluated using the sheet.

The volume resistivity was measured using a high-voltage resistance meter and a cell for the resistance meter (manufactured by Yokogawa Hewlett-Packard Company).

Tensile test is a shopper type tensile tester (made by Kamishima Seisakusho)
Was measured at a tensile speed of 500 / min.

In evaluating the flame retardancy, a sample was prepared by preparing an electric wire from a composition comprising the components shown in Table 1 in accordance with a conventional method, and cross-linking the composition with superheated steam.

The flame retardancy test is based on CU1581,
After applying a fixed amount of flame for 15 seconds from a burner with a constant inclination, 15
The flame was removed for a second, and this was repeated five times. If the wire did not burn beyond a certain amount, or if the ash dripped and did not burn into the underlying cotton, the test was passed.

As is evident from Table 1, it can be seen that the P-phenylenediamine-based antioxidant provides an effect excellent in electric insulation as compared with other antioxidants.

In addition, it can be seen that when talc is used as a filler, electric insulation and heat resistance are improved as compared with other fillers, and that when baked clay is used in combination, these properties are further improved.

When comparing the ratio of copolymers such as EVA and EMMA and chlorinated polyethylene by changing the blend outside the above range, the heat resistance greatly decreases when the amount of chlorinated polyethylene is large, and when it is small, the flame resistance is low. Does not pass the exam. Therefore, it is understood that the ratio of the blend of the chlorinated polyethylene and the copolymer mainly composed of ethylene is preferably in the above specified range.

[Effects of the Invention] As described above, according to the present invention, it has flame retardancy,
An insulating coating having good heat aging resistance and excellent electrical insulation properties can be obtained. Specifically, for example, the present invention can be applied to, for example, an electric wire for a vehicle or equipment wiring to exhibit high utility.

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Claims (2)

(57) [Claims] A talc (10 to 100 parts by weight) and a P-phenylenediamine-based compound (100 parts by weight) prepared by blending 20 to 50 parts by weight of a chlorinated polyethylene and 80 to 50 parts by weight of a copolymer mainly composed of ethylene. A flame-retardant resin composition containing 0.1 to 10.0 parts by weight of an antioxidant. 2. A blend of 20 to 50 parts by weight of chlorinated polyethylene and 80 to 50 parts by weight of a copolymer mainly composed of ethylene, 100 to 100 parts by weight of talc, 5 to 50 parts by weight of calcined clay, Parts by weight and P-phenylenediamine-based antioxidant
A flame-retardant resin composition containing 0.1 to 10.0 parts by weight and being crosslinked.