JPH10279736A - Abrasion-resistant and flame retardant resin composition, its production and insulated wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, excellent in softness and flexibility and further abrasion resistance in spite of a sufficient flame retardance possessed thereby without generating toxic gases at the time of incineration and useful for an insulated wire, etc., by compounding prescribed amounts of a specific aroyled polymer with a specified polyolefin resin. SOLUTION: This composition comprises (A) an aroylated polymer prepared by mixing polybutene with a polypropylene at (40/60) to (80/20) ratio with (B) a polyolefin resin having >=60 durometer hardness, (C) a metallic hydroxide (e.g. magnesium hydroxide) and (D) a copper inhibitor (e.g. 1,2,3-benzotrizole). The weight ratio of the components A to B is (95/5) to (50/50) and the amounts of the components based on 100 pts.wt. sum of the components A and B are 50-200 pts.wt. component C and 0.2-5 pts.wt. component D. The components A and C are previously kneaded and then the component B is added thereto and kneaded therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear-resistant flame-retardant resin composition containing a polyolefin resin as a main component, a method for producing the same, and an insulated wire.

[0002]

2. Description of the Related Art For example, as an insulating covering material used for insulated wires for automobiles, from the viewpoint of appropriate flexibility and flame retardancy,
Polyvinyl chloride resin is used more often than ever. However, when this wire is incinerated and disposed of with the scrapping of vehicles, the insulation coating burns in the incinerator, generating hydrogen chloride gas, damaging the incinerator or being discharged into the atmosphere, resulting in environmental pollution. Has the problem of causing

Therefore, in recent years, an electric wire using a flame-retardant resin composition containing no halogen component such as chlorine as an insulating coating material has been studied.
As shown in JP-A-01996, a mixture of a polyolefin-based resin and a metal hydroxide is generally used.

[0004]

However, conventional flame-retardant resin compositions of this type are inferior in flexibility and flexibility as compared with polyvinyl chloride, and have a large amount of metal to impart flame retardancy. There is a problem that mechanical strength such as abrasion resistance and tensile strength is reduced due to mixing of hydroxide.

Accordingly, an object of the present invention is to provide an abrasion-resistant flame-retardant material which does not generate harmful gas upon incineration, has excellent flexibility and bendability, and has sufficient abrasion resistance while having sufficient flame retardancy. It is an object of the present invention to provide a resin composition, a method for producing the same, and an insulated wire.

[0006]

The abrasion-resistant flame-retardant resin composition according to the present invention comprises the following components (a) to (d): (a) 40/60 of polybutene and polypropylene. ~ 2
Alloyed polymer obtained by mixing at a ratio of 0/80. (B) Polyolefin resin having a durometer hardness of 60 or more. (C) Metal hydroxide. (D) Copper inhibitor. Weight ratio of (a) to (b). Is 95/5 to 50/50, and (c) is 50 to 200 parts by weight and (d) is 0.2 to 5 parts by weight based on 100 parts by weight of the total of (a) and (b). It has features in some places.

In the method for producing a wear-resistant flame-retardant resin composition according to the second aspect of the present invention, the above-mentioned raw material components (a) and (c) are kneaded, and then the above-mentioned (b) is added. It is characterized by the fact that it is kneaded. (D) may be added at any stage.

According to a third aspect of the present invention, there is provided an insulated wire in which the resin composition according to the first aspect of the present invention is formed so as to surround the outer periphery of the core conductor to form an insulating coating.

The alloying material such as the component (a) used in the present invention has a structure in which polybutene and polypropylene are not mixed, and one polymer is dispersed in one polymer like an island. This is considered to be unsuitable for insulation coating of electric wires because of its low withstand voltage, and its use as an insulation coating polymer has not been studied at all. However, the inventor of the present invention has investigated that when a polyolefin resin having a predetermined hardness is blended with the resin, abrasion resistance and flexibility are developed in a well-balanced manner, and the required abrasion resistance and strength of the electric wire can be obtained. This has led to the invention. That is, the component (a) imparts flexibility, cold resistance, and whitening resistance to the resin composition, and the component (b) improves strength, such as abrasion resistance and tensile strength, required for the electric wire. It is thought that if the polypropylene ratio of the alloyed polymer of polybutene and polypropylene is increased, the strength is improved,
When the polypropylene ratio is increased to 80% or more, the cold resistance and the whitening resistance are greatly reduced and the flexibility is lost, although the degree of improvement in the wear resistance is small. However, as in the present invention, the ratio of polybutene to polypropylene is 40/6.
When it is set in the range of 0 to 20/80 and a polyolefin resin having a durometer hardness of 60 or more is added thereto, both improvement in strength such as abrasion resistance and flexibility are satisfied in a well-balanced manner. Even if an alloyed polymer is used, it can be used without problems in applications where the working voltage is low, such as for automobiles.

As the component (b), high-density polyethylene or polypropylene can be used.
0 or more is required, and the weight ratio between (a) and (b) is 9
It is necessary to be blended within the range of 5/5 to 50/50. If it is less than this range, sufficient strength is not secured in the resin composition, and if it exceeds this range, flexibility is lacking. Then, 50 to 200 parts by weight of the metal hydroxide is required for 100 parts by weight of the polymer components of (a) and (b), and if the metal hydroxide is less than this range, it is required for the electric wire. If the flame retardancy is insufficient, and if it exceeds 200 parts by weight, the mechanical strength such as the wear resistance and tensile strength of the electric wire will be insufficient. As the metal hydroxide of (c), magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like are suitable. The average particle diameter of these metal hydroxides is preferably from 0.1 to 5 μm from the viewpoint of dispersibility in a polymer, workability, electric wire characteristics, and the like. The purpose can be achieved. Also,
Surface treated with silane coupling agent, titanate coupling agent, fatty acid and its metal salt for the purpose of preventing aggregation of metal hydroxide, improving dispersibility in polymer and improving adhesion to polymer It is preferable to use Further, in order to enhance the flame retardancy, a flame retardant auxiliary such as hydrotalcites, silica, carbon black, zinc borate, and a phosphorus compound may be added, and an antioxidant, a lubricant, a dispersant, A copper damage inhibitor, a cross-linking agent, a cross-linking assistant or a coloring agent may be added, and the polymer may be cross-linked by various cross-linking methods.

[0011] The component (d) of copper damage inhibitor includes 1,
There are 2,3-benzotriazole, 3- (N-salicyloyl) amino-1,2,4-triazole and the like, which suppress copper degradation of polypropylene. When the amount of the copper damage inhibitor is 0.2 parts by weight or less, the effect of preventing copper damage is small, and when it is 5 parts by weight, the effect of preventing copper damage reaches the upper limit.

When the above-mentioned raw material components are kneaded with each other, the alloyed polymer (a) and the metal hydroxide (c) are kneaded in advance, and then (b)
It is preferable to add and knead the polyolefin resin. The reason is presumed to be as follows. Originally,
Since the adhesion between the polyolefin and the metal hydroxide of (b) is extremely poor, the addition of an amount such that sufficient flame retardancy is obtained results in a large decrease in the strength of the entire resin composition, which results in abrasion resistance and tensile strength. This was a major cause of strength reduction and whitening. However, the alloyed polymer (a) has a slightly higher affinity for metal hydroxide than (b),
When the alloyed polymer and the metal hydroxide are kneaded, the alloyed polymer surrounds the entire metal hydroxide powder. Then, when this is kneaded with the polyolefin resin, the metal hydroxide powder wrapped by the other alloyed polymer is dispersed in the polyolefin resin. Since the affinity between the polyolefin resin and the alloyed polymer is similar, it is much better than the affinity between the polyolefin resin and the metal hydroxide. Therefore, the metal hydroxide powder is surrounded by an alloyed polymer having relatively good affinity, and the alloyed polymer is surrounded by the polyolefin resin. This is significantly improved as compared with the conventional structure that often touches. For this reason, as the resin composition as a whole, while maintaining sufficient flame retardancy by adding a metal hydroxide in the same ratio as before, the mechanical strength such as abrasion resistance and tensile strength is increased, and Flexibility and whitening resistance can be improved.

[0013]

As described above, according to the flame-retardant resin composition of the first aspect of the present invention, a predetermined amount of an alloyed polymer of polybutene and polypropylene and a polyolefin resin having a predetermined hardness are blended. In addition, the abrasion resistance and the flexibility are expressed in a well-balanced manner, and the required strength can be ensured, while the flexibility, the cold resistance and the whitening resistance are obtained.

According to the production method of the second aspect, the metal hydroxide and the alloyed polymer having excellent affinity are kneaded in advance, and then the polyolefin resin is kneaded. The adhesion between the metal hydroxide and the metal hydroxide, so that abrasion resistance, tensile strength,
An excellent effect that the flexibility and the whitening resistance can be further enhanced is obtained.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Some embodiments of the present invention will be described below.

As Examples 1 to 3 of the present invention, (butene /
(Propylene) + polypropylene alloyed polymer, magnesium hydroxide, and red phosphorus are kneaded at the ratio shown in Table 1, and then polypropylene (durometer hardness = 69) is added at the ratio shown in the table, and the kneaded resin composition is added. Produced.

On the other hand, as Comparative Examples 1 to 6, (Butene / propylene) + polypropylene alloyed polymer, ethylene-ethyl acrylate copolymer (ethyl acrylate content = 35%), magnesium hydroxide and red phosphorus are shown in Table 2. After kneading at a ratio, polypropylene and linear low-density polyethylene (durometer hardness = 58) were added at the ratio shown in the same table to prepare a kneaded resin composition.

In Comparative Example 7 having the proportions shown in the table, a resin composition was prepared by simultaneously kneading all the raw material components.

The (butene / propylene) + polypropylene alloyed polymer used was CAP (trade name) manufactured by Ube Lexen, the ethylene-ethyl acrylate copolymer was manufactured by Mitsui Dupont Chemical Co., and the polypropylene was manufactured by Tokuyama One used.

The following characteristics were evaluated using a thin electric wire prepared by extruding these resin compositions to a thickness of 0.3 mm on the outer periphery of a copper core wire. Flame retardancy: A 300 mm long wire sample is supported horizontally, and the tip of the reducing flame is applied from below the center of the sample using a Bunsen burner with a diameter of 10 mm until it burns within 30 seconds.
After gently removing the flame, the degree of combustion of the sample was determined. Abrasion resistance: At room temperature of 23 ± 5 ° C., the insulating coating surface of a 750 mm long wire sample fixed on a table is reciprocated and abraded by a blade over a length of 10 mm or more in the axial direction. When the blade is reciprocated 50 or 60 times per minute,
The number of reciprocations until the blade contacts the core conductor due to wear of the insulator is measured. Next, the sample is moved 100 mm, rotated 90 degrees clockwise, and the above measurement is repeated.
This measurement was performed a total of four times with the same sample, and the minimum value was defined as abrasion resistance. Whitening resistance: The film was gently wound several times around a cylinder having a radius of 6 mm, and the degree of whitening of the surface was visually checked in that state. Extrusion processability: Comprehensively judged from high-speed extrusion, electric wire appearance, and the like.

The evaluation results are shown in Tables 1 and 2.

[0022]

[Table 1]

[0023]

[Table 2] First, as shown in Table 1, in Examples 1 to 3 relating to the resin composition of the present invention, all of the flame retardancy, the whitening resistance, the extrudability, and the flexibility were good. Further, the abrasion resistance greatly exceeded the target value of 300 times, and a characteristic value with good tensile strength and elongation was obtained. On the other hand, in Comparative Examples 1 and 2, in which the weight ratio of (butene / propylene) + polypropylene alloyed polymer to polypropylene is out of the limited range, the whitening resistance and flexibility are reduced. In Comparative Example 2, a linear low-density polyethylene having a durometer hardness lower than the specified value was included, and the extrudability was also reduced in addition to the above.
In Comparative Example 3 containing no polypropylene, good abrasion resistance cannot be obtained. In Comparative Example 4 in which the ratio of magnesium hydroxide was smaller than the limit value, the flame retardancy was reduced, and in Comparative Example 5, all of the evaluation items other than the flame retardancy and extrudability were reduced. In Comparative Example 6 containing no (butene / propylene) + polypropylene alloyed polymer, the abrasion resistance was reduced most, and the tensile strength and the extrudability were also reduced. Also, in Comparative Example 7, in which all components were kneaded at the same time, the abrasion resistance was significantly reduced.

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Claims (3)

[Claims] 1. It comprises the following components (a) to (d): (a) 40/60 to 2 of polybutene and polypropylene
Alloyed polymer obtained by mixing at a ratio of 0/80. (B) Polyolefin resin having a durometer hardness of 60 or more. (C) Metal hydroxide. (D) Copper inhibitor. Weight ratio of (a) to (b). Is 95/5 to 50/50, and (c) is 50 to 200 parts by weight and (d) is 0.2 to 5 parts by weight based on 100 parts by weight of the total of (a) and (b). An abrasion-resistant flame-retardant resin composition. 2. A method for producing an abrasion-resistant flame-retardant resin composition containing the following components (a) to (d), wherein (a) polybutene and polypropylene are used in a ratio of 40/60 to 2:
Alloyed polymer obtained by mixing at a ratio of 0/80. (B) Polyolefin resin having a durometer hardness of 60 or more. (C) Metal hydroxide. (D) Copper inhibitor. Weight ratio of (a) to (b). Is 95/5 to 50/50, and (c) is 50 to 200 parts by weight and (d) is 0.2 to 5 parts by weight based on 100 parts by weight of the total of (a) and (b). Yes, after kneading (a) and (c) in advance, (b)
A method for producing a wear-resistant flame-retardant resin composition, characterized by adding and kneading. 3. An insulated wire in which an insulating coating is formed around a conductive core wire with a resin composition, wherein the resin composition contains the following components (a) to (d): (a) polybutene And polypropylene 40 / 60-2
Alloyed polymer obtained by mixing at a ratio of 0/80. (B) Polyolefin resin having a durometer hardness of 60 or more. (C) Metal hydroxide. (D) Copper inhibitor. Weight ratio of (a) to (b). Is 95/5 to 50/50, and (c) is 50 to 200 parts by weight and (d) is 0.2 to 5 parts by weight based on 100 parts by weight of the total of (a) and (b). An insulated wire characterized by the following.