JP2002146118A - Flame-retardant resin composition and flame-retardant insulated wire using the same as coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition having high abrasion resistance and flame retardance required for an insulated wire of automobiles, household appliances, etc., without emitting a toxic halogen gas during combustion at all and to provide the insulated wire using the flame-retardant resin composition as a wire coating material. SOLUTION: This flame-retardant resin composition is obtained by mixing 30-200 pts.wt. of a metallic hydroxide with 100 pts.wt. of the sum total of 60-95 pts.wt. of a polyolefin resin and 5-40 pts.wt. of a polyamide resin or mixing 30-200 pts.wt. of the metallic hydroxide with 100 pts.wt. of the sum total of 20-94 pts.wt. of the polyolefin resin, 5-50 pts.wt. of the polyamide resin and 1-30 pts.wt. of a carboxylic acid-modified polymer or an ionic copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and more particularly to a flame-retardant resin composition which emits no harmful halogen gas at the time of combustion in a fire or recycling, and has high heat resistance and low heat resistance in use. The present invention relates to a flame-retardant resin composition having flame retardancy and particularly suitable as a wire covering material for automobiles or home electric appliances, and a flame-retardant insulated wire using the same as a wire covering material.

[0002]

2. Description of the Related Art In recent years, with the development of electronics,
The performance and functionality of products having an electric / electronic control mechanism, such as automobiles and home electric appliances, have been rapidly advanced, and the amount of electric / electronic circuits used has increased accordingly. As described above, while the demand in the electric / electronic control field is increasing, the enlargement of the electric wire, which increases the volume occupied by the electric wire in the circuit, has become a serious problem, and space saving of these wirings has been desired.

As one of the measures for space saving, reduction in the diameter of an electric wire used in a circuit and reduction in the thickness of an insulating coating material have been promoted. However, if the thickness of the wire insulation coating material is promoted, there arises a problem that the wear resistance of the insulation coating material is significantly reduced. Therefore, polyvinyl chloride is currently mainly used as a material that satisfies the conditions of maintaining the wear resistance of the insulating coating material and reducing the thickness.

[0004] Recently, the preservation of the global environment has come to attract attention as a global issue, and the recycling of resources and processed goods and the treatment of industrial waste have been regarded as important on a global level in a wide range of fields such as automobiles. For this reason, corrosive halogen-based gas is generated during combustion of polyvinyl chloride, which is used as an insulating coating material for cable wires for automobiles, and is regarded as a problem as one of the sources of global environmental pollution. Due to such social trends, flame-retardant materials made of non-halogen-based substances that generate less corrosive gas have been attracting attention.

[0005] As such a material, there is a non-halogen polyolefin resin composition formed by blending a non-halogen metal hydroxide such as magnesium hydroxide as a flame retardant in an appropriate amount to a polyolefin resin containing no halogen component. Some have already been presented.

[0006] For example, Japanese Patent Application Laid-Open No. 6-215644 discloses a non-halogen resin composition obtained by adding nylon 12 to a polyolefin resin, adding a carboxylic acid-modified polymer, and blending magnesium hydroxide as a flame retardant. Further, an insulated wire using the same as a wire covering material is disclosed.

[0007] For example, Japanese Patent Application Laid-Open No. 6-290650 discloses a method in which polyethylene, maleic anhydride-added polyethylene and polyamide resin are blended, and the resulting composition is coated on a conductor and then subjected to electron beam crosslinking. Techniques are disclosed. In this publication, it is disclosed that, by irradiating a resin composition with an electron beam to form a crosslink, the elongation characteristics and wear resistance of an insulated wire using the resin composition as a coating material can be significantly improved.

[0008]

However, as disclosed in JP-A-6-215644, in order to make the above-mentioned non-halogenated resin composition flame-retardant enough to have self-extinguishing property, In addition, a large amount of metal hydroxide, which is a flame retardant, must be blended, and a composition obtained by blending such a large amount of metal hydroxide has poor mechanical properties such as abrasion resistance and elongation. However, there arises a problem that individual characteristics of the compounded composition cannot be utilized.

Further, as disclosed in JP-A-6-290650, the resin composition is irradiated with an electron beam or the like to form a crosslink, thereby improving the wear resistance, elongation, etc. of the resin composition. However, a cross-linking step is required in addition to the usual composition production step, which leads to an increase in the number of steps for producing the resin composition and the production cost of the product, which is not preferable.

The present inventors have conducted intensive studies to improve mechanical properties such as heat resistance and abrasion resistance. As a result, the present inventors have found that a halogen-free polymer resin and a polyamide resin are replaced with a halogen-free polymer resin. By adding, sufficient heat resistance without performing treatment such as crosslinking,
The present inventors have found a flame-retardant resin composition exhibiting abrasion resistance and the like and balancing these properties, and have completed the present invention.

An object of the present invention is to provide a flame-retardant resin which does not generate any harmful halogen gas at the time of combustion and has high abrasion resistance and flame retardancy required for insulated wires of automobiles and the like. The present invention provides a composition and an insulated wire using the same as a wire covering material.

[0012]

To solve the above-mentioned problems, the flame-retardant resin composition according to the first aspect of the present invention comprises 60 to 95 parts by weight of a polyolefin resin and 5 parts by weight of a polyamide resin.
It is intended that the metal hydroxide be mixed with 30 to 200 parts by weight based on 100 parts by weight of the total amount of these compounds. When the polyolefin resin and the polyamide resin deviate from the above mixing amount,
Heat deformability and elongation properties are reduced, while metal hydroxide
If the amount is less than 0 parts by weight, sufficient flame retardancy cannot be obtained.
If the amount is more than 0 parts by weight, abrasion resistance is reduced. In other words, when each mixture is within the above-mentioned mixing ratio, a resin composition having suitable flame retardancy, abrasion resistance and the like can be obtained.

As the polyolefin resin, it is preferable to use polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene rubber, ethylene-butene copolymer, etc. These may be used alone or in combination of two or more.

As the polyamide resin, nylon 1
Examples thereof include polymers containing an amide group such as 1, nylon 12, nylon 6, nylon 66, nylon 612, nylon 610, nylon 1010, and polyamide elastomer. The molecular structure and density are not particularly limited, but from the viewpoint of heat resistance. It is desirable to use nylon 6, nylon 66 or the like having a relatively high melting point.

The flame-retardant resin composition according to claim 2 of the present invention comprises 20 to 94 parts by weight of a polyolefin resin and 5 to 5 parts of a polyamide resin having a melting point of 200 ° C. or more.
0 to 1 part by weight, containing 1 to 30 parts by weight of a carboxylic acid-modified polymer, wherein the total amount of these compounds is 100 parts by weight, and 30 to 200 parts by weight of a metal hydroxide is mixed. It is.

Examples of the polyamide resin having a melting point of 200 ° C. or higher include nylon 6 (melting point: 225 ° C.) and nylon 66 (melting point: 265 ° C.). Melting point 2
Nylon 11 (melting point: 186 ° C.), nylon 12 (melting point: 177)
C.), a flame-retardant resin composition having sufficient heat resistance and the like cannot be obtained.

The carboxylic acid-modified polymer is obtained by grafting or copolymerizing a carboxylic acid to a resin such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. A typical example of the acid is maleic anhydride. This carboxylic acid-modified polymer also uses a non-halogen type. Also, the polyolefin resin and the polyamide resin mixed simultaneously with the carboxylic acid-modified polymer have the property that the former is a non-polar material and the latter is a polar material, and are inherently difficult to mix, but by attaching 1 to 30 parts by weight of the carboxylic acid-modified polymer. The compatibility between the two is improved, and as a result, the heat resistance, elongation and the like of the resin composition are improved.

Also in this case, the metal hydroxide needs to be contained in an amount of 30 to 200 parts by weight based on 100 parts by weight of the total of the polyolefin resin, the polyamide resin and the carboxylic acid-modified polymer. That is, if the amount is less than 30 parts by weight, the desired flame retardancy cannot be imparted, and if it exceeds 200 parts by weight, the wear resistance is significantly impaired.

The flame-retardant resin composition according to the third aspect of the present invention comprises 20 to 94 parts by weight of a polyolefin resin, 5 to 50 parts by weight of a polyamide resin, and 1 to 30 parts by weight of an ionic copolymer. Including the total amount of these formulations is 100
The gist is that 30 to 200 parts by weight of a metal hydroxide is mixed with respect to parts by weight. In this case, as the polyolefin resin and the polyamide resin, resin materials having various compositions as described above can be used, and the molecular structure, density, and the like are not particularly limited.

The ionic copolymer is one or more types of α
-Consisting of an olefin and one or more α, β-unsaturated organic carboxylic acids partially or completely neutralized with zinc ions; the molecular structure, density and the like are not particularly limited; You need to be a system. By adding an appropriate amount of this ionic copolymer similarly to the carboxylic acid-modified polymer described above, the compatibility between the polyolefin resin and the polyamide resin is improved, and as a result, the heat resistance property, elongation property, etc. of the resin composition are improved. Is done.

Also in this case, the metal hydroxide needs to be used in an amount of 30 to 200 parts by weight based on 100 parts by weight of the total of the polyolefin resin, the polyamide resin and the ionic copolymer. That is, if the amount is less than 30 parts by weight, the desired flame retardancy cannot be imparted, and if it exceeds 200 parts by weight, the wear resistance is significantly impaired.

Examples of the metal hydroxide include compounds composed of divalent or trivalent metal ions such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide. Among them, magnesium hydroxide is generally used. . Further, the average particle diameter is 0.1 to 20 μm from the viewpoint of physical properties.
It is desirable to use those.

Further, it is common to use a surface-treated one for improving dispersibility and affinity with a polymer. As the method, aminosilane coupling agents, vinylsilane coupling agents, epoxysilane coupling agents are used. Although the treatment with the ring agent and the methacryloxysilane coupling agent has an effect on the improvement of the abrasion resistance, the use of the metal hydroxide surface-treated with the epoxysilane coupling agent as described in claim 4 is particularly effective. A remarkable improvement in wear resistance is observed. As the epoxy silane coupling agent, β- (3,4 epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

As a method of treating the surface of a metal hydroxide with this silane coupling agent, a method of treating the surface of a metal hydroxide is generally used. A method using an integral blend that is sometimes added simultaneously may be used. When performing a surface treatment on the metal hydroxide, after diluting the silane coupling agent with an organic solvent such as alcohol, or acetic acid water,
The spraying is generally performed by spraying the powder on a metal hydroxide powder or adding the powder to a water slurry. The metal hydroxide subjected to the surface treatment in this manner may be used in combination with one that has been surface-treated with another treating agent, for example, one that has been treated with a fatty acid or a phosphate ester.

Further, in the present invention, in addition to the above-mentioned compounding agents, compounding agents usually compounded in the olefin resin, for example, an antioxidant,
Metal deactivators (such as copper damage inhibitors), processing aids (such as lubricants and waxes), coloring agents, and flame retardants (such as zinc borate and silicon-based flame retardants) may be appropriately added.

Furthermore, compounding agents which are usually compounded with polyamide resins, for example, nitrogen-based flame retardants (melamine cyanurate, etc.), flame-retardant assistants (zinc borate, silicon-based flame retardants, etc.),
Reinforcing agents (clay, calcium carbonate, talc), antioxidants, metal deactivators, processing agents (lubricants, etc.), coloring and the like can be added as appropriate, in which case they are pre-blended with the polyamide resin. Is also good.

[0027] Further, an insulated wire according to claim 5 of the present invention is characterized in that the flame-retardant resin composition according to claims 1 to 4 is used as a wire covering material. According to the insulated wire having the above configuration, not only excellent flame retardancy and abrasion resistance are developed, but also no harmful halogen gas is generated at the time of combustion at the time of fire or recycling. It can exhibit sufficient flame retardancy. Furthermore, there is no need to perform cross-linking by electron beam irradiation as a means for improving the mechanical strength of the insulated wire, and it is possible to reduce the number of man-hours for manufacturing the insulated wire and thus the product cost.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.

In the following Examples and Comparative Examples, the manufacturers and trade names of each compounding agent used are as follows. That is, the propylene-ethylene block copolymer is "Tokuyama Polypro" (trade name) manufactured by Tokuyama Co., and the ethylene-vinyl acetate copolymer is "Evaflex" (trade name) manufactured by Mitsui Dupont Chemical Co., Ltd .; HDP
E) "HIZEX" manufactured by Dupont Mitsui Chemicals, Inc.
(Trade name), maleic anhydride-modified propylene homopolymer and maleic anhydride-modified low-density polyethylene were manufactured by Nippon Polyolefin Co., Ltd. “Adtex ER” (trade name),
Maleic anhydride-modified ethylene-vinyl acetate copolymer is "HPR" (trade name) manufactured by DuPont-Mitsui Chemicals, nylon 6 and nylon 66 are "Ube nylon" (trade name) manufactured by Ube Industries, Ltd., epoxy silane coupling As untreated magnesium hydroxide for surface treatment with an agent, M
ARTINSWERK “Magnifin H5” (trade name), magnesium hydroxide surface-treated with fatty acid is “Kisuma 5 (grade 5A)” (trade name) manufactured by Kyowa Chemical Industry Co., Ltd. "Tominox" (trade name) manufactured by Seiko Chemical Co., Ltd. "Nonflex DCD" (trade name) manufactured by Seiko Chemical Co., Ltd.
It is.

In order to prepare compositions having compositions corresponding to the following Examples and Comparative Examples, and to evaluate the properties of the obtained compositions in the state of electric wires, a conductor (twenty soft copper wires were stranded and the outer surface of the conductor was used). Which was compressed into a circle in order to smooth out).
The resin composition was coated with an extruder with a coating thickness of 5 mm ² and a coating thickness of 0.2 mm. The dies and nipples used at this time are 1.25 mmφ and 0.88 mmφ, and the extrusion temperature is set at a die of 210 to 230 ° C. and a cylinder of 200 to 240 ° C., and the linear speed is 100 m / mi.
n. The manufacturing method of this electric wire is common to all the examples and comparative examples shown below.

Next, the method of measuring the flame retardancy, abrasion resistance, tensile elongation, and heat deformability performed as evaluation means for these manufactured samples will be described below.

(1) Flame Retardancy This flame retardancy test was carried out according to the Japan Society of Automotive Engineers Standard “JAS
OD 611-94 ". First,
An insulated wire is cut out to a sample length of 300 mm from each of the product of the example and the product of the comparative example of the present invention. Next, each sample was placed in an iron test box and supported horizontally, and a reducing flame of a Bunsen burner was applied to the specimen until it burned within 30 seconds. After that, the residual flame time was measured. A residual flame time of less than 15 seconds was determined to be acceptable, and a flame time exceeding 15 seconds was determined to be unacceptable.

(2) Abrasion Resistance This abrasion resistance test was conducted according to the standards of the Japan Society of Automotive Engineers of Japan.
This test is based on “SO D 611-94”. Here, a blade reciprocating method is employed. First, 750 insulated wires were obtained from each of the examples and comparative examples of the present invention.
The sample is cut out to a length of mm. Next, at 23 ° C. ±
Each sample was fixed on a table at a room temperature of 5 ° C., and the blade was reciprocated at a speed of 50 times with a load of 7N over a length of 10 mm or more in the axial direction of the surface of the insulated wire.

Then, the number of reciprocations until the blade came into contact with the conductor due to surface wear was measured. Further, the sample is moved by 100 mm, rotated 90 degrees clockwise, and the above measurement is repeated. This measurement was performed four times on the same sample,
The minimum value was used as a pass / fail judgment value. In this wear resistance test, the number of reciprocations of 300 or more was determined to be acceptable, and the number of reciprocations less than 300 was determined to be unacceptable. In Tables 1 to 3 showing the results of the following examples and comparative examples, the evaluation values are indicated by symbols A to E, and A: less than 150 times, respectively.
B: 150 to 299 times, C: 300 to 449 times, D: 4
50 to 599 times, E: 600 times or more. That is, A and B are rejected products, and CE are acceptable products.

(3) Tensile Elongation This tensile test was conducted according to the Japan Automotive Engineers Association standard “JAS
OD 611-94 ". First,
An insulated wire was cut out to a length of 150 mm from each of the examples and comparative examples of the present invention to prepare test pieces, and marked lines were marked at the center at intervals of 50 mm. Next, chucks were attached to both ends of the test piece at room temperature of 23 ° C. ± 5 ° C.
The tensile elongation was evaluated by pulling at a pulling speed of 00 mm / min and measuring the load at the time of cutting the test piece and the length between the marked lines. Those having a tensile elongation exceeding 125% were judged to be acceptable, and those having a tensile elongation of less than 125% were judged to be unacceptable.

(4) Heat Deformability After the electric wire was left in an atmosphere of 180 ° C. for 10 minutes, when a load of 300 g was applied to the electric wire for 1 minute, it was determined whether or not the coated insulation was melted and the conductor was exposed. That is,
If the conductor was not exposed, it was judged as acceptable, and the coated insulating skin did not retain its shape, and if the conductor was exposed, it was judged as unacceptable.

(Examples 1 to 8 and Comparative Examples 1 to 5) As a polyolefin resin, a propylene-ethylene block copolymer (density: 0.90 g / cm ³⁾ melt flow rate: 230 ° C., 2.16 kg, 0.1 kg 5g / 10min
(Meaning that 0.5 g of the polymer melt flows out of the pores at a load of 2.16 kg at a temperature of 230 ° C. in 10 minutes. The description is omitted below)), high-density polyethylene (density: 0) 0.95 g / cm ³ Melt flow rate: 190 ° C., 2.16 kg, 3.0 g / 10
min) and ethylene-vinyl acetate copolymer (density:
0.95g / ^cm 3. Melt flow rate: 190 ° C,
2.16 kg, 2.0 g / 10 min), and nylon 6 (density:
1.14 g / cm ³ ) and nylon 66 (density: 1.1
4 g / cm ³ ), and the total amount is 100 parts by weight, and magnesium hydroxide treated with an epoxysilane coupling agent or a fatty acid (the former is magnesium hydroxide A, The latter is added in the range of 30 to 200 parts by weight of magnesium hydroxide B, and a binder phenol-based and amine-based anti-aging agent (the former is referred to as anti-aging agent A, and the latter is referred to as anti-aging agent B). Was added.

Here, magnesium hydroxide A treated with an epoxy silane coupling agent is prepared by adding glycidoxypropyltrimethoxysilane (“KBM402” (trade name) manufactured by Shin-Etsu Chemical) as an epoxy silane coupling agent to an organic solvent or aqueous acetic acid. And then untreated magnesium hydroxide ("Magnifin H" manufactured by MARTINSWERK)
5 "(trade name)) or by adding it to a water slurry.

Various components were mixed in a twin-screw kneader according to the components shown in Examples 1 to 8 and Comparative Examples 1 to 5 in Table 1, and then pelletized. Thereafter, insulated wires were manufactured according to the above-described procedure, and evaluated for flame retardancy, abrasion resistance, tensile elongation, and heat deformability.

In Examples 1 to 8 of the present invention shown in Table 1, good results were obtained in any of the evaluations of flame retardancy, abrasion resistance, tensile elongation and heat deformability. On the other hand, as in Comparative Example 1, when the polyamide resin was not added, the melting point of the entire composition was lowered, resulting in inferior wear resistance and heat deformability. Further, even when the polyamide resin (nylon 66) was added as in Comparative Example 2, if the amount was less than 5 parts by weight, sufficient heat deformability was not obtained. On the other hand, when the polyamide resin (nylon 6) was added in a large amount of 90 parts by weight as in Comparative Example 3, the abrasion resistance was extremely poor and the tensile elongation was extremely low, resulting in an undesirable result. Further, as in Comparative Example 4, when magnesium hydroxide (magnesium hydroxide B) treated with a fatty acid was used as a flame retardant, a sample using magnesium hydroxide (magnesium hydroxide A) treated with an epoxysilane coupling agent was used. No improvement in wear resistance was observed. On the other hand, even when magnesium hydroxide (magnesium hydroxide A) treated with an epoxy silane coupling agent is used as in Comparative Example 5, the compounding amount is 30%.
When the amount is less than the weight part, the effect as the flame retardant was not sufficiently obtained, and the resulting composition was inferior in flame retardancy.

[0041]

[Table 1]

(Examples 9 to 17 and Comparative Examples 6 to 10) As polyolefin resins, propylene-ethylene block copolymer (density and melt flow rate are the same as above), low density polyethylene (density and melt flow rate are as described above) And ethylene-vinyl acetate copolymer (density and melt flow rate are the same as described above), and nylon 6 and nylon 66 (any of them) as polyamide resins having a melting point of 200 ° C. or more. And the density is the same as above), and as a carboxylic acid-modified polymer,
Maleic anhydride-modified propylene homopolymer (density:
0.91g / ^cm 3. Melt flow rate: 230 ° C,
2.16 kg, 20.0 g / 10 min), maleic anhydride-modified ethylene-vinyl acetate copolymer (density: 0.9
6 g / cm ³ . Melt flow rate: 190 ° C, 2.1
6 kg, 8.0 g / 10 min), maleic anhydride-modified low-density polyethylene (density: 0.91 g / cm ³⁾ Melt flow rate: 190 ° C., 2.16 kg, 3.5 g /
10 min), and the mixture 100
Magnesium hydroxide treated with an epoxysilane coupling agent treatment or a fatty acid treatment with respect to parts by weight (the former is referred to as magnesium hydroxide A and the latter as magnesium hydroxide B)
Was added in the range of 30 to 200 parts by weight, and a binder phenol-based and amine-based anti-aging agent (the former is referred to as anti-aging agent A, and the latter is referred to as anti-aging agent B).

Examples 9 to 17 and Comparative Examples 6 to 10 in Table 2
After mixing the various components with a twin-screw kneader according to the compounding components shown in (1), the mixture was pelletized. Thereafter, insulated wires were manufactured according to the above-described procedure, and evaluated for flame retardancy, abrasion resistance, tensile elongation, and heat deformability.

In Examples 9 to 17 of the present invention shown in Table 2, good results were obtained in any evaluation of flame retardancy, abrasion resistance, tensile elongation and heat deformability. On the contrary,
As in Comparative Example 6 shown in Table 2, when only the carboxylic acid-modified polymer was added without adding the polyamide resin,
The result was very poor abrasion resistance and poor heat deformability. On the other hand, as in Comparative Example 7, when the carboxylic acid-modified polymer was not blended in the composition and the metal hydroxide was less than 30 parts by weight, the polyolefin resin (propylene-ethylene block copolymer) was used. There was no improvement in compatibility with the polyamide resin (nylon 6), so that heat deformability was poor and flame retardancy was not sufficiently imparted. Also, as in Comparative Example 8, when the carboxylic acid-modified polymer was not blended and the polyamide resin (nylon 6) was blended in a large amount of 90 parts by weight, the abrasion resistance was deteriorated and the tensile elongation was extremely high. And the result was unfavorable. Also, as in Comparative Example 9, even if the carboxylic acid-modified polymer is blended in an appropriate amount of 30 parts by weight, if magnesium hydroxide treated with a fatty acid is used as a flame retardant, epoxy silane coupling-treated magnesium hydroxide is used. No improvement was observed in the abrasion resistance observed in the sample. Also, as in Comparative Example 10, when a large amount of the modified carboxylic acid-modified polymer was added without adding any olefin resin, the abrasion resistance was extremely poor.

[0045]

[Table 2]

(Examples 18 to 22 and Comparative Examples 11 to 1)
4) As polyolefin resin, propylene-ethylene block copolymer (density, melt flow rate is the same as above), low density polyethylene (density, melt flow rate is the same as above), ethylene-vinyl acetate copolymer (density, One or two of the above melt flow rates) and a polyamide resin having a melting point of 200 ° C. or more, either nylon 6 or nylon 66 (both having the same density as above) and an ionic copolymer. As a polymer, a copolymer of ethylene and methacrylic acid partially neutralized with zinc ions is blended, and 100 parts by weight of the blend is treated with an epoxysilane coupling agent treatment or a fatty acid treatment. Magnesium oxide (the former is described as magnesium hydroxide A, the latter as magnesium hydroxide B) is 30 to 20.
The mixture was added in an amount of 0 parts by weight, and a binder phenol-based and amine-based anti-aging agent (the former was referred to as an anti-aging agent A, and the latter was referred to as an anti-aging agent B).

Examples 18 to 22 and Comparative Examples 11 to 22 in Table 3
Various components were mixed in a twin-screw kneader according to the components shown in No. 14, and then pelletized. Thereafter, insulated wires were manufactured according to the above procedure, and evaluated for flame retardancy, wear resistance, tensile elongation, and heat deformability.

In Examples 18 to 22 of the present invention shown in Table 3, good results were obtained in any of the evaluations of flame retardancy, abrasion resistance, tensile elongation and heat deformability. On the other hand, when the ionic copolymer was blended without adding the polyamide resin as in Comparative Example 11 shown in Table 3, sufficient abrasion resistance could not be obtained, and heat deformability was not obtained. The result was inferior. Further, even when the ionic copolymer was not added as in Comparative Example 12, even if an appropriate amount of magnesium hydroxide as a flame retardant was added, sufficient flame retardancy was not obtained. Also, as in Comparative Example 13, when the ionic copolymer was not blended and the polyamide resin (nylon 6) was added in excess, the abrasion resistance was extremely poor, and the tensile elongation was extremely low. The result was unfavorable. On the other hand, as in Comparative Example 14, when the amount of the ionic copolymer was excessively large as 40 parts by weight, sufficient abrasion resistance and tensile elongation were not obtained.

[0049]

[Table 3]

Although the embodiments have been described above, various modifications can be made without departing from the spirit of the present invention. For example, nylon 6 and nylon 66 were used as polyamide resins having a melting point of 200 ° C. or higher.
10 (melting point: 227 ° C.), nylon 1010 (melting point: 2
(10 ° C.) and a polyamide resin having a melting point of 200 ° C. or more. Magnesium hydroxide used as a flame retardant was treated with an epoxy silane coupling agent from the viewpoint of providing excellent abrasion resistance, but other surface treatment agents such as amino silane coupling agent and vinyl silane coupling agent were used. It may have been treated with an agent.

[0051]

The flame-retardant resin composition according to claim 1 of the present invention contains 60 to 95 parts by weight of a polyolefin resin and 5 to 40 parts by weight of a polyamide resin, and the total amount of these compounds is 100 parts by weight. On the other hand, since the resin composition is obtained by mixing 30 to 200 parts by weight of the metal hydroxide, the obtained resin composition not only has sufficient flame retardancy and abrasion resistance, but also has a fire or a fire in recycling. Since it does not generate harmful halogen gas sometimes, it has excellent environmental load characteristics.

The flame-retardant resin composition according to claim 2 of the present invention comprises 20 to 94 parts by weight of a polyolefin resin,
5 to 50 parts by weight of a polyamide resin having a melting point of 0 ° C. or more, 1 to 30 parts by weight of a carboxylic acid-modified polymer, and 30 to 200 parts by weight of a metal hydroxide based on 100 parts by weight of the total of these compounds. A resin composition having more excellent abrasion resistance can be obtained by blending a polyamide resin having a melting point of 200 ° C. or more as a polyamide resin, and adding an appropriate amount of a carboxylic acid-modified polymer. Thereby, the compatibility between the polyolefin resin and the polyamide resin is improved, and excellent heat resistance such as heat deformability, elongation characteristics, and the like can be exhibited.

Further, the flame-retardant resin composition according to claim 3 of the present invention comprises 20 to 94 parts by weight of a polyolefin resin,
5 to 50 parts by weight of polyamide resin, 1 to ionic copolymer
30 parts by weight, and 30 to 200 parts by weight of a metal hydroxide with respect to 100 parts by weight of the mixture with respect to 100 parts by weight of the total amount of these compounds. The compatibility of the polyolefin resin and the polyamide resin is also improved by blending the coalesced, and excellent heat resistance such as heat deformability and elongation characteristics can be exhibited.

Further, the metal hydroxide compounded as a flame retardant is subjected to a surface treatment with an epoxy silane coupling agent, an amino silane coupling agent, a vinyl silane coupling agent, a methacryloxy silane coupling agent or the like, so that the abrasion resistance and the like are improved. Mechanical properties such as abrasion resistance, etc., which can be particularly improved by blending a metal hydroxide surface-treated with an epoxy silane coupling agent. .

Accordingly, an insulated wire using the flame-retardant resin composition according to the present invention as a wire covering material has not only excellent mechanical properties such as excellent flame retardancy and abrasion resistance, but also fire or recycling. In this case, there is an advantage that no harmful halogen gas is generated at the time of combustion and the environmental characteristics are excellent. Further, since it is a non-crosslinked type, it is not necessary to perform a cross-linking treatment by electron beam irradiation as a means for improving the mechanical strength of the insulated wire, and it is possible to reduce the man-hour and manufacturing cost of the insulated wire, which is a unique effect of the present application. Is played.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01B 3/30 H01B 3/30 C 3/44 3/44 FG 7/295 (C08L 23/02 // (C08L 23 / 02 77:00) 701) H01B 7/34 B (72) Inventor Masafumi Sato 1-14 Nishisuehirocho, Yokkaichi-shi, Mie Sumitomo Wiring Systems, Ltd. (72) Inventor Hirohiko Sugita Yokkaichi-shi, Mie 1-14 Nishi-Suehiro-cho, Sumitomo Wiring Systems, Ltd. (72) Inventor Koji Fujimoto 1-114, Nishi-Suehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems, Ltd. No. 1-14, Sumitomo Wiring Systems Co., Ltd. F-term (reference) 4J002 BB031 BB051 BB061 BB071 BB084 BB151 BB171 BB181 BB213 CL012 CL032 CL082 DE076 DE086 DE146 FB096 FD136 GQ01 5G303 AA06 AB12 AB20 BA01 CB01 A02 CB136 AB25 AB35 BA15 BA22 BA26 CA01 CA20 CA51 CA55 CA60 CC03 CD13 5G315 CA03 CB01 CC08 CD02 CD09 CD14

Claims (5)

[Claims] 1. A polyolefin resin of 60 to 95 parts by weight,
It contains 5 to 40 parts by weight of a polyamide resin.
A flame-retardant resin composition characterized by mixing 200 parts by weight. 2. 20 to 94 parts by weight of a polyolefin resin,
5 to 50 parts by weight of a polyamide resin having a melting point of 200 ° C. or more, including 1 to 30 parts by weight of a carboxylic acid-modified polymer,
A flame-retardant resin composition characterized by mixing 30 to 200 parts by weight of a metal hydroxide with respect to 100 parts by weight of the total amount of these compounds. 3. 20 to 94 parts by weight of a polyolefin resin,
5 to 50 parts by weight of polyamide resin, 1 to ionic copolymer
A flame-retardant resin composition comprising 30 parts by weight, and 30 to 200 parts by weight of a metal hydroxide mixed with 100 parts by weight of the total amount of these compounds. 4. The flame-retardant resin composition according to claim 1, wherein the metal hydroxide is surface-treated with an epoxy silane coupling agent. 5. A flame-retardant insulated wire, wherein any one of the flame-retardant resin compositions according to claim 1 is used as a wire covering material.