JPH05230292A - Flame-retardant olefin resin composition and electric wire and cable excellent in flame retardancy and abrasion resistance wherein flame-retardant olefin resin composition is used - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. capable of being formed into electric wire and cable excellent in flame retardancy and abrasion resistance by incorporating polypropylene and potassium titanate into a flame-retardant olefin resin compsn. comprising an olefin resin and a metal hydrate. CONSTITUTION:Polypropylene and potassium titanate are incorporated into a flame-retardant olefin resin compsn. comprising an olefin resin (e.g. high- density polyethylene or ethylene-vinyl acetate copolymer) and a metal hydrate (e.g. magnesium hydroxide) to obtain a flame-retardant olefin resin compsn. The incorporation of the polypropylene and potassium titanate into the resin compsn. can improve the abrasion resistance thereof without a decrease in the amt. of the metal hydrate contained in the olefin resin for the purpose of improving the flame retardancy thereof, while no strongly toxic gas polluting the environment is generated even when a fire breaks out to burn the compsn. used as an insulating material, because it does not contain any halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition used as a covering insulating material for electric wires and cables,
In particular, a flame-retardant olefin resin composition capable of improving flame retardancy and wear resistance using a non-halogen flame-retardant compound, and flame retardancy using a flame-retardant olefin resin composition
Electric wire and cable with excellent wear resistance.

[0002]

2. Description of the Related Art In recent years, excellent synthetic resins have come to be produced at low cost, and because of their ease of molding and good durability, they are used for all kinds of daily sundries such as kitchen utensils. It has arrived. In particular, a thermoplastic resin composition is used which exhibits plasticity when heated, solidifies when cooled, and exhibits plasticity when reheated. Further, this thermoplastic resin composition is used for a civil engineering sheet for underground burying because of its excellent water resistance. On the other hand, since this thermoplastic resin composition has excellent electrical properties and a low dielectric constant and low dielectric loss, it can be used as an insulator or sheath for an insulated wire or cable formed by coating it on a conductor or an insulated wire. It is used.

Conventionally, as a thermoplastic resin composition, a polyvinyl chloride resin composition has been widely used because of its relatively high withstand voltage and insulation resistance and low production cost. In addition, this polyvinyl chloride resin composition alone has excellent flame retardancy.

However, in the conventional thermoplastic resin composition using such a polyvinyl chloride resin composition,
For example, when electric wires and cables are burned for incineration and disposal, hydrogen chloride gas is generated from the polyvinyl chloride resin composition. This hydrogen chloride gas is a corrosive gas and has a problem that it is harmful.

Therefore, in recent years, an olefin resin composition such as polyethylene is used as an insulator without using a halide in an electric wire at a portion which emits a high temperature, such as a wire harness of an automobile.
Attempts have been made to use it for cable insulation. This olefin resin composition alone does not have flame retardancy,
It is made flame-retardant by mixing metal hydrates such as magnesium hydroxide.

[0006]

However, an insulator mainly composed of such an olefinic resin composition has a problem that its wearability is deteriorated when a metal hydrate such as magnesium hydroxide is mixed, and thus the wear resistance is deteriorated. In order to suppress the deterioration of the properties, it is necessary to reduce the amount of mixed metal hydrate such as magnesium hydroxide. However, in some cases, for example, an insulator of a wire harness for an automobile, it may be necessary to focus on flame retardancy rather than abrasion resistance depending on the purpose of use. In order to make this flame retardancy equal to the flame retardancy when a conventional polyvinyl chloride resin composition is used as an insulator, a large amount of metal hydrate such as magnesium hydroxide must be mixed, It has a problem that the wear property is significantly reduced. The present invention is mainly composed of an olefin resin composition,
A flame-retardant olefin-based resin composition which does not contain a halide and has a flame retardancy equal to or higher than that of a conventional polyvinyl chloride resin composition and which can prevent a decrease in wear resistance.
Another object of the present invention is to provide an electric wire / cable that uses a flame-retardant olefin resin composition and has excellent flame retardancy and abrasion resistance.

[0007]

To achieve the above object, in the flame-retardant olefin resin composition of the present invention, a flame-retardant olefin resin composition obtained by mixing a metal hydrate with an olefin resin. In addition, it contains polypropylene and potassium titanate.

In order to achieve the above object, the flame-retardant olefin resin composition of the present invention contains 100 parts by weight of olefin resin and 5 to 5 parts of polypropylene.
50 parts by weight, 10 to 200 parts by weight of metal hydrate, and 3 to 15 parts by weight of potassium titanate are blended.

Further, in order to achieve the above object, the flame-retardant property of the flame-retardant olefin resin composition of the present invention is
For electric wires and cables having excellent wear resistance, a flame-retardant olefin resin composition containing polypropylene and potassium titanate in a flame-retardant olefin resin composition prepared by mixing a metal hydrate with an olefin resin. An object is coated on a conductor as an insulator.

[0010]

[Function] Since a flame-retardant olefin resin composition obtained by mixing a metal hydrate with an olefin resin contains polypropylene and potassium titanate, it is possible to improve the flame retardancy of the olefin. The wear resistance can be improved without reducing the amount of metal hydrate contained in the resin. Further, since no halide is added, even if a fire occurs and the insulator burns, a highly toxic gas is not generated and the environment is not polluted.

To obtain these effects, 100 parts by weight of an olefin resin and 5 to 5 parts of polypropylene are used.
50 parts by weight, 10 to 200 parts by weight of metal hydrate, and 3 to 15 parts by weight of potassium titanate may be added.

Further, a flame-retardant olefin resin composition obtained by mixing a metal hydrate with an olefin resin is added to the flame-retardant olefin resin composition containing polypropylene and potassium titanate as an insulator. Since it is coated on top of it, abrasion resistance can be improved without reducing the amount of metal hydrate contained in the olefin resin to improve flame retardancy, and the insulator has an abnormally high temperature. Even if exposed to heat, it will not melt and cause dielectric breakdown to cause a short circuit, and since halide is not added, even if the insulator burns due to fire or incineration disposal, a highly toxic gas is generated. It does not pollute the environment.

[0013]

EXAMPLES Specific examples of the present invention will be described below in comparison with comparative examples.

Example 1 In this example, an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.) was used.
C-EEA) 70 parts by weight, ethylene-vinyl acetate copolymer (EVA, specifically Evatate manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight, polypropylene (PP, specifically Nippon Petrochemical Co., Ltd.) Company made Nisseki Polypro) 3
0 parts by weight, 150 parts by weight of magnesium hydroxide, and 13 parts by weight of potassium titanate are mixed.

Example 2 This example is an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.).
50 parts by weight of polypropylene (PP, specifically, Nisseki Polypro manufactured by Nippon Petrochemical Co., Ltd.), 200 parts by weight of magnesium hydroxide, and 15 parts by weight of potassium titanate were mixed with 100 parts by weight of C-EEA). It is a thing.

Example 3 In this example, linear low density polyethylene (LLDPE,
Specifically, 70 parts by weight of Nippon Oil Chemical Co., Ltd. Nisseki Linilex, ethylene-vinyl acetate copolymer (EV)
A, specifically, Emitate manufactured by Sumitomo Chemical Co., Ltd.) 3
20 parts by weight of polypropylene (PP, specifically Nisseki Polypro manufactured by Nippon Petrochemical Co., Ltd.), 300 parts by weight of magnesium hydroxide, 0.5 parts by weight of red phosphorus, and 10 parts by weight of potassium titanate per 0 parts by weight. It is a mixture of parts.

Example 4 In this example, an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.) was used.
C-EEA) 30 parts by weight, linear low density polyethylene (LLDPE, specifically manufactured by Nippon Petrochemical Co., Ltd.)
20 parts by weight of polypropylene (PP, specifically Nisseki Polypro manufactured by Nippon Petrochemical Co., Ltd.), 100 parts by weight of magnesium hydroxide, and 8 parts by weight of potassium titanate were mixed with 70 parts by weight of Nisseki Linilex. It is a thing.

Example 5 In this example, an ethylene-ethyl acrylate copolymer (EEA, specifically NV manufactured by Nippon Unicar Co., Ltd.) was used.
C-EEA) 70 parts by weight, linear low-density polyethylene (LLDPE, specifically manufactured by Nippon Petrochemical Co., Ltd.)
10 parts by weight of Nisseki Linilex, 10 parts by weight of high-density polyethylene (HDPE, specifically Nippon Petrochemical Co., Ltd. Nisseki Stafren), polypropylene (PP, specifically, Nippon Petrochemical Co., Ltd.) Nisseki Polypro) 5 parts by weight, magnesium hydroxide 100 parts by weight,
0.5 parts by weight of red phosphorus and 6 parts by weight of potassium titanate are mixed.

Example 6 In this example, an ethylene-ethyl acrylate copolymer (EEA, specifically NV manufactured by Nippon Unicar Co., Ltd.) was used.
C-EEA) 70 parts by weight, ethylene-vinyl acetate copolymer (EVA, specifically Evatate manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight, polypropylene (PP, specifically Nippon Petrochemical Co., Ltd.) Company-made Nisseki Polypro) 5
By weight, 10 parts by weight of magnesium hydroxide and 3 parts by weight of potassium titanate are mixed.

Example 7 In this example, an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.) was used.
To 100 parts by weight of C-EEA, 40 parts by weight of polypropylene (PP, specifically Nisseki Polypro manufactured by Nippon Petrochemical Co., Ltd.), 150 parts by weight of magnesium hydroxide, and 5 parts by weight of potassium titanate were blended. It is a thing.

Comparative Example 1 Comparative Example 1 is a linear low density polyethylene (LLDPE,
Specifically, 70 parts by weight of Nippon Petrochemical Co., Ltd. Nisseki Linilex, high-density polyethylene (HDPE, specifically, Nippon Petrochemical Co., Ltd. Nisseki Stafren) 3
80 parts by weight of magnesium hydroxide and 15 parts by weight of potassium titanate are mixed with 0 parts by weight.

Comparative Example 2 Comparative Example 2 is an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.).
C-EEA) 70 parts by weight, ethylene-vinyl acetate copolymer (EVA, specifically Evatate manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight, polypropylene (PP, specifically Nippon Petrochemical Co., Ltd.) Company-made Nisseki Polypro) 5
It is a mixture of 0 parts by weight and 150 parts by weight of magnesium hydroxide.

Conventional Example 1 Conventional Example 1 is an ethylene-ethyl acrylate copolymer (EEA, specifically NV manufactured by Nippon Unicar Co., Ltd.).
C-EEA) 70 parts by weight, ethylene-vinyl acetate copolymer (EVA, specifically, Evatate manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight, and 10 parts by weight of magnesium hydroxide are mixed.

Conventional Example 2 Conventional Example 2 is an ethylene-ethyl acrylate copolymer (EEA, specifically, NV manufactured by Nippon Unicar Co., Ltd.).
C-EEA) 70 parts by weight, linear low-density polyethylene (LLDPE, specifically manufactured by Nippon Petrochemical Co., Ltd.)
100 parts by weight of magnesium hydroxide and 0.5 parts by weight of red phosphorus with respect to 10 parts by weight of Nisseki Linilex) and 10 parts by weight of high-density polyethylene (HDPE, specifically Nisseki Stafren manufactured by Nippon Petrochemical Co., Ltd.). It is a mixture of.

Conventional Example 3 Conventional Example 3 is a linear low density polyethylene (LLDPE,
Specifically, 70 parts by weight of Nippon Petrochemical Co., Ltd. Nisseki Linilex, high-density polyethylene (HDPE, specifically, Nippon Petrochemical Co., Ltd. Nisseki Stafren) 3
80 parts by weight of magnesium hydroxide is blended with 0 part by weight.

Conventional Example 4 Conventional Example 4 is an ethylene-ethyl acrylate copolymer (EEA, specifically NV manufactured by Nippon Unicar Co., Ltd.).
C-EEA) 70 parts by weight, ethylene-vinyl acetate copolymer (EVA, specifically Evatate manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight, and magnesium hydroxide 150
It is a mixture of 1 part by weight and 0.5 part by weight of red phosphorus.

Conventional Example 5 Conventional Example 5 is an ethylene-ethyl acrylate copolymer (EEA, specifically NV manufactured by Nippon Unicar Co., Ltd.).
C-EEA) is mixed with 200 parts by weight of magnesium hydroxide.

In Example 3, Example 5, Conventional Example 2 and Conventional Example 4, 0.5 parts by weight of red phosphorus is added as a flame retardant aid, and magnesium hydroxide (flame retardant )
This is because the flame-retardant effect can be enhanced without increasing the compounding amount.

Each of the flame-retardant olefin-based resin composition based on these examples, the flame-retardant olefin-based resin composition based on the comparative example, and the flame-retardant olefin-based resin composition based on the conventional example has a thickness of 0.4 mm. An automotive low voltage electric wire (AV wire) coated with an insulator was prepared, and the oxygen index was measured by a scrape test and a combustion test. The comparison results are shown in Tables 1 and 2.

Table 1 Table 2 The scrape tests in Tables 1 and 2 are performed as shown in FIG. That is, the sample 1 cut into 750 mm is supported and fixed to the support fixture 3 provided on the table 2. The metal plunger 4 is brought into contact with the insulator of the sample 1 which is supported and fixed to the support fixture 3, and the metal plunger 4 is reciprocated by 100 mm at a speed of 50 to 60 times / minute. The reciprocating motion of the metal plunger 4 is repeated until the tip breaks the insulator and contacts the conductor. At the tip of this metal plunger 4, JI
Φ0.45 ± using tungsten carbide equivalent to G type 2 specified in S ・ H ・ 5501 (Cemented Carbide)
A 0.01 mm sphere 5 is attached. A weight 6 of 7N (714 g) is attached to the rear end of the metal plunger 4. Therefore, the metal plunger 4
Is reciprocating 100 mm at a speed of 50 to 60 times / minute, the ball 5 at the tip of the metal plunger 4 receives 7N
A load of (714 g) is applied.

Further, the conductor 11 at one end of the sample 1 supported and fixed to the support fixture 3 and the metal plunger 4 are connected via the current measuring device 7. This electricity measuring device 7
While applying a load of 7 N (714 g) on the insulator of Sample 1, set the metal plunger 4 at a speed of 50 to 60 times / minute.
The reciprocating motion of 00 mm causes the reciprocating motion of the ball 5 at the tip of the metal plunger 4 to abrade the insulator of the sample 1, and the time point at which the ball 5 at the tip of the metal plunger 4 breaks the insulator and contacts the conductor. It is something to detect. Therefore, in the wear characteristic test of the insulator of sample 1, the ball 5 at the tip of the metal plunger 4 broke the insulator of sample 1 and
The reciprocating motion of the metal plunger 4 is repeated at a speed of 50 to 60 times / minute until the conductor 11 is brought into contact with the conductor 11, and the number of reciprocating times until the ball 5 comes into contact with the conductor 11 is measured. In this scrape test, one sample 1 was measured at one location, and then this sample 1 was measured at 100 mm.
It is moved four times, that is, moved and rotated clockwise by 90 degrees to be fixed, the same test is performed again, the same operation is performed again, and the test is performed again. That is, one sample 1 is measured four times, and the lowest value among the measured values is set as the measured value of the sample. All the measurement results were measured with the ball 5 at the tip of the metal plunger 4 at a speed of 50-60 times / minute.
The reciprocating motion of 00 mm is performed to make one reciprocating motion, and the number of reciprocating motions until the sphere 5 comes into contact with the conductor 11 of the sample 1 due to wear of the insulator is displayed.

The oxygen indexes in Tables 1 and 2 indicate the amount (%) of oxygen required to start combustion. That is, if the oxygen index is 70, it means that combustion cannot start without 70% oxygen. Oxygen index 1
If it is 0, it will not start burning unless there is 10% oxygen.
Alternatively, it means that if 10% or more of oxygen is present, it will start burning. Therefore, the larger the oxygen index, the higher the flame retardancy.

The target value of the scrape resistance (standard value when the polyvinyl chloride resin composition is used as an insulator) is 3
At 00 times, the target value of the oxygen index (standard value when the polyvinyl chloride resin composition is used as an insulator) is 25 or more.

In each of Examples 1 to 7 in Table 1, the scrape resistance (wear resistance) is 309 to 780, which exceeds the target value. In addition, Examples 1 to 5 and Example 7
Has an oxygen index of 27 to 37, which exceeds the target value. Looking at Example 6, the compounding amount of magnesium hydroxide is extremely low at 10 parts by weight as compared with the other Examples. From this, it can be seen that the blending amount of magnesium hydroxide is greatly related to the oxygen index. This means that
Also appears significantly in. This prior art example 1 is also the embodiment 6
Similarly, the compounding amount of magnesium hydroxide is extremely low at 10 parts by weight, and the oxygen index is 19, which is the same result as in Example 6. That is, when the blending amount of magnesium hydroxide is small, the oxygen index (flame retardancy) is low.

Further, the third embodiment, the first embodiment, and the sixth embodiment.
Comparing with, the amount of magnesium hydroxide in Example 3 was 300 parts by weight, the amount of magnesium hydroxide in Example 1 was 150 parts by weight, and the amount of magnesium hydroxide in Example 6 was 10 parts by weight. It has a big difference from the weight part. Comparing the scrape resistance of these three examples, Example 3
No. 310, Example 1 is 480, and Example 6 is 780. From this, it can be seen that the compounding amount of magnesium hydroxide is greatly related to the scrape resistance. This is also noticeable in the conventional example. It can be seen clearly by comparing the conventional example 1 and the conventional example 5. The compounding amount of magnesium hydroxide in Conventional Example 1 is 10
By weight, the compounding amount of magnesium hydroxide in Conventional Example 5 is 20.
The conventional example 1 has a scrape resistance of 400, while the conventional example 5 has a scrape resistance of 60, which is a large difference. That is, the smaller the content of magnesium hydroxide, the higher the scrape resistance.

In both Comparative Examples 1 and 2, the oxygen index exceeds the target value, but the scrape resistance is below the target value. In addition, in Conventional Example 1, the scrape resistance is higher than the target value, but the oxygen index is lower than the target value. In each of Conventional Example 2 to Conventional Example 5, the oxygen index exceeds the target value, but the scrape resistance is far below the target value.

Comparison will be made between Examples 1 to 7, Comparative Examples 1 and 2, and Conventional Examples 1 to 5. Example 1
Comparing Comparative Example 2 with Conventional Example 4, magnesium hydroxide was used for 70 parts by weight of ethylene-ethyl acrylate copolymer (EEA) and 30 parts by weight of ethylene-vinyl acetate copolymer (EVA). The basic composition of blending 150 parts by weight is the same. However, comparing Comparative Example 2 with Conventional Example 4, Comparative Example 4 has a scrape resistance of 120 and an oxygen index of 32.
Has a scrape resistance of 290 and an oxygen index of 30, and the scrape resistance is dramatically improved. Looking at the compositions of Comparative Example 2 and Conventional Example 4, in Comparative Example 2, 50 parts by weight of polypropylene (PP) is added to the composition of Conventional Example 4. Therefore, it can be seen that the blending of polypropylene (PP) contributes to the improvement of scrape resistance (wear resistance).
Further, comparing Example 1 and Comparative Example 2, Comparative Example 2 has a scrape resistance of 290 and an oxygen index of 30, whereas Example 1 has a scrape resistance of 480 and an oxygen index of 2.
8, the oxygen index was slightly reduced, but the scrape resistance was dramatically improved. Looking at the compositions of Example 1 and Comparative Example 2, although the compounding amount of polypropylene (PP) of Example 1 is different from that of Comparative Example 2, potassium titanate is added to the composition of Comparative Example 2. Therefore, it can be seen that the composition of potassium titanate greatly contributes to the improvement of scrape resistance (wear resistance).

This can be clearly understood by comparing the second embodiment with the conventional example 5. Looking at the compositions of Example 2 and Conventional Example 5, in Example 2 50 parts by weight of polypropylene (PP) and 15 parts by weight of potassium titanate are added to the composition of Conventional Example 5. Therefore, the scrape resistance of Conventional Example 5 is 60.
It can be seen that the oxygen index is 30 and the scraping resistance of Example 2 is 520 and the oxygen index is 30, and thus the scraping resistance is remarkably improved.

As described above, the oxygen index is improved by mixing magnesium hydroxide into the olefin resin, but in the present invention, the scrape resistance (wear resistance) which is lowered by the mixing of magnesium hydroxide is different from that of polypropylene. It is improved by mixing potassium titanate.

[0040]

Since the present invention is constructed as described above, it has the following effects.

Since the flame-retardant olefin-based resin composition obtained by mixing a metal hydrate with an olefin-based resin contains polypropylene and potassium titanate, it is possible to improve the flame-retardant property by using an olefin. The wear resistance can be improved without reducing the amount of metal hydrate contained in the resin. Further, since no halide is added, even if a fire occurs and the insulator burns, a highly toxic gas is not generated and the environment is not polluted.

In order to obtain these effects, 5 to 5 parts of polypropylene are added to 100 parts by weight of olefin resin.
0 parts by weight, 10 to 200 parts by weight of metal hydrate, and 3 to 15 parts by weight of potassium titanate may be added.

Further, a flame-retardant olefin resin composition comprising polypropylene and potassium titanate is added to a flame-retardant olefin resin composition prepared by mixing a metal hydrate with an olefin resin as an insulator. Since it is coated on top of it, abrasion resistance can be improved without reducing the amount of metal hydrate contained in the olefin resin to improve flame retardancy, and the insulator has an abnormally high temperature. Even if exposed to, it will not melt and cause dielectric breakdown to cause a short circuit, and since halide is not added, even if the insulator burns by a fire, highly toxic gas is not generated, Does not pollute the environment.

[Brief description of drawings]

FIG. 1 is a diagram showing a scrape test method.

[Explanation of symbols]

1 ……………………………………………………………………
Sample 2 ……………………………………………………………………
Stand 3 ……………………………………………………………………
Support fixture 4 ……………………………………………………………………
Metal plunger 5 ……………………………………………………………………
Sphere 6 ……………………………………………………………………
Weight 7 …………………………………………………………………………
Power meter 11 ……………………………………………………………………
conductor

Claims (5)

[Claims] 1. A flame-retardant olefin resin composition comprising a flame-retardant olefin resin composition obtained by mixing an olefin resin with a metal hydrate, and polypropylene and potassium titanate. 2. 100 parts by weight of an olefin resin, 5 to 50 parts by weight of polypropylene, and 10 to 20 parts of a metal hydrate.
A flame-retardant olefin resin composition comprising 0 part by weight and 3 to 15 parts by weight of potassium titanate. 3. The olefin resin is an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a linear low density polyethylene, an ethylene-methyl methacrylate copolymer, an ethylene-acrylic acid copolymer, The flame-retardant olefin resin composition according to claim 1 or 2, which is one or a mixture of two or more of ethylene-methacrylic acid copolymer and high-density polyethylene. 4. The flame-retardant olefin resin according to claim 1, 2 or 3, wherein the metal hydrate is any one of magnesium hydroxide, aluminum hydroxide and calcium hydroxide, or a mixture of two or more thereof. Composition. 5. A flame-retardant olefin resin composition obtained by mixing polypropylene and potassium titanate in a flame-retardant olefin resin composition obtained by mixing a metal hydrate with an olefin resin as a conductor. Wires and cables with excellent flame retardancy and abrasion resistance that are coated on top.