JP4956234B2 - Flame retardant resin composition and insulated wire coated with the resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition and an insulated wire coated with the resin composition. More specifically, the present invention relates to a flame retardant resin composition used for automobiles, electrical / electronic devices, and the like, and an insulated wire coated with the resin composition.

  Insulating coating materials for components such as automobiles, electrical / electronic devices, and insulated wires installed in these components include various materials such as flame resistance and wear resistance in addition to heat resistance, cold resistance, and moisture resistance. Characteristics are required. Polyvinyl chloride (PVC) resins and polyolefin resins containing halogen-based flame retardants containing bromine (Br) atoms or chlorine (Cl) atoms in the molecule are widely used as resin materials constituting them. It had been. On the other hand, when products using such materials are discarded without appropriate treatment, various problems have occurred. For example, when these products are disposed of in landfills, There is a problem that lead compounds, etc. will be eluted as phosphorus compounds, plasticizers and heavy metal stabilizers contained in the product, while corrosive halogen gases and dioxins will be generated when discarded by incineration. There was a problem.

  For this reason, non-halogen flame retardant resin compositions that do not generate harmful heavy metals or corrosive halogen-based gases have been studied and some have been put into practical use. Non-halogen flame retardant resin compositions that have been studied or put into practical use are widely known to use a polyolefin resin as a base polymer and are filled with a large amount of metal hydrates such as magnesium hydroxide and aluminum hydroxide. In addition, as the base polymer of the resin composition, an ethylene copolymer that easily disperses a large amount of metal hydrate has been used.

  On the other hand, since the mechanical properties and heat resistance of such a halogen-free flame retardant resin composition are lower than those of currently used polyvinyl resins, the halogen-free flame retardant properties equivalent to polyvinyl chloride resins are used. Development of materials is expected. And in order to solve such a problem, the resin composition which uses the polypropylene excellent in a mechanical characteristic and heat resistance as a base polymer (for example, refer patent document 1), the difficulty which uses an ethylene-type copolymer as a base polymer. A method of crosslinking a flammable resin composition by chemical crosslinking or electron beam crosslinking has been studied (for example, see Patent Document 2).

JP 2001-354826 A ([Claim 1], [0007]) JP 2002-332385 A ([Claim 3], [0019])

  However, it has been difficult for the above-described conventional resin compositions to have various properties such as flame retardancy, mechanical properties, heat resistance, and cold resistance in a well-balanced manner. Furthermore, an insulated wire coated with a flame retardant resin composition that has been studied or put into practical use is inferior in wear resistance compared to an insulated wire that has been coated with a conventional polyvinyl chloride resin. There was also a need for improvement.

  The present invention has been made in view of the above problems, and is coated with a flame retardant resin composition excellent in wear resistance and further balanced in flame retardancy and mechanical properties, and the resin composition. It is to provide an insulated wire.

In order to solve the above problems, the flame retardant resin composition of the present invention comprises (a) 40 to 80% by mass of a polypropylene resin, (b) 5 to 20% by mass of an ethylene copolymer, and (c) 100 mass of a resin mixture comprising 5-20 mass% of a styrenic thermoplastic elastomer modified with a saturated carboxylic acid and / or derivative thereof, and (d) 5-20 mass% of a polyolefin modified with an unsaturated carboxylic acid and / or derivative thereof. (E) 40 to 150 parts by mass of magnesium hydroxide and (f) 1 to 20 parts by mass of a clay mineral not subjected to surface treatment are contained.

  In the flame-retardant resin composition of the present invention, the (e) magnesium hydroxide is preferably not subjected to surface treatment.

In the flame-retardant resin composition of the present invention, the mass ratio of (b) the ethylene copolymer and (c) the styrene thermoplastic elastomer modified with the unsaturated carboxylic acid and / or derivative thereof is ethylene-based. Styrenic thermoplastic elastomer modified with copolymer / unsaturated carboxylic acid and / or derivative thereof is preferably 2/1 to 1/2.

The insulated wire of the present invention is characterized in that a conductor is extrusion coated with the flame retardant resin composition of the present invention.

The flame retardant resin composition of the present invention uses a polypropylene resin as a base polymer, and other styrenic thermoplastic elastomers and non-modified olefins modified with a specific amount of an ethylene copolymer, an unsaturated carboxylic acid and / or a derivative thereof. The resin mixture consisting of polyolefins modified with saturated carboxylic acid and / or its derivatives is composed of a specific amount of magnesium hydroxide and clay minerals that are not surface treated . In addition, it is excellent in abrasion resistance, flame resistance and mechanical properties are also good, and it becomes a flame retardant resin composition having these properties in a well-balanced manner.

  Moreover, the flame-retardant resin composition of this invention can improve the abrasion resistance of the said resin composition by employ | adopting the magnesium hydroxide by which surface treatment is not given as magnesium hydroxide.

Furthermore, the flame-retardant resin composition of the present invention, the mass ratio of the ethylene-based copolymer with an unsaturated carboxylic acid and / or its derivatives and modified styrene-based thermoplastic elastomer, ethylene copolymer / non Since the styrenic thermoplastic elastomer modified with a saturated carboxylic acid and / or a derivative thereof is 2/1 to 1/2, the wear resistance of the resin composition can be further improved.

  And since the insulated wire of the present invention is formed by extrusion-coating the above-mentioned flame-retardant resin composition of the present invention on a conductor, it enjoys the effects exhibited by the above-described resin composition of the present invention, and has heat resistance and cold resistance. In addition, the insulated wire has a well-balanced wear resistance, flame retardancy, and mechanical properties.

Hereinafter, the flame retardant resin composition of the present invention will be described. The flame-retardant resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) includes (a) 40 to 80% by mass of a polypropylene resin, and (b) 5 to 20 mass of an ethylene copolymer. %, (C) 5-20% by mass of a styrenic thermoplastic elastomer modified with an unsaturated carboxylic acid and / or its derivative, and (d) 5-20% by mass of a polyolefin modified with an unsaturated carboxylic acid and / or its derivative. (E) 40 to 150 parts by mass of magnesium hydroxide, and (f) 1 to 20 parts by mass of a clay mineral not subjected to surface treatment .

(A) Polypropylene resin:
The polypropylene constituting the flame retardant resin composition of the present invention serves as a base polymer of the resin composition, and makes the mechanical properties, heat resistance and cold resistance of the resin composition good. Examples of usable polypropylene resins include those obtained by polymerizing only propylene and those obtained by copolymerizing propylene with an α-olefin such as ethylene and 1-butene. Specific examples include homopolypropylene, block polypropylene, random polypropylene, propylene-ethylene random copolymer, and propylene-butene random copolymer.

  Moreover, as such a polypropylene resin, the hardness (HRR) is 65 or more, considering that the resin composition of the present invention is used as an insulating coating material for members and insulated wires that require wear resistance, It is preferable to use polypropylene having a flexural modulus of 1000 MPa or more.

  In the present invention, these polypropylenes have a melt flow rate (MFR) defined in JIS K7210 of 10.0 g / 10 min or less (230 ° C., 2 ° C.) from the viewpoint of improving the kneadability of the resin composition. .16 kgf load).

(B) Ethylene copolymer:
The ethylene copolymer constituting the flame retardant resin composition of the present invention is a resin composition that is used in combination with (c) a styrene thermoplastic elastomer modified with an unsaturated carboxylic acid and / or a derivative thereof described later. It has the function of improving the mechanical properties and wear resistance. Examples of the ethylene copolymer that can be used in the present invention include an ethylene / vinyl acetate copolymer, an ethylene / acrylic acid copolymer, an ionomer, an ethylene / methyl acrylate copolymer, an ethylene / ethyl acrylate copolymer, And ethylene / butyl acrylate copolymer.

  In the present invention, these ethylene copolymers have a melt flow rate (MFR) defined in JIS K7210 of 10.0 g / 10 from the viewpoint of improving the kneadability of the resin composition, similarly to polypropylene resins. It is preferable that it is less than a minute (190 degreeC, 2.16kgf load). Examples of such ethylene-based copolymers include “Evaflex”, “Nuclele”, “High Milan” (all manufactured by Mitsui DuPont Polychemical Co., Ltd.), “Lotril” (manufactured by Atofina), and the like.

(C) Styrenic thermoplastic elastomer modified with unsaturated carboxylic acid and / or derivative thereof (modified styrene thermoplastic elastomer) :
A modified styrenic thermoplastic elastomer that constitutes the flame-retardant resin composition of the present invention and improves the mechanical properties and abrasion resistance of the resin composition by using in combination with the (b) ethylene copolymer, A styrenic thermoplastic elastomer is modified with an unsaturated carboxylic acid and / or a derivative thereof.

  Styrenic thermoplastic elastomers that can be used include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-butylene-styrene block copolymer (SEBS). ), Styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like. Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, and fumaric acid. Examples of the unsaturated carboxylic acid derivative include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, Itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester and the like can be mentioned.

In the present invention, the styrenic thermoplastic elastomer modified with these unsaturated carboxylic acids and / or derivatives thereof improves the kneadability of the resin composition in the same manner as the polypropylene resin and the ethylene copolymer. Therefore, the melt flow rate (MFR) specified in JIS K7210 is preferably 10.0 g / 10 min or less (230 ° C., 2.16 kgf load). Examples of styrenic thermoplastic elastomers modified with such unsaturated carboxylic acids and / or derivatives thereof include, for example, “modified DYNARON” (manufactured by JSR Corporation), “Tuftec M” (manufactured by Asahi Kasei Corporation), “ Clayton FG1901X "(manufactured by Clayton Polymer).

(D) Polyolefin modified with unsaturated carboxylic acid and / or derivative thereof (modified polyolefin):
Polyolefins modified with unsaturated carboxylic acids and / or derivatives thereof have improved dispersibility in resin compositions of (e) magnesium hydroxide, which is a non-resin component described later, and (f) clay minerals that have not been surface-treated. In addition, it has the function of improving mechanical properties and wear resistance.

  The modified polyolefin is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid and / or a derivative thereof. Examples of the polyolefin resin that can be used include polypropylene and polyethylene. Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, and fumaric acid. Examples of the unsaturated carboxylic acid derivative include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, There are itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester and the like.

In the present invention, the polyolefin modified with these unsaturated carboxylic acids and / or their derivatives improves the kneadability of the resin composition in the same manner as the polypropylene resin and the like, and the melt specified in JIS K7210. The flow rate is preferably 10.0 g / 10 min or less (190 ° C., 2.16 kgf load) or less. Polyolefins modified with such unsaturated carboxylic acids and / or their derivatives include “Polybond” (Uniroy Chemical Co., Ltd.), “Adtex” (Nihon Polyethylene Co., Ltd.), and “Olevac” (Atofina Co., Ltd.). ) And the like.

(E) Magnesium hydroxide:
Magnesium hydroxide that constitutes the flame-retardant resin composition of the present invention improves the flame retardancy of the resin composition and improves the wear resistance. In addition, examples of magnesium hydroxide used in the present invention include those that have been surface-treated with a fatty acid, a silane coupling agent, or the like, and those that have not been surface-treated, but are not subjected to surface treatment. It is preferable to employ magnesium, whereby the wear resistance of the resin composition can be further improved. Examples of magnesium hydroxide not subjected to surface treatment include “Magnifine H7” (manufactured by Albemarle), “Kisuma 5” (manufactured by Kyowa Chemical Industry Co., Ltd.), and the like. Examples thereof include “Kisuma 5L” (manufactured by Kyowa Chemical Industry Co., Ltd.) subjected to surface treatment with a silane coupling agent or the like.

  In order to make the dispersibility with respect to the resin mixture good, the magnesium hydroxide preferably has, for example, an average particle diameter in the range of 0.3 to 1.5 μm and almost no aggregation. The average particle size is particularly preferably about 0.5 to 1.0 μm.

(F) Clay mineral without surface treatment :
The clay mineral which is not subjected to the surface treatment that constitutes the flame-retardant resin composition of the present invention has a function of improving the wear resistance by being contained in the resin composition. Examples of the clay mineral that can be used in the present invention include kaolinite, calcined kaolinite, montmorillonite, sepiolite, talc, mica and the like, and it is particularly preferable to use calcined kaolinite. These clay minerals may be used alone or in combination of two or more. Also, as with magnesium hydroxide, surface treatment or such as fatty acid or a silane coupling agent, an alkyl ammonium salt, alkyl sulfonium salts, it adopts clay minerals not subjected to surface treatment with an organic treatment by alkyl phosphonium salts. By not subjecting the clay mineral to a surface treatment such as an organic treatment, the wear resistance of the resulting resin composition can be further improved.

  In the present invention, the clay mineral preferably has an average particle size of 10 μm or less, has an average particle size in the range of 0.3 to 2.0 μm, and has almost no aggregation. It is particularly preferable to do this. Examples of such clay minerals include “SATINTONE”, “TRANSLINK” (manufactured by ENGELHARD), “PANGEL” (manufactured by TOLSA), and the like.

Next, the content of each component in the flame retardant resin composition of the present invention will be described.
The content of (a) polypropylene in the resin composition is the entire resin component, that is, (a) polypropylene resin, (b) ethylene copolymer, (c) unsaturated carboxylic acid and / or derivative thereof. modified styrene thermoplastic elastomer, relative to (d) total resin mixture consisting of modified polyolefin with an unsaturated carboxylic acid and / or its derivatives, 40 to 80 wt%. When the content of the polypropylene resin is less than 40% by mass, the wear resistance and heat resistance of the resin composition may be lowered. On the other hand, when the content exceeds 80 % by mass, the mechanical properties of the resin composition are reduced. And cold resistance may decrease. The content of the polypropylene resin is preferably 70 to 80% by mass with respect to the entire resin mixture.

(B) Styrenic thermoplastic elastomers modified with an ethylene copolymer and (c) an unsaturated carboxylic acid and / or derivative thereof can be used in combination with polypropylene rather than mechanical properties and abrasion resistance. Improves. The content of the ethylene copolymer is 5 to 20% by mass with respect to the entire resin mixture, and the content of the styrene thermoplastic elastomer modified with the unsaturated carboxylic acid and / or its derivative is also the resin mixture. It is 5-20 mass% with respect to the whole. If the content of the styrenic thermoplastic elastomer modified with an ethylene copolymer or an unsaturated carboxylic acid and / or derivative thereof is less than 5% by mass, the mechanical properties and cold resistance may be reduced. When the amount exceeds 20% by mass, wear resistance and heat resistance may be lowered. The content of the styrenic thermoplastic elastomer modified with an ethylene copolymer, an unsaturated carboxylic acid and / or a derivative thereof is preferably 5 to 10% by mass with respect to the entire resin mixture.

The mass ratio of the styrene thermoplastic elastomer modified with the ethylene copolymer and the unsaturated carboxylic acid and / or derivative thereof is the styrene type modified with the ethylene copolymer / unsaturated carboxylic acid and / or derivative thereof. The thermoplastic elastomer is preferably 2/1 to 1/2, and particularly preferably approximately equal (1/1). Wear resistance is further improved by making both within the range of this mass ratio.

The total content of the styrene thermoplastic elastomer modified with the ethylene copolymer and the unsaturated carboxylic acid and / or derivative thereof is preferably 10 to 40% by mass with respect to the entire resin mixture. If the total content is less than 10% by mass, the mechanical properties and cold resistance of the resin composition may be lowered. On the other hand, if it exceeds 40% by mass, the wear resistance and heat resistance of the resin composition may be reduced. May decrease. The total content of the styrene thermoplastic elastomer modified with the ethylene copolymer and the unsaturated carboxylic acid and / or derivative thereof is particularly preferably 10 to 20% by mass.

The content of the polyolefin modified with (d) the unsaturated carboxylic acid and / or derivative thereof in the resin composition is 5 to 20% by mass of the entire resin mixture. When the content of the polyolefin modified with the unsaturated carboxylic acid and / or derivative thereof exceeds 20% by mass, the fluidity of the resin composition is lowered, and there may be a problem in molding processability. The content of the polyolefin modified with the unsaturated carboxylic acid and / or derivative thereof is preferably 5 to 10% by mass with respect to the entire resin mixture. Incidentally, in the flame-retardant resin composition of the present invention, by containing a polyolefin modified with an unsaturated carboxylic acid and / or derivatives thereof, not containing modified polyolefin with an unsaturated carboxylic acid and / or its derivatives Compared with the flame retardant resin composition, dispersibility of magnesium hydroxide is improved, which leads to improvement in wear resistance and flame retardancy.

  The content of (e) magnesium hydroxide in the resin composition is 40 to 150 parts by mass with respect to 100 parts by mass of the resin mixture. If the content of magnesium hydroxide is less than 40 parts by mass, sufficient flame retardancy cannot be imparted to the resin composition, while if it exceeds 150 parts by mass, the mechanical properties and cold resistance of the resin composition are not achieved. The specific gravity is adversely affected and the specific gravity is increased. It is preferable that content of magnesium hydroxide shall be 60-120 mass parts with respect to 100 mass parts of resin mixtures.

The content of (f) the clay mineral not subjected to the surface treatment in the resin composition is 1 to 20 parts by mass with respect to 100 parts by mass of the resin mixture. When the content of the clay mineral is less than 1 part by mass, the abrasion resistance of the resin composition is not improved. On the other hand, when it exceeds 20 parts by mass, the mechanical properties of the resin composition are deteriorated. The content of the clay mineral not subjected to the surface treatment is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin mixture.

  It should be noted that various resin components and rubber components other than those described above and various additives may be appropriately added to the resin composition of the present invention as necessary within the range not hindering the object and effect of the present invention. it can. As additives, conventionally known ones can be used, for example, lubricants, antioxidants, light stabilizers, process oils, silicon oils, ultraviolet absorbers, carbon black, dispersants, pigments, dyes, antiblocking agents. Agents, cross-linking agents, cross-linking aids, etc., and depending on the application, conventionally used red phosphorus, polyphosphate compounds, zinc hydroxystannate, zinc stannate, zinc borate, calcium carbonate, hydrotalcite A flame retardant aid such as antimony oxide may be added.

  The flame-retardant resin composition of the present invention is obtained by melt-kneading the above-described components and additives added as necessary with a conventionally known kneading apparatus such as a twin-screw kneading extruder, a Banbury mixer, a kneader, or a roller. It can manufacture more simply. Moreover, when a twin-screw extruder is used, a process can be implemented continuously.

In the production of the flame retardant resin composition, a polypropylene resin, magnesium hydroxide, and a clay mineral (and additives, if necessary) not surface-treated are melt-kneaded in advance. After that, the remaining material (an ethylene copolymer, a styrenic thermoplastic elastomer modified with an unsaturated carboxylic acid and / or a derivative thereof, a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof) is added to the melt-kneaded product. May be further melt-kneaded. Moreover, it is preferable to set as kneading | mixing temperature below the decomposition temperature of component (e) magnesium hydroxide (for example, 340 degrees C or less).

  Moreover, you may make it perform the crosslinking process as needed for the flame-retardant resin composition of this invention. As a crosslinking method, a conventional electron beam irradiation crosslinking method or chemical crosslinking method can be employed. In the case of the electron beam irradiation cross-linking method, the cross-linking can be performed by irradiating an electron beam by a conventional method after molding the flame retardant resin composition of the present invention. On the other hand, in the case of the chemical crosslinking method, an organic peroxide or the like may be added to the resin composition as a conventionally known crosslinking agent, and after the molding, heat treatment may be performed by a conventional method for crosslinking.

The flame retardant resin composition of the present invention uses a polypropylene resin as a base polymer, and other styrenic thermoplastic elastomers and non-modified olefins modified with a specific amount of an ethylene copolymer, an unsaturated carboxylic acid and / or a derivative thereof. Since the resin mixture composed of polyolefin modified with saturated carboxylic acid and / or its derivative is adopted to contain a specific amount of magnesium hydroxide and clay mineral not subjected to surface treatment , heat resistance and In addition to cold resistance, it is excellent in wear resistance, and also has good flame retardancy and mechanical properties, and it becomes a flame retardant resin composition having these properties in a well-balanced manner. And it is easy to recycle even after disposal, and even if it is disposed of such as buried, it does not cause environmental pollution problems due to lead-based compounds or phosphorus compounds, and even if it is incinerated, harmful halogen gas, dioxin, etc. It is environmentally friendly.

  Insulated wires obtained by extrusion-coating the flame-retardant resin composition of the present invention on conductors and optical fibers such as copper wires, tin-plated copper wires, and aluminum wires have mechanical properties such as flame resistance, wear resistance, and tensile properties. It can be widely used as an electric wire having characteristics and adaptability to the environment. In particular, when an electric wire extrusion-coated with the flame retardant resin composition of the present invention is used as an electric wire disposed in an automobile or electronic device that requires high wear resistance, flame resistance, mechanical properties, etc. The effect can be maximized. Such an insulated wire can be easily obtained by extrusion-coating the resin composition of the present invention on the outer periphery of the conductor using a known extrusion molding method.

  In addition, in the insulated wire of this invention, the thickness of insulation coating material does not have a restriction | limiting in particular, It can form as desired thickness. Further, the insulated wire has no problem even if the insulating layer has a multi-layer structure, such as separately providing an intermediate layer between the insulating coating material made of the resin composition of the present invention and the conductor.

  Moreover, the flame-retardant resin composition of this invention can provide the resin molding which enjoys the above-mentioned outstanding effect by setting it as a resin molding. There is no restriction | limiting in particular in the shape of this resin molding, For example, a power plug, a connector, a sleeve, a box, a tape base material, a tube, a sheet | seat etc. can be mentioned. These resin moldings can be obtained by molding the resin composition of the present invention by a conventionally known molding method such as an extrusion molding method or an injection molding method.

Hereinafter, examples, is a more detailed description of the present invention based on the reference Rei及 beauty Comparative Example, the present invention is not limited thereto.

[Examples 1 , 2 , 4 , Reference Examples 3 , 5 and Comparative Examples 1-6]
Table 1, composition of flame retardant resin compositions of Comparative Examples 1 to 6 (uses) Table 1, composition of flame retardant resin compositions of Examples 1 , 2 , 4 and Reference Examples 3 and 5 (contents used) Table 2 shows the materials and contents obtained.

  The details of the materials used are as follows. The melt flow rate (MFR) was measured under the following temperature and load conditions in accordance with JIS K7210. Here, the contents in Table 1 and Table 2 are shown as parts by mass when the entire resin mixture is 100 parts by mass (for each of the resin materials constituting the resin mixture consisting of (1) to (4)). This is the same as the content (mass%) when the entire resin mixture is 100 mass%.)

(1) Polypropylene (polypropylene resin)
Product name: E-200GP (manufactured by Prime Polymer Co., Ltd.)
MFR: 2.0 g / 10 min (230 ° C., 2.16 kgf load)

(2) Ethylene / vinyl acetate copolymer (ethylene copolymer):
Product name: Everflex V527-4 (Mitsui DuPont Polychemical Co., Ltd.)
MFR: 0.7 g / 10 min (190 ° C., 2.16 kgf load)

(3) Modified styrenic thermoplastic elastomer Product name: Kraton FG1901X (manufactured by Kraton Polymer Co., Ltd.)
MFR: 6.4 g / 10 min (230 ° C., 2.16 kgf load)

(4) Modified polyolefin Product name: Adtex L6100M (manufactured by Nippon Polyethylene Co., Ltd.)
MFR: 1.1 g / 10 min (190 ° C., 2.16 kgf load)

(5) Magnesium hydroxide A
Product Name: Kisuma 5L (Kyowa Chemical Industry Co., Ltd.)
Surface treatment: Yes (Surface treatment with silane coupling agent)
Average particle size: 0.8μm

(6) Magnesium hydroxide B
Product Name: Magnificin H7 (Albemarle)
Surface treatment: None Average particle size: 1.0 μm

(7) Clay mineral A
Product name: Satinton SP33 (manufactured by Engelhard)
Surface treatment: None Average particle size: 1.4 μm

(8) Clay mineral B
Product Name: Nanofil 5 (Zudchemy)
Surface treatment: Yes (Organized with alkyl ammonium salt)
Average particle size: 8.0 μm

(9) Antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals)

(10) Lubricant Neowax ACL (manufactured by Yasuhara Chemical Co., Ltd.)

(Composition of resin composition: Examples, Reference examples)

(Composition of resin composition: Comparative example)

[Test Example 1]
The flame retardant resin compositions of Example 1, Example 2, Example 4 , Reference Example 3, Reference Example 5 and Comparative Example 1 to Comparative Example 6 were extruded with a general-purpose extrusion machine for electric wire production. Using the conditions, an insulated wire was manufactured by continuously extruding the outer periphery of an annealed copper wire having a conductor diameter of φ0.85 mm at a thickness of 0.2 mm as an insulating coating material. The obtained insulated wires were compared and evaluated for “tensile properties”, “flame resistance” and “abrasion resistance” according to the following criteria. The results are shown in Table 3.

(Tensile properties)
The tensile strength (MPa) and tensile elongation (%) of the insulation coating material of the obtained insulated wire were measured at a marked line of 50 mm and a tensile speed of 200 mm / min in accordance with JIS C3005. The tensile strength was 16 MPa or more, and the tensile elongation was 125% or more.

(Flame retardance)
A horizontal combustion test specified in JIS C3005 was carried out to confirm flame retardancy. If the flame disappeared within 15 seconds, it was considered acceptable.

(Abrasion resistance)
A load of 7 N was applied to a blade having a piano wire of φ0.45 mm attached to the tip, the wire surface was reciprocated at 60 times / minute, and the number of reciprocations until the blade penetrated the coating and contacted the conductor was measured. The test was accepted after 150 times.

(result)

From the results shown in Table 3, the insulated wires obtained by extrusion coating the resin compositions shown in the examples of the present invention exhibited excellent tensile properties, wear resistance and flame retardancy. In particular, Example 2 using magnesium hydroxide that had not been surface-treated was superior in wear resistance to Example 1 containing the same amount of surface-treated magnesium hydroxide. Note that Reference Example 3 containing no modified polyolefin showed excellent tensile properties, abrasion resistance and flame retardancy, although each characteristic was slightly inferior to Example 1 and the like. Reference Example 5 using an organically treated clay mineral as a clay mineral shows excellent tensile properties, abrasion resistance and flame retardancy, although the abrasion resistance is slightly inferior to Example 1 and the like. It was.

  On the other hand, Comparative Example 1 containing no clay mineral had a problem in wear resistance, and Comparative Example 2 in which the content of magnesium hydroxide exceeded 150 parts by weight had a problem in tensile properties (tensile elongation). Moreover, the comparative example 3 which a resin mixture consists only of a polypropylene had a problem in a tensile characteristic (tensile elongation), and its abrasion resistance was also bad. Comparative Example 4 having a polypropylene content of less than 40% by mass has an abrasion resistance, and Comparative Example 5 having no modified styrene thermoplastic elastomer has an ethylene copolymer for tensile properties (tensile elongation) and abrasion resistance. Comparative Example 6 not containing each had a problem in wear resistance.

The flame retardant resin composition of the present invention is a flame retardant resin composition that is excellent in wear resistance and balanced in various properties such as flame retardancy and mechanical properties. -It can be advantageously used as an insulating coating material for electric wires arranged in electronic equipment, as a constituent member of the automobile or the like.

Claims (4)

(A) Polypropylene resin 40 to 80% by mass, (b) Ethylene copolymer 5 to 20% by mass, (c) Styrenic thermoplastic elastomer 5 to 20% modified with unsaturated carboxylic acid and / or derivative thereof % And (d) 100 parts by mass of a resin mixture comprising 5 to 20% by mass of a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof,
(E) 40 to 150 parts by mass of magnesium hydroxide, and (f) 1 to 20 parts by mass of a clay mineral not subjected to surface treatment .   The flame retardant resin composition according to claim 1, wherein the (e) magnesium hydroxide is not subjected to a surface treatment.   The mass ratio of the (b) ethylene copolymer to the (c) styrenic thermoplastic elastomer modified with the unsaturated carboxylic acid and / or derivative thereof is ethylene copolymer / unsaturated carboxylic acid and / or The flame-retardant resin composition according to claim 1 or 2, wherein the styrenic thermoplastic elastomer modified with the derivative is 2/1 to 1/2.   An insulated wire obtained by extrusion-coating a flame retardant resin composition according to any one of claims 1 to 3 on a conductor.