JP2005314516A - Non-halogen flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-halogen flame-retardant resin composition having flame retardance clearing UL standard VW-1, heat resistance, mechanical properties, flexibility and heat distortion properties enabling use under high temperature of ≥100°C and not emitting halogen-containing substances such as harmful dioxins upon combustion. <P>SOLUTION: The non-halogen flame-retardant resin composition is obtained by compounding 100 pts. mass base polymer containing (A) 5-50 pts. mass ethylene-vinyl acetate copolymer and/or ethylene-(meth)acrylic ester copolymer, (B) 5-30 pts. mass polypropylene resin, (C) 5-50 pts. mass block copolymer composed of a vinyl aromatic compound and a conjugated diene compound and/or a block copolymer obtained by hydrogenating the block copolymer, (D) 5-40 pts. mass ethylene-acrylic ester copolymer rubber, (E) 0-15 pts. mass ethylene-propylene copolymer rubber and (F) 5-30 pts. mass modified polyolefin resin modified with an unsaturated carboxylic acid or its derivative with (G) 100-300 pts. mass metal hydrate treated with a silane coupling agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a non-halogen flame retardant resin composition that is excellent in environmental safety since no halogen gas is generated during combustion. Particularly, the present invention relates to flame retardancy, mechanical characteristics, heat resistance, flexibility, heat deformation characteristics, molding. The present invention relates to a non-halogen flame retardant resin composition having excellent processability and the like. More specifically, the present invention relates to a non-halogen flame retardant resin composition suitable as a covering material for insulated wires, electric cables, electric cords and the like used for internal and external wiring of electric and electronic devices.

Conventionally, various halogen-free flame retardant resin compositions that do not generate harmful halogen gas such as dioxin during combustion have been developed and put into practical use as covering materials for insulated wires, electric cables and the like. As such a non-halogen flame retardant resin composition, for example, a composition in which 100 to 300 parts by mass of a metal hydrate such as magnesium hydroxide as a flame retardant is known to 100 parts by mass of a polyolefin resin. ing. Inorganic flame retardants such as magnesium hydroxide have the advantages of exhibiting a flame retardant action by releasing crystal water during combustion, resulting in a small amount of smoke generation and low toxicity and corrosivity.
Among polyolefin resins, for example, ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-α olefin copolymer are excellent in flexibility, workability, weather resistance, etc., but have a low melting point. When used in a high-temperature atmosphere, the strength and elongation are remarkably reduced, so that it is difficult to use in fields requiring heat resistance. However, on the other hand, non-halogen flame retardant resin compositions using these ethylene-based copolymers do not generate harmful halogen gas during combustion and have advantages such as no elution of heavy metals and phosphorus compounds.

As a means of improving the heat resistance of the non-halogen flame retardant resin composition using the ethylene-based copolymer, there is a method of cross-linking the copolymer with an electron beam, but material recycling becomes impossible, and its application field is It will be limited.
As another means for improving the heat resistance, a method of blending a thermoplastic polymer having a high melting point such as polypropylene can be considered. For example, the heat resistance is improved by blending of polypropylene, but the temperature is 100 ° C. or higher. In order to obtain a flame retardant resin composition that can withstand a high temperature range, it is necessary to blend a considerable amount of polypropylene. As a result, the flexibility of the resulting resin composition is impaired, and due to the lack of compatibility of both the ethylene copolymer and polypropylene, only a resin composition having a small elongation can be obtained, and the shell is not damaged during combustion. The conventional non-halogen flame retardant resin composition blended with polypropylene is insufficient in flame retardancy and mechanical strength because it is difficult to form and drip.

On the other hand, electric wires and cables used in the electric and electronic fields are required to have high flame resistance from the viewpoint of safety, and it is necessary to pass VW-1 of the vertical combustion test specified in UL1581. . In addition to flame retardancy, UL standards and electrical appliance regulations regulations require high mechanical properties with a breaking strength of 10.3 MPa or higher, elongation of 100% or higher, and heat deformation characteristics at 100 ° C. or higher.
In order to realize these requirements, a material having both high flame retardancy and mechanical strength by blending ethylene-acrylic acid ester copolymer rubber and metal hydrate with the above-mentioned ethylene-based copolymer. In recent years, however, many have been developed by various companies (see, for example, Patent Documents 1 to 3). These materials are both materials that have both flame retardancy and mechanical strength that pass UL-standard VW-1 and heat resistance under high temperature atmospheres of 100 ° C or higher. Further improvements in heat resistance, flexibility, heat distortion characteristics, moldability, manufacturing methods, and the like are required.

  More specifically, the above-mentioned Patent Document 1 discloses (a) an ethylene / α-olefin copolymer and / or an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylic acid ester copolymer. 100 parts by mass of a thermoplastic resin component comprising 97% to 3% by mass of (b) a polyolefin resin modified with acrylic acid and / or methacrylic acid and / or an ethylene- (meth) acrylic acid copolymer On the other hand, each component of metal hydrate in which at least 50% by mass or more of metal hydrate (c) is treated with a reactive silane coupling agent is heat-treated in the presence of an organic peroxide to dynamically A flame retardant resin composition that crosslinks is described. Although the composition has good flame retardancy, mechanical properties, heat resistance, and the like, it requires a complicated melt-kneading step, and thus the production method needs to be improved.

  Moreover, in the said patent document 2, 150-280 mass parts of metal hydrate, diester acrylate, and 100 mass parts of resin components which consist of 95-40 mass% of ethylene-type copolymers and 5-60 mass% of acrylic rubbers are mentioned. A flame retardant resin composition containing 1 to 16 parts by mass of diester methacrylate and having a surface treatment of 50% by mass or more of the metal hydrate with a reactive silane coupling agent is described. Although the composition has good flame retardancy, mechanical properties, heat resistance, and the like, it does not contain a thermoplastic polymer having a high melting point such as polypropylene, so that further improvement in heat resistance, heat deformation properties, etc. can be achieved. is necessary.

  Further, Patent Document 3 discloses that 100-mass part of a base polymer including 40-70 parts by mass of an ethylene-vinyl acetate copolymer, 20-30 parts by mass of acrylic rubber, and 10-30 parts by mass of a maleic acid-modified polyolefin polymer. On the other hand, a composition containing 80 to 180 parts by mass of metal hydrate and 2 to 10 parts by mass of red phosphorus is described. Although the composition also has good flame retardancy, mechanical properties, heat resistance, etc., it does not contain a thermoplastic polymer having a high melting point such as polypropylene, so that further improvement in heat resistance, heat deformation properties, etc. is required.

JP 2003-160704 A JP 2002-042553 A JP 2003-160709 A

  Problems in the present invention include flame retardancy that passes VW-1 of the UL standard, high mechanical properties, excellent heat resistance, flexibility, heat deformation properties, moldability, etc., and harmful dioxins during combustion It is an object to provide a non-halogen flame retardant resin composition that does not generate a halogen-containing substance and can be produced by a relatively simple process.

As a result of intensive studies to solve the above problems, the present inventors have found that an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylate ester copolymer, a polypropylene resin, a vinyl aromatic compound, and a conjugated diene. A block copolymer comprising a compound, and / or a block copolymer obtained by hydrogenation thereof, an ethylene-acrylic acid ester copolymer rubber, an ethylene-propylene copolymer rubber, an unsaturated carboxylic acid or a derivative thereof; It consists of a modified modified polyolefin resin, a composition of a metal hydrate treated with a silane coupling agent, and when their blending amount is in a specific range, dynamic crosslinking as in the prior art described in the above publication Non-halogen flame retardant resin that has various physical properties better than conventional ones in a single non-crosslinking melt-kneading process without the need for processes Found that growth was obtained. In particular, the non-halogen flame retardant resin composition obtained by such a one-step non-crosslinking melt-kneading process and the molded product obtained therefrom are flame retardant that passes UL standard VW-1, at a high temperature of 100 ° C. or higher. It has been found that it has excellent heat resistance, mechanical properties, flexibility, and heat distortion properties that can be used, and does not generate harmful halogen-containing substances such as dioxins during combustion.
That is, the present invention comprises (A) an ethylene-vinyl acetate copolymer and / or 5 to 50 parts by mass of an ethylene- (meth) acrylate copolymer, (B) 5 to 30 parts by mass of a polypropylene resin, (C) 5 to 50 parts by mass of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound and / or hydrogenation of the block copolymer, and (D) ethylene-acrylic acid ester copolymer A base comprising 5 to 40 parts by mass of a combined rubber, (E) 0 to 15 parts by mass of an ethylene-propylene copolymer rubber, and (F) 5 to 30 parts by mass of a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. It is a non-halogen flame retardant resin composition in which 100 to 300 parts by mass of (G) a metal hydrate treated with a silane coupling agent is blended with 100 parts by mass of a polymer.

  According to the present invention, flame retardant that passes UL standard VW-1, heat resistance that can be used at a high temperature of 100 ° C or higher, mechanical properties, flexibility, heat deformation properties, and harmful dioxins during combustion Thus, it is possible to obtain a non-halogen flame retardant resin composition that does not generate any halogen-containing substance.

Hereinafter, the present invention will be described in detail based on embodiments. First, each component of the non-halogen flame retardant resin composition of the present invention will be described. As described above, the non-halogen flame retardant resin composition of the present invention contains a predetermined amount of the component (G) in the base polymer comprising the components (A) to (F) (however, the component (E) is optional). It is a thing.
(A) In ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylic acid ester copolymer, the ethylene-vinyl acetate copolymer is flame retardant which passes UL standard VW-1. In order to impart the above, the vinyl acetate content is preferably 15 to 50% by mass, more preferably 23 to 50% by mass, and still more preferably 25 to 50% by mass. The ethylene-vinyl acetate copolymer preferably has an MFR (melt flow rate) of 0.01 to 10 g / min. The value of MFR in the present invention is determined according to JIS K7210 under conditions suitable for generally used materials.
The ethylene- (meth) acrylic acid ester copolymer preferably has a (meth) acrylic acid ester content of 10 to 30% by mass and an MFR of 0.01 to 10 g / min.
Further, when the component (A) is a blend of an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer, the ethylene-vinyl acetate copolymer is 50% by mass or more and less than 100% by mass. And it is preferable that ethylene- (meth) acrylic acid ester copolymer is 50 mass% or less.
The blending amount of the component (A) is 5 to 50 parts by mass in 100 parts by mass of the base polymer, and if it is less than 5 parts by mass, the flexibility of the composition is insufficient, and if it exceeds 50 parts by mass, mechanical properties and heat resistance are deteriorated. descend. In addition, you may use (A) component combining multiple different things.

(B) As the polypropylene resin, either a homotype polypropylene or a block of propylene and a small amount of other α-olefin such as 1-butene, 1-hexene, 4-methyl-1-pentene, etc., or random Copolymers can be used. Further, in order to impart sufficient heat resistance and heat deformation characteristics, it is desirable to use a material having a melting point of 140 ° C. or higher, particularly 155 ° C. or higher. In addition, in order to obtain a composition excellent in moldability, mechanical properties, and heat resistance, the MFR of (B) polypropylene resin is 0.1 to 100 g / 10 min under the conditions of a temperature of 230 ° C. and a load of 2160 g. It is preferable to use it, more preferably 0.5 to 50 g / 10 minutes, still more preferably 0.5 to 10 g / 10 minutes.
The blending amount of the component (B) is 5 to 30 parts by mass in 100 parts by mass of the base polymer. If it is less than 5 parts by mass, the heat deformation characteristics of the composition are insufficient, and if it exceeds 30 parts by mass, the composition becomes extremely hard. Not only mechanical properties are degraded.

Examples of the block copolymer (C) composed of a vinyl aromatic compound and a conjugated diene compound and / or a block copolymer obtained by hydrogenating the vinyl copolymer include ABA type block copolymers. Here, A can be a polymer block mainly composed of vinyl aromatic compounds, and B can be a block mainly composed of conjugated diene compounds, both of which are hydrogenated to unsaturated double bonds based on conjugated dienes. Including.
The polymer block A mainly composed of a vinyl aromatic compound is made of only a vinyl aromatic compound, or preferably a copolymer block of 70% by mass or more of a vinyl aromatic compound and a (hydrogenated) conjugated diene compound. It is. In the block copolymer of the component (C), the content of the polymer block A is 5 to 70% by mass, preferably 20 to 50% by mass.
On the other hand, the block B mainly composed of a conjugated diene compound consists of only a (hydrogenated) conjugated diene compound, or preferably 70% by mass or more of (a hydrogenated) conjugated diene compound and a vinyl aromatic compound. It is a copolymer block.
The weight average molecular weight of the above (hydrogenated) block copolymer is preferably from 100,000 to 500,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 2 or less. The molecular structure of the (hydrogenated) block copolymer may be linear, branched, radial, or any combination thereof.
Specific examples of the above (hydrogenated) block copolymer of component (C) include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (hydrogenated SBS), SEPS (hydrogen). SIS). In the present invention, SEPS can be mentioned as a particularly preferred (hydrogenated) block copolymer of the component (C).
The blending amount of component (C) is 5 to 50 parts by mass in 100 parts by mass of the base polymer, and if it is less than 5 parts by mass, the mechanical properties and heat deformation characteristics of the composition are deteriorated. , Flame retardancy, etc. are reduced.

(D) As ethylene-acrylic acid ester copolymer rubber, there are monomer components such as ethylene and acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate, and monomers having various functional groups. A small amount copolymerized may be mentioned. In particular, methyl acrylate is used as a monomer component, and a binary copolymer with ethylene or a copolymer obtained by further copolymerizing an unsaturated hydrocarbon or vinyl acetate having a carboxyl group can be used. . Specifically, in the case of a binary copolymer, Baymac DP (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) is used. In the case of a terpolymer having a carboxyl group, Baymac G and Baymac GLS are used. In the case of a binary copolymer obtained by copolymerizing vinyl acetate (trade names, all manufactured by Mitsui & DuPont Polychemical Co., Ltd.), Denka ER5300 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) may be used. it can. Further, in the present invention, a terpolymer composed of an ethylene-acrylic acid alkyl ester-carboxyl group-containing monomer of 50% by mass or more and less than 100% by mass, an ethylene-acrylic acid alkyl ester binary copolymer, and / or A blend of ethylene-acrylic acid alkyl ester-vinyl acetate terpolymer of 50% by mass or less can also be suitably used. In this case, when both the ethylene-acrylic acid alkyl ester binary copolymer and the ethylene-acrylic acid alkyl ester-vinyl acetate ternary copolymer are used, their blending ratio is arbitrary. By adding the component (D), the flame retardancy of the molded article such as the composition and the electric wire is greatly improved.
The blending amount of the component (D) is 5 to 40 parts by mass in 100 parts by mass of the base polymer, and if it is less than 5 parts by mass, the flame retardancy of the composition is lowered. The characteristics etc. are degraded.

(E) The ethylene-propylene copolymer rubber is a rubber-like copolymer of ethylene and propylene, and the ethylene component content is desirably 85 to 40% by mass. If the ethylene component content is outside the above range, the mechanical properties of the composition may be reduced.
(E) The Mooney viscosity, ML _{1 + 4} (100 ° C.) of the ethylene-propylene copolymer rubber is preferably 10 to 100, more preferably 40 to 100, and the weight average molecular weight is in the range of 50,000 to 500,000. desirable. By adding this component (E), the moldability and mechanical properties of the composition are improved. Although the component (E) is not an essential component, it is better to add it in order to give the above effects.
The amount of component (E) is 0 to 15 parts by mass in 100 parts by mass of the base polymer.

(F) In the modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, examples of the polyolefin resin include linear polyethylene, ultra-low density polyethylene, and high density polyethylene. Examples of the unsaturated carboxylic acid or derivative thereof include maleic acid, itaconic acid, fumaric acid, and the like. Examples of the unsaturated carboxylic acid derivative include maleic acid monoester, maleic diester, maleic anhydride, itaconic acid mono Examples thereof include esters, itaconic acid diesters, itaconic anhydride, fumaric acid monoesters, fumaric acid diesters, and fumaric anhydride. The amount of modification with an unsaturated carboxylic acid or the like is about 0.1 to 5% by mass. By adding this component (F), the adhesion between the resin, rubber component and metal hydrate component becomes stronger, and the mechanical properties and heat resistance of the resulting composition are improved.
The blending amount of the component (F) is 5 to 30 parts by mass in 100 parts by mass of the base polymer, and if it is less than 5 parts by mass, there is no effect of improving mechanical properties and heat resistance. In addition, molding processability deteriorates.

(G) For a metal hydrate that has been surface-treated with a silane coupling agent, the metal hydrate before the treatment is treated with a metal hydrate that has not been surface-treated, or with an unsaturated fatty acid or saturated fatty acid. The metal hydrate that is a treated metal hydrate and subjected to surface treatment with a reactive silane coupling agent is not particularly limited, and examples thereof include magnesium hydroxide and aluminum hydroxide. For example, since aluminum hydroxide has a peak in the release of adsorbed water at about 250 ° C. and moisture is released under the temperature conditions before and after that, magnesium hydroxide is more preferable because the decomposition and dehydration temperature is higher than this. Moreover, examples of the unsaturated fatty acid used for the surface treatment include oleic acid, and examples of the saturated fatty acid include stearic acid. The average particle size of the metal hydrate is preferably 0.05 to ²⁰ μm, particularly 0.1 to 5 μm, and the specific surface area is preferably 1 to 50 m ² / g.

  Examples of the silane coupling agent used for the surface treatment of metal hydrate include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycol. Silane coupling agents having terminal vinyl groups and epoxy groups such as sidoxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, etc. Examples include silane coupling agents having a mercapto group at the end, silane coupling agents having an amino group at the end, such as aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and the like. Those having an epoxy group at the terminal is preferred. These may be used alone or in combination of two or more.

The adhesion amount of the silane coupling agent to the metal hydrate is preferably 0.1 to 30% by mass, and particularly preferably 0.2 to 2.0% by mass. Note that the surface treatment may be performed by a dry method, a wet method, or the like. In the present invention, not only a metal hydrate surface-treated with a silane coupling agent in advance is used, but also a silane coupling agent is blended with an untreated metal hydrate, and surface treatment is performed on the spot. A metal hydrate may be used. The component (G) is a metal hydrate obtained by surface-treating 50% by mass or more of the metal hydrate with a silane coupling agent, preferably 50% by mass or more, more preferably 70% by mass of the total metal hydrate. At least mass% is made to be a metal hydrate surface-treated with a silane coupling agent. When the metal hydrate treated with the silane coupling agent is not used in an amount of 50% by mass or more, the mechanical properties, heat resistance, heat deformation properties, etc. of the composition are lowered.
The blending amount of the component (G) is 100 to 300 parts by mass with respect to 100 parts by mass of the base polymer. If the amount is less than 100 parts by mass, the flame retardancy and heat deformation characteristics of the composition are inferior. When it exceeds 300 parts by mass, the mechanical properties, particularly the breaking strength and the elongation are lowered.

In addition to the above components, the non-halogen flame retardant resin composition of the present invention contains an antioxidant, a processing aid, a metal deactivator, a flame retardant aid, a filler, etc. in addition to the above components. Can do.
Here, as the antioxidant, for example, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-t-butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol-bis [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyben Le) benzene.
Examples of phosphorus antioxidants include 2,2′-methylenebis (4,6-di-t-butylphenol) octyl phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol phosphite. And bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite.
Examples of the sulfur-based antioxidant include pentaerythritol tetrakis (3-lauryl thiopropionate).
Examples of the amine-based antioxidant include 4,4 ′-(α, α-dimethylbenzyl) diphenylamine. Examples of other antioxidants include 2-mercaptobenzimidazole and its zinc salt.
As for the compounding quantity of antioxidant, 0.2-30 mass parts is desirable with respect to 100 mass parts of base polymers.

Examples of the processing aid include stearic acid, calcium stearate, zinc stearate, magnesium stearate, fatty acid amide, polyethylene wax, silicone oil and the like.
As for the compounding quantity of a processing aid, 0.2-30 mass parts is desirable with respect to 100 weight part of base polymers.

  Examples of the metal deactivator include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2 , 4-triazole and the like.

  Examples of the flame retardant aid and filler include melamine cyanurate compound, hydrotalcite, zinc stannate, zinc hydroxystannate, zinc borate, zinc oxide, tin oxide titanium oxide, magnesium oxide, molybdenum oxide, molybdenum sulfide , Carbon, clay, silica, alumina, calcium carbonate, magnesium carbonate, talc, zeolite, antimony trioxide, silicone compound, glass fiber and the like.

The non-halogen flame retardant resin composition of the present invention has a storage strength at 10 ° C or more, usually 10 to 15 MPa, elongation at break of 100% or more, usually 100 to 300%, 100 ° C. E ′ is 10 ⁷ Pa or more, usually 10 ⁷ to 10 ⁸ Pa.

  According to the present invention excellent in various characteristics by a very simple process of kneading a mixture containing the above components (A) to (G) and optionally other components in a single step in a heat-melted state. A non-crosslinked non-halogen flame retardant resin composition can be produced. Here, “non-crosslinked” in the present specification refers to a mixture containing the above-described components (A) to (G) and optionally other components, without adding a crosslinking agent such as an organic peroxide, and one-step heating. It means manufacturing in the melt-kneading process. In producing the non-crosslinked non-halogen flame retardant resin composition according to the present invention, the kneading temperature is preferably selected from the range of 120 to 250 ° C. Among them, the first half of the kneading is performed at a temperature of 120 to 170 ° C., and the second half of the kneading is performed at a temperature of 150 to 220 ° C., so that the physical properties and molding processability of the obtained non-halogen flame retardant resin composition are good. This is preferable. When kneading is performed at a temperature outside the range of 120 to 170 ° C. in the first half of the kneading, the above components (A) to (G) are not finely dispersed in the composition, and the physical properties of the obtained non-halogen flame retardant resin composition and It is not preferable because molding processability is lowered. In the present specification, the first half of kneading generally refers to the time from the start of kneading to about half of the total kneading time, and the latter is called the second half of kneading.

  The non-halogen flame-retardant resin composition of the present invention is a method conventionally used in the melt-kneading of a thermoplastic polymer, for example, a single-screw extruder or a twin-screw extruder. It is manufactured by using a melt kneader such as a Banbury mixer or various kneaders and kneading each component in a heated and melted state without adding a crosslinking agent such as an organic peroxide. Among them, from the viewpoint of temperature control at the time of kneading, a method of performing melt kneading in one step using a Banbury mixer, various kneaders, etc. is preferably adopted because it can more easily produce a non-crosslinked non-halogen flame retardant resin composition. Is done.

The non-halogen flame retardant resin composition of the present invention is molded into various molded products such as various sheets and tubes, and in particular, insulated wires, electric cables, electric cords and the like used for internal or external wiring of electric and electronic devices. Suitable for coating materials for other wiring materials. When the flame retardant resin composition is used as a coating material for a wiring material, the conductor is preferably coated around the conductor by extrusion coating. As the conductor of the wiring material, for example, a known one such as a single wire or a stranded wire of annealed copper can be used.
The wiring material (including wiring components) of the present invention can be produced by extrusion-coating the non-halogen flame retardant resin composition around a conductor using a general-purpose extrusion coating apparatus. It is desirable that the temperature of the extrusion coating apparatus at this time is about 220 ° C. at the cylinder portion and about 230 ° C. at the crosshead portion. In the wiring material of the present invention, the thickness of the coating layer formed around the conductor is usually about 0.2 to 1.0 mm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by a following example.

(Examples 1-5, Comparative Examples 1-5)
A resin composition having the composition shown in Table 1 (unit: parts by mass) was prepared, dry blended at room temperature, and then the composition was put into a pressure kneader and kneaded and discharged at 200 ° C. The discharged product was formed into a sheet with a 180 ° C. roll to prepare each sample sheet (thickness 1 mm). At that time, it was confirmed whether or not the discharged material adhered to the roll, and the roll processability was evaluated (○: discharged material did not adhere to the roll, roll workability was good, ×: the discharged material adhered to the roll. , Roll workability is poor). The results are shown in Table 2.

  Next, for each sample sheet, the hardness, breaking strength, elongation at break, breaking strength after heat aging, elongation at break, and storage elastic modulus E ′ were measured and evaluated as mechanical properties and heat resistance. . The hardness was based on the JIS K7215A type, and the strength at break and elongation at break were performed according to the method described in JIS K7113. With respect to the strength at break and elongation at break after heat aging, the strength at break and elongation at break after heat aging at 113 ° C. for 168 hours were measured, and the residual strength at break and residual elongation at break were calculated. For the storage elastic modulus E ′, using a dynamic viscoelasticity measuring device manufactured by SII, the temperature was raised from −30 to 200 ° C. at a frequency of 1 Hz and a heating rate of 3 ° C./min, and the storage elasticity at 100 ° C. The value of the rate E ′ was measured. As for the characteristics of the sample sheet, the hardness is 96A or less, the strength at break is 10.3 MPa or more, the elongation at break is 100% or more, the residual strength at break after heat aging is 70% or more, the elongation at break The remaining rate was 65% or more. The results are shown in Table 2.

Next, the insulation coating resin composition melted in advance on the conductor (conductor diameter: 0.3 mm) was extrusion-coated using an extrusion coating apparatus for manufacturing an electric wire to produce an insulated wire having an outer diameter of 10 mm.
About the obtained coating layer of the insulated wire, the vertical combustion test (VW-1), the heating deformation test, the heating bending test, and the low temperature bending test were performed, and each characteristic was evaluated. The vertical combustion test was performed based on V158-1 of UL1581, and VW-1 passed 5/5. In the heat deformation test, a heat deformation test of UL1581 was performed, and the heat characteristics were shown by the deformation ratio (%) after 1 hour at a temperature of 100 ° C. and a load of 250 gf. A value of 50% or less was accepted. In the heat bending test, an insulated wire was wound around a mandrel having a self-diameter, and a case where no crack was generated after 168 hours at 113 ° C. was passed, and a case where a crack was generated was rejected. In the low-temperature bending test, an insulated wire was wound around a mandrel having a self-diameter, and a test piece in which cracks did not occur after 1 hour at −20 ° C. was accepted and a test piece in which cracks occurred was rejected. Moreover, extrusion processability ((circle): a thing without a problem at all, x: a thing with high load and difficult actual production) was evaluated by the load of the extruder at the time of electric wire manufacture.

In Table 1, the materials used are as follows.
Component (A) / EVA (abbreviation of ethylene-vinyl acetate copolymer): EV-270, ethylene vinyl acetate copolymer component content 28% by mass, trade name, Mitsui DuPont Polychemical Co., Ltd./EEA (ethylene-acrylic acid) Abbreviation of ethyl copolymer): A714, ethylene-ethyl acrylate copolymer component content 25% by mass, trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd. EMA (abbreviation of ethylene-methyl acrylate copolymer): AC1125, Ethylene-methyl acrylate copolymer component content 25% by mass, trade name, (B) component made by Mitsui DuPont Polychemical Co., PP (polypropylene resin): J452HP, block polypropylene, melting point 163 ° C., MFR 3 g / 10 min (230 ° C. , 2160gf), trade name, manufactured by Idemitsu Petrochemical Co., Ltd. (C) component · SEPS (styrene-ethylene / propylene-styrene triblock copolymer): Septon 4055, content of styrene component 30 mass %, Product name, Kuraray Co., Ltd. (D) component, ACM-1 (acrylic rubber-1): Baymac GLS, ternary acrylic rubber, product name, Mitsui DuPont Polychemical Co., Ltd., ACM-2 (acrylic rubber-2) ): Baymac DP, binary acrylic rubber, trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd./ACM-3 (acrylic rubber-3): Denka ER5300, ternary acrylic rubber, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd. (E ) Component / EPM (Ethylene-propylene copolymer rubber): EP07P, Ethylene component content 73% by weight, Trade name, (F) Component / MAH-PO (Maleic acid modified polyolefin): XE070, Maleic acid modified by JSR Polyethylene (LLDPE), trade name, Mitsui Chemicals (G) component, Mg (OH) ₂ (metal hydrate surface-treated with a silane coupling agent): Kisuma 5L, silane coupling with vinyl group at the end Hydroxide surface-treated with chemicals Magnesium fluoride, trade name, other components and antioxidants manufactured by Kyowa Chemical Co., Ltd .: Irganox 1010, phenolic antioxidant, trade name, manufactured by Ciba Specialty Chemicals, processing aid: polyethylene wax AC-6A (lubricant) , Trade name, made by Allied Chemical

(Evaluation)
As is apparent from the results in Table 2, the non-halogen flame retardant resin compositions obtained in Examples 1 to 5 have roll processability and extrusion processability with no practical problems, and the composition Sheets and electric wires using materials have required hardness, strength at break, elongation at break, residual strength at break after heat aging and residual elongation at break, and vertical combustion test ( VW-1), a heat deformation test, a heat bending test, and a low temperature bending test are all good.
On the other hand, in Comparative Examples 1 to 5, required hardness, strength at break, elongation at break, residual strength at break and residual elongation at break after thermal aging, vertical combustion test (VW-1), There was a problem in any of the heat deformation test, the heat bending test, the low temperature bending test, the roll processability, and the extrusion processability, and an electric wire having good characteristics was not obtained.
In addition, all the compositions according to Examples 1 to 5 satisfying the above characteristics are produced as a non-crosslinked composition in a relatively simple melt-kneading process without adding a crosslinking agent such as an organic peroxide during melt-kneading. be able to.

Claims (9)

  (A) ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylate copolymer 5-50 parts by mass, (B) polypropylene resin 5-30 parts by mass, and (C) vinyl aromatic A block copolymer comprising a compound and a conjugated diene compound, and / or a block copolymer obtained by hydrogenating the block copolymer, and 5 to 50 parts by mass; (D) an ethylene-acrylate copolymer rubber of 5 to 40 parts by mass Part (E) ethylene-propylene copolymer rubber 0-15 parts by mass, and (F) base polymer 100 parts by mass comprising 5-30 parts by mass of a modified polyolefin resin modified with an unsaturated carboxylic acid or derivative thereof (G) A non-halogen flame retardant resin composition containing 100 to 300 parts by mass of a metal hydrate surface-treated with a silane coupling agent.   (A) an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylic ester copolymer is an ethylene-vinyl acetate copolymer having a vinyl acetate component content of 25 to 50% by mass, (meth) acrylic An ethylene- (meth) acrylic acid ester copolymer having an acid ester content of 10 to 30% by mass or an ethylene-vinyl acetate copolymer of 50% by mass to less than 100% by mass, and an ethylene- (meth) acrylic acid ester copolymer The non-halogen flame retardant resin composition according to claim 1, which is a blend of 50% by mass or less of a coalescence.   (D) Ethylene-acrylic acid ester copolymer rubber is a terpolymer composed of ethylene-acrylic acid alkyl ester-carboxyl group-containing monomer, and the ethylene-acrylic acid alkyl ester binary. The non-halogen flame retardant resin composition according to claim 1 or 2, comprising a copolymer and / or a blend of 50% by mass or less of an ethylene-acrylic acid alkyl ester-vinyl acetate terpolymer.   (G) In the metal hydrate surface-treated with a silane coupling agent, the silane coupling agent is a silane compound having a vinyl group and / or an epoxy group at the terminal. The non-halogen flame retardant resin composition described.   (G) In the metal hydrate surface-treated with the silane coupling agent, the metal hydrate is magnesium hydroxide, The non-halogen flame retardant resin composition according to any one of claims 1 to 4.   The non-halogen flame retardant resin composition according to any one of claims 1 to 5, which is produced by a one-step non-crosslinking melt-kneading step without adding a crosslinking agent during melt-kneading. The non-halogen flame retardant resin composition according to any one of claims 1 to 6, having a breaking strength of 10 MPa or more, an elongation at break of 100% or more, and a storage elastic modulus E 'at 100 ° C of 10 ⁷ Pa or more. Stuff.   A molded article obtained by molding the non-halogen flame retardant resin composition according to any one of claims 1 to 7. A wiring member comprising the conductor coated with the non-halogen flame retardant resin composition according to claim 1.