JP5863781B2 - Flame retardant resin composition and molded article - Google Patents

Description

  The present invention relates to a flame retardant resin composition excellent in heat resistance, flame retardancy and mechanical properties. The present invention also relates to a molded article having excellent heat resistance, flame retardancy and mechanical properties using the same.

  Conventionally, insulated wires, cables, cords, optical fiber cores, optical fiber cords, etc. used for internal and external wiring of electrical and electronic equipment have flexibility and heat resistance in addition to flame resistance and mechanical properties. Various characteristics are required. Similarly, sheets and tubes are required to have flexibility and heat resistance in addition to flame retardancy and mechanical properties.

  Standards such as flame retardancy and mechanical properties (for example, tensile properties) required for wiring materials of electric / electronic devices are determined according to required levels in UL, JIS, and the like. In particular, for flame retardancy, the test method is further determined according to the application. For example, Vertical Flame Test (VW-1) defined in UL1581 (Reference Standard for Electrical Wires, Cables and Flexible Cords), JIS C 3005 Examples include horizontal tests and tilt tests specified in (Rubber / Plastic Insulated Wire Test Methods).

  Up to now, when trying to obtain a highly non-halogen flame retardant resin composition that passes the VW-1 and inclination test, 100 parts by mass of the resin component is highly filled with a metal hydrate that is a flame retardant. For example, it was necessary to mix 100 parts by mass or more. For this reason, non-halogen flame retardant insulated wires using an ethylene-vinyl acetate copolymer as the resin component, in particular, an ethylene-vinyl acetate copolymer have been proposed as a resin component (for example, patents). Reference 1). However, in order to ensure the mechanical properties required for molded articles such as electric wires, heat resistance is often insufficient when an ethylene-vinyl acetate copolymer or the like is used as a base resin component.

  In addition to high flame retardancy, an ethylene-based copolymer containing an ethylene-α-olefin copolymer having a density equal to or lower than a specific value as a resin composition for coating an electric wire excellent in peelability from an electric wire In addition, a resin component containing a block copolymer having an alkyl methacrylate and an alkyl acrylate as constituent components is proposed in which a metal hydrate is contained (see, for example, Patent Document 2). However, when trying to satisfy a high degree of flame retardancy, mechanical properties such as tensile properties and wear resistance, wear resistance, and oil resistance may be significantly reduced.

  Molded articles such as electric wires are required to have heat deformation resistance at high temperatures as heat resistance. A molded article using a conventional PVC material has heat deformation resistance at 120 ° C. or higher, whereas a molded article using a non-halogen flame-retardant resin composition has poor heat resistance, and heat deformation resistance is It was insufficient.

JP 2001-135142 A JP 2008-94977 A

The present invention solves the above-mentioned problems, is excellent in flame retardancy, mechanical properties, oil resistance and wear resistance, and further has excellent thermal deformation (heat deformation resistance) at high temperatures. It is another object of the present invention to provide a molded article.
More particularly, the present invention has a sufficient heat aging characteristic without impairing a high degree of flame retardancy and wear resistance, does not whiten even when bent, is not easily damaged, and has excellent oil resistance. It is an object to provide a conductive resin composition. Another object of the present invention is to provide a molded article such as a wiring material, a sheet, and a tube having a high degree of flame resistance and wear resistance, sufficient heat resistance, and excellent mechanical properties and oil resistance. It is what.

  As a result of intensive studies on the above problems, the present inventor has found that an unmodified ethylene-α-olefin copolymer having a density equal to or higher than a specific value and an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid. The resin composition containing magnesium hydroxide as a non-halogen flame retardant is excellent in flame retardancy, mechanical properties, oil resistance and wear resistance, and is excellent in thermal deformation at high temperatures. I found. The present invention has been made based on this finding.

According to the present invention, the following means are provided.
<1> (a) 5% by mass to 70% by mass of unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more, (b) ethylene-α- modified with unsaturated carboxylic acid 7% by mass or more and 70% by mass or less of an olefin copolymer, (c) 0% by mass or more and 35% by mass or less of an unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ , and (d) polypropylene A flame-retardant resin composition containing 100 parts by mass or more and 280 parts by mass or less of magnesium hydroxide (B) with respect to 100 parts by mass of a resin component (A) composed of 0% by mass to 50% by mass of resin.
<2> The flame-retardant resin composition according to <1>, wherein the content of the (d) polypropylene resin in the resin component (A) is 10% by mass or more and 50% by mass or less.
<3> The flame-retardant resin composition according to <1> or <2>, wherein the content of the (d) polypropylene resin in the resin component (A) is 25% by mass or less and 50% by mass or less.
<4> Any of the above items <1> to <3>, wherein the ethylene-α-olefin copolymer modified with (b) an unsaturated carboxylic acid includes a copolymer having a density of 903 kg / m ³ or more. The flame retardant resin composition according to Item 1.
<5> The ethylene-α-olefin copolymer modified with (b) an unsaturated carboxylic acid is modified with maleic anhydride, according to any one of the items <1> to <4>. Flame retardant resin composition.
<6> 0% by mass or more of at least one selected from the group consisting of (e) an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid alkyl ester copolymer with respect to the resin component (A). The flame-retardant resin composition according to any one of <1> to <5>, which is contained in an amount of 10% by mass or less.
<7> The above <1> to <1>, wherein the magnesium hydroxide (B) is at least one selected from the group consisting of untreated magnesium hydroxide and magnesium hydroxide surface-treated with a silane coupling agent. The flame retardant resin composition according to any one of items 6>.
<8> A molded article formed by using the flame retardant resin composition according to any one of <1> to <7> as a coating layer on an outer periphery of a conductor.
<9> A molded article molded using the flame retardant resin composition according to any one of <1> to <8>.

  INDUSTRIAL APPLICABILITY The present invention can provide a flame retardant resin composition and a molded article that are excellent in flame retardancy, mechanical properties, oil resistance, and abrasion resistance, and further excellent in thermal deformation (heat distortion resistance) at high temperatures. .

  These and other features and advantages of the present invention will become more apparent from the following description.

The flame-retardant resin composition of the present invention comprises (a) an unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more and 5% by mass to 70% by mass, (b) an unsaturated carboxylic acid. 7% by mass or more and 70% by mass or less of the ethylene-α-olefin copolymer modified with (0) 0% by mass or more and 35% by mass or less of the ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ , and (D) 100 mass parts or more and 280 mass parts or less of magnesium hydroxide (B) are contained with respect to 100 mass parts of the resin component (A) consisting of 0 mass% or more and 50 mass% or less of polypropylene resin.
In the present invention, the “unmodified ethylene-α-olefin copolymer” refers to one in which the ethylene-α-olefin copolymer is not modified by grafting or the like.
First, each component which comprises the resin component (A) among the flame-retardant resin compositions of this invention is demonstrated.

The flame retardant resin composition (a) density of 903kg / m ³ or more unmodified ethylene -α- olefin copolymer present invention, as essential components, the density is not modified in 903kg / m ³ or more Contains an ethylene-α-olefin copolymer. Examples of the ethylene-α-olefin copolymer of component (a) include a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. Specific examples of the α-olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. The component (a) does not include a copolymer of ethylene and propylene.
Specific examples of the ethylene-α-olefin copolymer include LLDPE (linear low density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), EPR (ethylene propylene rubber), and EBR (ethylene- 1-butene rubber), and ethylene-α-olefin copolymers synthesized in the presence of a metallocene catalyst. Among these, an ethylene-α-olefin copolymer synthesized in the presence of a metallocene catalyst is preferable.

As the component (a), an unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more is used. As will be described later, as an optional resin component, (c) an unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ can be contained, but the component (a) is a resin component (A). 5 mass% or more and 70 mass% or less, or 5 to 70 mass% is required to be included. Thereby, the resin composition excellent in heat resistance, abrasion resistance, oil resistance, and workability can be obtained. Moreover, when using as an electric wire for press contact, the thing excellent in press contact property can be obtained. If this amount is too small, the oil resistance, wear resistance, and pressure contact properties will be reduced. Moreover, when there is too much this quantity, elongation will fall. The content of the component (a) in the resin component (A) is preferably 8% by mass or more, preferably 55% by mass or less, more preferably 50% by mass or less, preferably 5 to 55% by mass, and 8 to 50% by mass. Is more preferable. The density of the component (a) may be 903 kg / m ³ or more. However, if the density is too large, the elongation characteristics, the low temperature characteristics, and the heat aging characteristics are significantly deteriorated. For this reason, it is preferable that the density of (a) component is 940 kg / m < ³ > or less. More preferably, it is 935 kg / m ³ or less.

Molded products including electric wires are required to have heat deformation resistance. By using an unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more, a certain degree of heat deformation resistance can be maintained. Furthermore, by adding a polypropylene resin as the component (d) described later, higher heat deformation resistance can be maintained, and oil resistance can be largely maintained. Furthermore, by using a specific amount of an unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more, the wire is wound when the wire is wound around a bobbin while maintaining the press-workability of the wire. Can be minimized, and the cause of problems in processing using the electric wire can be reduced. Further, by adding the polypropylene resin as the component (d), it is possible to maintain high heat aging resistance while maintaining a certain hardness and strength.

(B) Ethylene-α-olefin copolymer modified with unsaturated carboxylic acid (b) The ethylene-α-olefin copolymer modified with unsaturated carboxylic acid as component (b) has an unsaturated carboxylic acid of ethylene-α -Resin grafted to olefin copolymer. The component (b) does not include a copolymer of ethylene and propylene.
The amount of modification with the unsaturated carboxylic acid is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 6% by mass or less with respect to the ethylene-α-olefin copolymer. The following is more preferable, 0.2 to 6% by mass is preferable, and 0.5 to 2% by mass is more preferable. The melt flow rate (JIS K 6922) of an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid is preferably 0.3 g / min or more in order to ensure sufficient heat aging resistance and low temperature resistance. 0.5 g / 10 min or more is more preferable, 0.5 g / 10 min or more is more preferable, 15 g / 1 min or less is preferable, 10 g / 10 min or less is more preferable, 8 g / 10 min or less is more preferable, 0 3 to 15 g / 1 min is preferable, 0.5 to 10 g / 10 min is more preferable, and 0.5 to 8 g / 10 min is further more preferable.
The modification of the ethylene-α-olefin copolymer can be performed, for example, by heating and kneading the ethylene-α-olefin copolymer resin and the unsaturated carboxylic acid in the presence of an organic peroxide. In the present invention, the ethylene-α-olefin copolymer modified with (b) the unsaturated carboxylic acid includes a copolymer having a density of 903 kg / m ³ or more, and the ethylene modified with the unsaturated carboxylic acid. The -α-olefin resin is preferably an ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more. Thereby, oil resistance and abrasion resistance increase remarkably.

  The unsaturated carboxylic acid that modifies the ethylene-α-olefin copolymer is not particularly limited, but maleic anhydride is preferred. Specific examples of the ethylene-α-olefin copolymer modified with maleic anhydride include, for example, E226Y (trade name, manufactured by DuPont), Adtex L-6100M (trade name, manufactured by Nippon Polyethylene), Admer XE070, Admer AT2490, Tuffmer MH7020, MH5040 (all are trade names, manufactured by Mitsui Chemicals, Inc.) and the like.

As the component (b), a flame retardant resin composition using an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid, preferably maleic anhydride, has a very high strength and oil resistance. The present inventors have found that it is excellent in maintenance. The mechanism is not yet clear, but it can be considered as follows.
That is, the modified portion in the ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid is strongly ionically bonded to magnesium hydroxide, and the strength in the vicinity of the interface between magnesium hydroxide and the copolymer is increased. Becomes very high. (B) When an ethylene-α-olefin copolymer having a high crystallinity and a density of 903 kg / m ³ or more is used as the component, not only the scratch resistance, wear resistance and mechanical strength, but also flame retardancy is achieved. This is preferable because the oil resistance is dramatically improved. Further, when used for a pressure welding electric wire, there is almost no cracking at the pressure welding blade and a strain relief rises, and an excellent pressure welding electric wire can be obtained.

  In the present invention, (b) the ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid is 7% by mass or more and 70% by mass or less, or 7 to 70% by mass in the resin component (A). The content of the ethylene-α-olefin copolymer modified with (b) an unsaturated carboxylic acid in the resin component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more. More preferably, 30 mass% or more is especially preferable, 70 mass% or less is preferable, 20-70 mass% is preferable, 25-70 mass% is more preferable, 30-70 mass% is further more preferable. If the content of the component (b) is too small, there will be problems in wear resistance and oil resistance, and if it is too much, the elongation characteristics, heat aging characteristics, and trauma resistance will deteriorate. In particular, when this amount is 25 to 70% by mass, a flame retardant resin composition that is very balanced in terms of mechanical strength, heat aging resistance, oil resistance, trauma resistance, abrasion resistance, and press contact is obtained. Can be obtained.

(C) Unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ (c) Inclusion of unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ used as a component The amount is 0% by mass or more and 35% by mass or less, or 0 to 35% by mass in the resin component (A). (C) By including a component, elongation and a flame retardance can be improved. When there is too much (c) component, abrasion resistance and oil resistance will fall. The content of the component (c) in the resin component (A) is preferably 30% by mass or less, and more preferably 25% by mass or less.

Examples of the unmodified ethylene-α-olefin copolymer mentioned as the component (c) include those similar to the component (a). Among them, those having a density of less than 903 kg / m ³ are used. To do. The density of the component (c) may be less than 903 kg / m ^3, but if the density is too small, oil resistance, mechanical strength, and press contact properties are remarkably lowered, so that the density is preferably 868 kg / m ³ or more.
Examples of the component (c) ethylene-α-olefin copolymer include a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. Specific examples of the α-olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. The component (c) does not include a copolymer of ethylene and propylene.

(D) Polypropylene resin As the polypropylene resin of component (d), a propylene homopolymer (homopolypropylene), an ethylene-propylene random copolymer, an ethylene-propylene block copolymer, and the like can be used. By using an ethylene-propylene random copolymer, an ethylene-propylene block copolymer, or the like as the component (d), the moldability can be improved. The ethylene-propylene random copolymer that can be used as the component (d) is one having an ethylene component content of about 1% by mass to 5% by mass, and the ethylene-propylene block copolymer has an ethylene component content of 5% by mass. % To about 15% by mass or less.
MFR (ASTM-D-1238, L condition, 230 ° C.) of polypropylene to be mixed is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, preferably 60 g / 10 min or less, 25 g / 10 min or less is more preferable, 15 g / 10 min or less is more preferable, 0.1 to 60 g / 10 min is preferable, 0.1 to 25 g / 10 min is more preferable, and 0.3 to 15 g / 10 min is further preferable.

  (D) By blending a polypropylene resin, it is possible to maintain the appearance, strength, and press contact. Content of a polypropylene resin is 0 to 50 mass% in a resin component (A), or 0 to 50 mass%. The content of the component (d) in the resin component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, and 50% by mass or less. Preferably, 45 mass% or less is more preferable, 10-50 mass% is preferable, and 25-50 mass% is more preferable. When there is too much content of this polypropylene, the elongation after heat aging will fall. When the content of this polypropylene is 20 to 45% by mass, it is possible to maintain excellent pressure contact property, strength, and oil resistance. Furthermore, when the amount of this polypropylene is 30% by mass or more, it becomes possible to further improve the press contact property and oil resistance.

  A polypropylene obtained by modifying a part or all of this polypropylene with an unsaturated carboxylic acid may be used. By using this modified polypropylene, it is possible to improve strength, hardness, and pressure contact property of the electric wire.

(E) Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer As other components added to the resin component (A), (e) component ethylene-vinyl acetate copolymer and ethylene -At least 1 sort (s) chosen from the group which consists of a (meth) acrylic-acid alkylester copolymer can be added. By adding the component (e), heat aging resistance can be improved. (E) A component can be 0-10 mass% or 0-10 mass% in a resin component (A). The content of the component (e) in the resin component (A) is more preferably 0 to 6% by mass. (E) When there are too many components, intensity | strength, an oil-resistant characteristic, press-contact property, and heat deformation resistance will fall remarkably.

(F) Other components Styrenic elastomer modified with an unsaturated carboxylic acid, styrene copolymer modified with an unsaturated carboxylic acid, ethylene- (meta ) Acrylic acid copolymer, acrylic rubber, polyester and the like can be added. The addition amount is preferably 0% by mass or more, preferably 20% by mass or less, and preferably 0 to 20% by mass in the resin component (A).

By adding a styrene copolymer modified with an unsaturated carboxylic acid, the strength and elongation can be improved, so that the styrene copolymer modified with an unsaturated carboxylic acid in the resin component (A) The content is preferably 0% by mass or more, preferably 20% by mass or less, and preferably 0 to 20% by mass. The styrene copolymer modified with an unsaturated carboxylic acid is a copolymer obtained by grafting an unsaturated carboxylic acid onto a styrene copolymer by modification with an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride, and the like.
The styrene copolymer is a copolymer mainly composed of a block and random structure of a conjugated diene compound and an aromatic vinyl compound, and a hydrogenated product thereof. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene, Examples thereof include p-tert-butylstyrene. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.

The styrene copolymer can be modified by, for example, heating and kneading the styrene copolymer and an unsaturated carboxylic acid in the presence of an organic peroxide. The amount of modification with the unsaturated carboxylic acid is usually 0.5% by mass or more and 15% by mass or less, or 0.5 to 15% by mass.
Examples of the styrenic copolymer modified with an unsaturated carboxylic acid include Kraton 1901FG (trade name, manufactured by JSR Kraton), Tuftec (trade name, manufactured by Asahi Kasei), and the like.

(B) Magnesium hydroxide The flame-retardant resin composition of the present invention contains a resin component (A) and magnesium hydroxide (B).
In general, a flame retardant resin composition obtained by blending a resin component with a metal hydrate such as magnesium hydroxide has a marked decrease in wear resistance. However, in the present invention, even if a specific amount of magnesium hydroxide, which is a metal hydrate, is contained, the wear resistance is not lowered, but rather the wear resistance and oil resistance are improved, and flame retardancy and wear resistance are improved. And oil resistance can be achieved.

Even when magnesium hydroxide is added to a resin component containing a specific component, the wear resistance is not lowered, but rather the mechanism of improvement is not clear, but is considered as follows.
Magnesium hydroxide and the component (b) have a strong ionic bond, and the magnesium hydroxide and the whole polymer are finely and firmly bonded in the nano-micro state. By integrating the magnesium hydroxide and the resin component, it is considered that the inherent hardness, strength and reinforcement of the magnesium hydroxide are exhibited, and the abrasion resistance of the resin composition is remarkably improved. By this action, even when the surface of the molded body of the flame retardant resin composition of the present invention is rubbed, no whitening phenomenon occurs, and a very high-strength molded body can be obtained.
In addition, it is considered that a flame retardant resin composition excellent in strength, wear resistance, trauma resistance, and pressure contact property can be obtained by the presence of the highly crystalline component (a) in the vicinity of the magnesium hydroxide interface. It is done. Furthermore, the presence of the component (b) in a form compatible with the component (a) makes it possible to obtain an inexpensive material with high wear resistance and oil resistance. Furthermore, by mixing the component (c) in a form compatible with these components, relatively high flexibility can be maintained while maintaining high elongation characteristics, and high hot set characteristics when subjected to electron beam crosslinking or chemical crosslinking. Can be maintained.

  (B) As what can be used as magnesium hydroxide, the commercially available magnesium hydroxide can be used. In the present invention, magnesium hydroxide may be subjected to a surface treatment even without being treated. You may use both together. Examples of the surface treatment include fatty acid treatment, phosphoric acid treatment, titanate treatment, treatment with a silane coupling agent, and the like. In view of the action with the resin component (A), in the present invention, it is preferable to use untreated magnesium hydroxide, magnesium hydroxide surface-treated with a silane coupling agent, or a combination of both. . Further, magnesium hydroxide subjected to different surface treatments can be used in combination.

The silane coupling agent in the present invention preferably has a vinyl group, a methacryloxy group, a glycidyl group, or an amino group at the terminal. Specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyl Triethoxysilane, methacryloxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltripropyl Examples include methyldimethoxysilane and N- (β-aminoethyl) -γ-aminopropyltripropyltrimethoxysilane. Of these, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane and the like are preferable.
When treating magnesium hydroxide with a silane coupling agent, only one of the silane coupling agents or two or more of them may be used in combination.

  As a surface treatment method using a silane coupling agent, it is possible to perform the treatment by a commonly used method. For example, magnesium hydroxide that has not been surface-treated is previously dry-blended or wet-treated. Or by blending a silane coupling agent during kneading. The content of the silane coupling agent to be used is appropriately added in an amount sufficient for the surface treatment. Specifically, the content is preferably 0.1% by mass or more, and 0.2% by mass or more with respect to magnesium hydroxide. Is more preferably 0.3% by mass or more, preferably 2.5% by mass or less, more preferably 1.8% by mass or less, still more preferably 1.0% by mass or less, and 0.1 to 2.5%. % By mass is preferable, 0.2 to 1.8% by mass is more preferable, and 0.3 to 1.0% by mass is further preferable.

It is also possible to obtain magnesium hydroxide that has already been treated with a silane coupling agent. Specific examples of magnesium hydroxide surface-treated with a silane coupling agent include Kisuma 5L, Kisuma 5N, Kisuma 5P (all trade names, manufactured by Kyowa Chemical Co., Ltd.) and Magseeds S4 (trade names, Kamishima Chemical Co., Ltd.). Manufactured).
Examples of the untreated magnesium hydroxide include Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.), Magnifine H5 (trade name, manufactured by Albemarle), and the like.

  In the flame-retardant resin composition of the present invention, the content of magnesium hydroxide is 100 parts by mass or more and 280 parts by mass or less, or 100 to 280 parts by mass, and 120 parts by mass with respect to 100 parts by mass of the resin component (A). Part or more is preferable, and 120 to 280 parts by mass is preferable. When there is too little content, a problem will arise in a flame retardance and it will become easy to reduce abrasion resistance. If the amount is too large, the mechanical properties are remarkably deteriorated, and there are problems in wear resistance, appearance, and press contact. In particular, when magnesium magnesium hydroxide is added in an amount of 120 parts by mass or more based on 100 parts by mass of the resin component (A), the wear resistance can be remarkably improved.

  In addition, a melamine cyanurate compound can be added to improve flame retardancy. The melamine cyanurate preferably has a fine particle size. The average particle size of the melamine cyanurate compound used in the present invention is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. If the particle size is too small, secondary agglomeration tends to occur, so 0.6 μm or more is preferable. A melamine cyanurate compound surface-treated from the viewpoint of dispersibility is preferably used. Examples of the melamine cyanurate compound that can be used in the present invention include MC6000 (trade name, manufactured by Nissan Chemical Co., Ltd.), Merapua MF15 (trade name, manufactured by Ciba), and Stabilace MC15 (trade name, manufactured by Sakai Chemical Co., Ltd.). is there.

  Examples of the melamine cyanurate compound that can be used in the present invention include melamine cyanurate having the following structure.

The flame retardant resin composition of the present invention can contain at least one selected from zinc stannate, zinc hydroxystannate and zinc borate as necessary, and can further improve flame retardancy. . By using these compounds, the speed of shell formation during combustion is increased and the shell formation becomes stronger. Accordingly, the flame retardancy can be dramatically improved together with the melamine cyanurate compound that generates gas from the inside during combustion.
The average particle size of zinc borate, hydroxy hydroxystannate, and zinc stannate used in the present invention is preferably 5 μm or less, and more preferably 3 μm or less. If the particle size is too small, secondary aggregation tends to occur, so 0.5 μm or more is preferable.
Specific examples of zinc borate that can be used in the present invention include Alkanex FRC-500 (2ZnO / 3B ₂ O ₃ .3.5H ₂ O), Alkanex FRC-600 (both trade names, Mizusawa). Chemical)). Examples of zinc stannate (ZnSnO ₃ ) and hydroxy hydroxy stannate (ZnSn (OH) ₆ ) include Alkanex ZS and Alkanex ZHS (both trade names, manufactured by Mizusawa Chemical Co., Ltd.).

  The flame retardant resin composition of the present invention includes various additives generally used in molded articles, for example, antioxidants, metal deactivators, flame retardants (auxiliaries), fillers, and lubricants. And the like can be appropriately blended within a range not impairing the object of the present invention.

  Antioxidants include amine-based antioxidants such as 4,4'-dioctyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer Agents, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and other phenolic antioxidants, bis (2-methyl-4- ( Sulfur-based antioxidants such as 3-n-alkylthiopropionyloxy) -5-t-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, pentaerythritol-tetrakis (3-lauryl-thiopropionate), etc. Can be given.

Metal deactivators include N, N'-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4 -Triazole, 2,2′-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
Flame retardant (auxiliary) and filler include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, calcium carbonate, magnesium carbonate, white carbon Etc.
Examples of the lubricant include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based, and silicone-based materials. Among these, hydrocarbon-based and silicone-based materials are preferable.

  The flame retardant resin composition of the present invention is a kneading apparatus usually used such as a uniaxial kneading extruder, a biaxial kneading extruder, a Banbury mixer, a kneader, or a roll, preferably 150 ° C. or higher and 240 ° C. or lower. Alternatively, it can be obtained by melt-kneading at 150 to 240 ° C.

Next, a molded article using the flame retardant resin composition of the present invention will be described.
Examples of the molded article of the present invention include an insulated wire or cable in which the outer periphery of a conductor, optical fiber, or other molded body is coated with the flame retardant resin composition of the present invention. This insulated wire or cable can be produced by extruding and coating the flame retardant resin composition of the present invention around a conductor, an optical fiber, an assembled insulated wire or other molded body using a conventional extrusion molding machine. . The tube can be manufactured in the same manner.
For example, when used for an insulated wire, the thickness of the coating layer of the insulating resin composition formed on the outer periphery of the conductor is not particularly limited, but is preferably 0.15 mm or more, preferably 3 mm or less, and 0. 15-3 mm is preferable. The insulating layer may have a multilayer structure, and may have an intermediate layer in addition to the coating layer formed of the flame-retardant insulating resin composition of the present invention.
When the molded article of the present invention is used as a wiring material, it is possible to use the resin composition of the present invention by extrusion coating to form a coating layer as it is, but to improve heat resistance. For the purpose, it is preferable to crosslink the coating layer after extrusion.

As a method for crosslinking, a conventional electron beam irradiation crosslinking method or chemical crosslinking method can be employed. Among these, electron beam crosslinking is preferable.
In the case of the electron beam crosslinking method, the resin composition is extruded to form a coating layer, and then crosslinked by irradiating an electron beam by a conventional method. The electron beam dose is appropriately 1 to 30 Mrad, and in order to efficiently crosslink, the resin composition constituting the coating layer includes a methacrylate compound such as trimethylolpropane triacrylate, and an allyl group such as triallyl cyanurate. You may contain polyfunctional compounds, such as a compound, a maleimide type compound, and a divinyl type compound, as a crosslinking adjuvant.
In the case of the chemical cross-linking method, the resin composition contains an organic peroxide as a cross-linking agent and is extruded to form a coating layer, followed by heat treatment by a conventional method.

  The size and shape of the molded article of the present invention are not particularly limited, and examples thereof include a power plug, a connector, a sleeve, a box, a tape base material, a tube, and a sheet. The molded article of the present invention is molded from the flame retardant resin composition of the present invention by a molding method such as ordinary injection molding. Sheets, tubes, and the like can also be manufactured in the same manner as the wire coating, and if necessary, crosslinking can be performed in the same manner as the wiring material.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

Examples 1-13, Comparative Examples 1-10
Table 1 shows the content of each component of the resin compositions of Examples 1 to 13 and Table 2 of Comparative Examples 1 to 10 (the numerical values in the table are parts by mass). Each component shown in Tables 1 and 2 was dry-blended at room temperature and melt-kneaded at 195 to 205 ° C. using a Banbury mixer to produce each flame-retardant resin composition.

As each component material, the following were used.
(A) Component Unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more (a-1) Product name: SP1540 (manufactured by Prime Polymer Co., Ltd.) (density 913 kg / m ³ )
(A-2) Product name: SP2320 (manufactured by Prime Polymer) (density 920 kg / m ³ )
(A-4) Product name: Umerit 4040F (manufactured by Ube Maruzen Petrochemical Co., Ltd.) (density 937 kg / m ³ )
(A-5) Product name: Umerit 0540F (manufactured by Ube Maruzen Petrochemical Co., Ltd.) (density 904 kg / m ³ )

(B) Component Ethylene-α-olefin copolymer modified with unsaturated carboxylic acid The following (b-1) and (b-3) are both ethylene-α-olefin modified with maleic anhydride It is a copolymer.
(B-1) Product name: Husabond E226Y (manufactured by DuPont) (density 930 kg / m ³ )
(B-3) Product name: Admer XE070 (Mitsui Chemicals) (density 893 kg / m ³ )

(C) Component Unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ (c-1) Trade name: Kernel KS240T (manufactured by Nippon Polyethylene) (density 880 kg / m ³ )
(C-2) Product name: Kernel KF360T (manufactured by Japan Polyethylene Corporation) (density 898 kg / m ³ )

(D) Component Polypropylene resin (d-1) Ethylene-propylene block copolymer, trade name: BC8A (manufactured by Nippon Polypro)
(D-2) Propylene homopolymer, trade name: V200S (manufactured by Sun Allomer)
(D-3) Ethylene-propylene random copolymer, trade name: PB222A (manufactured by Sun Allomer)

(E) Component
(E-1) Ethylene-vinyl acetate copolymer, trade name: V-5274 (Mitsui DuPont Polychemical Co., Ltd.)
(E-2) Ethylene-ethyl acrylate copolymer, trade name: NUC6510 (manufactured by Dow Chemical Company)

(F) Component (f-1) Styrenic copolymer modified with maleic anhydride (MAH-SBC), trade name: Kraton 1901FG (manufactured by Kraton Polymer Co., Ltd.)

(B) Magnesium oxide (B-1) Magnesium hydroxide (magnesium hydroxide surface-treated with a silane coupling agent), trade name: Kisuma 5L (manufactured by Kyowa Chemical Co., Ltd.)
(B-2) Magnesium hydroxide (magnesium hydroxide surface-treated with a silane coupling agent), trade name: Magseeds S-6 (manufactured by Kamishima Chemical Co., Ltd.)

(X) Others (X-1) Copper damage inhibitor, trade name: CDA-1 (manufactured by ADECA)
(X-2) Lubricant (polyethylene-based WAX), trade name: PE-WAX (manufactured by Honeywell)
(X-3) Hindered phenol antioxidant, trade name: Irganox 1010 (manufactured by Ciba)

Next, the flame retardant of each of the above Examples 1 to 13 and Comparative Examples 1 to 10 previously melt-kneaded on a conductor (tin-plated annealed copper wire having a conductor diameter of 0.8 mmφ) using an extrusion coating apparatus for electric wire production The insulated resin composition was coated by an extrusion method to produce each insulated wire. The outer diameter was 1.3 mm, and the thickness of the insulating layer was 0.25 mm.
The following (1) to (9) were evaluated for each of the obtained insulated wires, and the obtained results are shown in Table 1 and Table 2, respectively.
Moreover, the tube of the flame-retardant resin composition of Example 1 was manufactured using the extruder. The outer diameter of the tube was 2.0 mm, and the inner diameter was 1.5 mm. The following (1), (2), and (4) were evaluated with respect to the obtained tube. In any evaluation, it was performed similarly to the evaluation of the insulated wire except that the tube was used as it was.

(1) Tensile test A tubular piece was prepared from the electric wire and a tensile test was performed. The test was performed at 25 mm between marked lines and a tensile speed of 50 mm / min, and the tensile strength and elongation were measured. An elongation of 100% or more and a tensile strength of 18 MPa or more are required.
Further, as heat aging characteristics, the tubular piece was heat-treated at 136 ° C. for 168 hours in a thermostatic bath, and after taking out, the tensile test was performed under the above conditions. The tubular piece had a tensile residual ratio of 70% or higher and an elongation residual ratio of 50% or higher.

(2) Abrasion resistance Using a blade of R = 0.225, a test was conducted by a blade reciprocation method based on JASO D608. The weight was 6N. The number of passes is 800 or more, but it is acceptable, but 1000 or more is more preferable.

(3) Flame retardance A horizontal combustion test was conducted based on JASO D608. Those that spread for 60 seconds or more were rejected and indicated by “x”, and “◯” was accepted.

(4) Trauma resistance In a blade reciprocation test method of wear resistance test based on JASO D 608, a blade with R = 0.125 mm was used and four reciprocal wears were performed at a load of 5N. Subsequent samples were observed. A sample having no trauma or whitening was indicated by “◯” and passed, and a sample having trauma or marked whitening was indicated by “x” and was rejected.

(5) Appearance As for the appearance, the presence or absence of fluctuations in the outer diameter of the insulated wire and the surface condition were visually inspected. Stable ones, rough ones on the surface, and ones with bleed were shown as “x” and rejected.

(6) Oil resistance 1
A tubular piece was prepared, immersed in JIS No. 2 test oil heated to 70 ° C., and taken out after 4 hours. After wiping off the oil immediately, it was left for 16 hours and then subjected to a tensile test under the condition (1). The tensile strength residual rate is 70% or more and the elongation residual rate is 65% or more, which is acceptable. Preferably, the tensile strength residual rate is 80% or more and the elongation residual rate is 80% or more.

(7) Oil resistance 2
A tubular piece was prepared, immersed in JIS No. 2 test oil heated to 85 ° C., and taken out after 4 hours. After wiping off the oil immediately, it was left for 16 hours and then subjected to a tensile test under the condition (1). Although the tensile strength residual rate is 80% or more and the elongation residual rate is 70% or more, it passes, but since oil resistance 2 is a test under severe conditions, it is preferable to pass, but the above oil resistance 1 is It only has to pass. More preferably, the residual tensile strength is 80% or more and the residual elongation is 80% or more.

(8) Heat deformation resistance The heat deformation resistance test was performed at 121 ° C. based on UL1581. The load was 2.5N. 50% or less was accepted.

(9) Pressure welding Using a CT connector manufactured by TYCO as a connector, pressure welding was performed. Thereafter, the workability was observed, and it was observed whether the deformed portion of the electric wire exceeded the arrowhead of the strain relief or cracked at the press contact blade.
The case where the deformed part of the electric wire crossed the arrowhead of the strain relief or was cracked at the press contact blade was indicated as “x” and rejected, and “◯” was accepted.

Tables 1 and 2 show the following.
(A) When an unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more is not included, the wear resistance and pressure workability are rejected, and the oil resistance 2 is also large. It turns out that it has fallen (Comparative Examples 2-4). On the contrary, when the component (a) was too much, the elongation was insufficient (Comparative Example 5). When the ethylene-α-olefin copolymer modified with the unsaturated carboxylic acid of component (b) was not included, the wear resistance, oil resistance, and press contact were unacceptable (Comparative Example 8). When there was too much said (b) component, elongation was inadequate and there existed a problem in the heat aging characteristic (comparative example 7). Moreover, when there was too much unmodified | denatured ethylene-alpha-olefin copolymer whose density of (c) component is less than 903 kg / m < ³ >, abrasion resistance and oil resistance were disqualified (Comparative Example 1). . When there was too much polypropylene resin of (d) component, the residual elongation rate after heat aging showed the characteristic which is inadequate (Comparative Example 6). When there is too little magnesium hydroxide (B), it turns out that a flame retardance is rejected and abrasion resistance falls significantly (Comparative Example 9). When there was too much magnesium hydroxide (B), abrasion resistance, oil resistance, trauma resistance, external appearance, and press-contact property were disqualified (Comparative Example 10).
In contrast, the flame retardant resin compositions of Examples 1 to 13 have sufficient heat aging characteristics while satisfying a high degree of flame retardancy, and are resistant to scratching without being whitened even when bent. Excellent wear resistance. Furthermore, regarding oil resistance, it exhibited an excellent characteristic of passing a particularly severe oil resistance 2 test. For this reason, the flame-retardant resin composition of the present invention can provide molded articles such as wiring materials, sheets, tubes and the like that are excellent in high flame retardancy, wear resistance, heat resistance, mechanical properties and oil resistance. it can.

  While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

  This application claims priority based on Japanese Patent Application No. 2011-102828 filed in Japan on May 2, 2011, which is hereby incorporated herein by reference. Capture as part.

Claims (9)

(A) unmodified ethylene-α-olefin copolymer having a density of 903 kg / m ³ or more 5% by weight to 70% by weight, (b) ethylene-α-olefin copolymer modified with unsaturated carboxylic acid 7% by mass to 70% by mass of coal, (c) 0% by mass to 35% by mass of unmodified ethylene-α-olefin copolymer having a density of less than 903 kg / m ³ , and (d) 0% by mass of polypropylene resin A flame retardant resin composition containing 100 parts by mass or more and 280 parts by mass or less of magnesium hydroxide (B) with respect to 100 parts by mass of the resin component (A) consisting of from 50% to 50% by mass.   The flame-retardant resin composition according to claim 1, wherein the content of the (d) polypropylene resin in the resin component (A) is 10% by mass or more and 50% by mass or less.   The flame-retardant resin composition according to claim 1 or 2, wherein a content of the (d) polypropylene resin in the resin component (A) is 25% by mass or more and 50% by mass or less. The flame retardant according to any one of claims 1 to 3, wherein the ethylene-α-olefin copolymer modified with (b) an unsaturated carboxylic acid includes a copolymer having a density of 903 kg / m ³ or more. Resin composition.   The flame-retardant resin composition according to any one of claims 1 to 4, wherein the ethylene-α-olefin copolymer modified with (b) an unsaturated carboxylic acid is modified with maleic anhydride.   0% by mass or more and 10% by mass of at least one selected from the group consisting of (e) an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid alkyl ester copolymer with respect to the resin component (A). The flame-retardant resin composition according to any one of claims 1 to 5, comprising:   The magnesium hydroxide (B) is at least one selected from the group consisting of untreated magnesium hydroxide and magnesium hydroxide surface-treated with a silane coupling agent. The flame-retardant resin composition according to Item.   The molded article which uses the flame-retardant resin composition of any one of Claims 1-7 as a coating layer on the outer periphery of a conductor. The molded article currently shape | molded using the flame-retardant resin composition of any one of Claims 1-8.