JP2008226850A - Flame-retardant thermoplastic elastomer resin composition and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant thermoplastic elastomer resin composition which has superior flame retardancy, tensile characteristics, and moldability, does not whiten when bent, and does not require a post-bridging step when processed into a wire, and to provide a manufacturing method for the elastomer resin composition. <P>SOLUTION: The flame-retardant thermoplastic elastomer resin composition for sheathing a wire includes (a) a (hydrogenated) block copolymer of 100 pts.wt. composed of at least two polymer blocks A mainly made of a vinyl aromatic group composition and at least one polymer block B mainly made of a conjugate diene compound, (b) a nonaromatic group rubber softening agent of 20 to 300 pts.wt., (c) a flame-retardant of 100 to 600 pts.wt. containing a metal hydroxide, (d) a peroxide-bridge olefin resin and/or a copolymer rubber containing the same of 0 to 150 pts.wt., and (e) a peroxide-decomposed olefin resin and/or a copolymer rubber containing the same of 10 to 150 pts.wt. According to a manufacturing method for the resin composition, the components (a) to (e) are kneaded all together under the presence or absence of an organic peroxide. According to another manufacturing method for the resin composition, all of the components (a) to (c), at least part of the component (D), and at least part of the composition (e) are blended together before bridging under the presence of the organic peroxide, and the rest of the components (d) and (e) are blended together after the bridging. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant thermoplastic elastomer resin composition.

  In recent years, thermoplastic elastomers that are rubber-like materials that do not require a vulcanization process and that have the same molding processability as thermoplastic resins have been used in the fields of automotive parts, home appliance parts, electric wire coverings, footwear, sundries, etc Attention has been paid. Examples of such thermoplastic elastomers include various types of polymers such as polyolefin, polyurethane, polyester, polystyrene, and polyvinyl chloride.

  Among them, polystyrene-based thermoplastic elastomers such as styrene / butadiene-block polymer (SBS), styrene / isoprene block polymer (SIS), and SIS derivatives are rich in flexibility, have good rubber elasticity at room temperature, and The thermoplastic elastomer composition obtained from these has excellent processability and is widely used as a substitute for vulcanized rubber.

  However, since these polymers have a double bond as a conjugated diene block in the molecule, there are problems in heat aging resistance (thermal stability) and weather resistance. In order to solve this, it is possible to obtain an elastomer resin composition having improved thermal stability by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene.

  Several thermoplastic elastomer resin compositions using these hydrogenated products have been proposed, and examples thereof include JP-A-50-14742 and JP-A-52-26551. As an improvement method thereof, for example, Japanese Patent Application Laid-Open No. 58-133202, Japanese Patent Application Laid-Open No. 58-145751, Japanese Patent Application Laid-Open No. 59-53548, Japanese Patent Application Laid-Open No. 62-48757, etc. A composition in which a hydrocarbon and an α-olefin polymer resin are blended with the prepared styrene-conjugated diene-block copolymer or a method for producing the same is disclosed.

  However, conventional thermoplastic elastomer resin compositions using these hydrogenated block copolymers have a problem in flame retardancy. Further, when flame retardancy is imparted, there is a problem that flexibility cannot be obtained.

  Therefore, to improve this point, a composition obtained by crosslinking a composition containing a flame retardant or a composition containing a hydrogenated derivative of such a block copolymer is crosslinked in the presence of an organic peroxide. For example, JP-A-58-98347 (PP / SEBS / crosslinking), JP-A-59-105040 (HDPE or LLDPE / SEBS / crosslinking), JP 63-172753 (PP / PE / EVA or SEBS / crosslinking).

  However, the hydrogenated block copolymer cross-linking composition disclosed in the above publication has problems of poor flexibility and difficult processing. For this reason, the present situation is that it is not satisfactory for articles that require particularly surface characteristics.

  The present invention is excellent in flame retardancy, tensile properties and molding processability, does not whiten even when bent, and does not require a post-crosslinking step when being processed into an electric wire, and is flame retardant thermoplastic conforming to JIS K6723. An object is to provide an elastomer resin composition and a method for producing the same.

The present invention
(A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them 100 parts by weight of the block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide,
(D) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide-decomposable olefin resin and / or copolymer rubber 10 containing the same. Provided is a flame retardant thermoplastic elastomer resin composition for covering an electric wire, comprising ~ 150 parts by weight.

The present invention further includes
(A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them. 100 parts by weight of a block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide,
(D) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide-decomposable olefin resin and / or copolymer rubber 10 containing the same. It is a manufacturing method of the flame-retardant thermoplastic elastomer resin composition for electric wire coating | cover containing -150 weight part, Comprising: The whole quantity of a component (a), a component (b) and a component (c), and a component (e) At least a portion, and if there is component (d), at least a portion of component (d) is crosslinked by heat treatment in the presence of an organic peroxide, and then the remainder of the crosslinked product and component (e), In addition, the present invention provides a method for producing a flame-retardant thermoplastic elastomer resin composition for covering an electric wire, wherein if there is a remainder of component (d), the remainder of component (d) is blended and melt-kneaded.

The present invention also provides
(A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them. 100 parts by weight of a block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide, (d) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide. A method for producing a flame retardant thermoplastic elastomer resin composition for wire coating, comprising 10 to 150 parts by weight of a decomposable olefin resin and / or copolymer rubber containing the same, comprising: component (a), component ( b), the total amount of component (c) and component (e), and if there is component (d), the total amount of component (d) is melt-kneaded all at once, and the flame retardancy for covering wires A method for producing a thermoplastic elastomer resin composition is provided. In this method, melt-kneading can be performed in the presence of an organic peroxide and a crosslinking aid to obtain a crosslinked product.

  Each component in the composition of the present invention will be described.

Component (a): Essential component The block copolymer is mainly made from a vinyl aromatic compound (hereinafter, may be mainly composed of a vinyl aromatic compound), and at least two polymer blocks A and a conjugated diene compound A block copolymer consisting of at least one polymer block B or a mixture obtained by hydrogenation thereof, or a mixture thereof (hereinafter sometimes referred to mainly as a conjugated diene compound) It is. For example, a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA or the like, or hydrogenating this What can be obtained can be mentioned. This block copolymer and / or hydrogenated block copolymer (hereinafter, the block copolymer and / or hydrogenated block copolymer may be referred to as a (hydrogenated) block copolymer) as a whole, The vinyl aromatic compound is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight. The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block composed solely of a vinyl aromatic compound or more than 50% by weight, preferably 70% by weight or more of optional components such as conjugates. From diene compounds and / or (hydrogenated) conjugated diene compounds (hereinafter, conjugated diene compounds and / or hydrogenated conjugated diene compounds may be referred to as (hydrogenated) conjugated diene compounds) It is a copolymer block to be made. The polymer block B mainly composed of a conjugated diene compound is a homopolymer block consisting only of (hydrogenated) conjugated diene compound, or more than 50% by weight of conjugated diene compound, preferably 70% by weight or more. A copolymer block made from components such as vinyl aromatic compounds. In addition, the polymer block A mainly composed of these vinyl aromatic compounds or the polymer block B mainly composed of conjugated diene compounds is derived from (hydrogenated) conjugated diene compounds or vinyl aromatic compounds in the molecular chain. The unit distribution may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of vinyl aromatic compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  As the vinyl aromatic compound that can be used, one or more kinds can be selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is preferable. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.

  In the polymer block B mainly composed of the conjugated diene compound, the microstructure can be arbitrarily selected. For example, in the polybutadiene block, the 1,2-microstructure is 20 to 50% by weight, preferably 25 to 45% by weight. It is preferable that at least 90% of the aliphatic double bonds derived from butadiene are hydrogenated. In the polyisoprene block, 70 to 100% by weight of isoprene has a 1,4-microstructure, and at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated.

  The weight average molecular weight of the (hydrogenated) block copolymer is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 100,000 to 550,000, particularly Preferably it is the range of 100,000-400,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less.

  The molecular structure of the (hydrogenated) block copolymer may be linear, branched, radial, or any combination thereof.

  Many methods for producing these block copolymers have been proposed. As typical methods, for example, a lithium catalyst or a Ziegler-type catalyst is prepared by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium. Any known method can be used for hydrogenation. For example, a hydrogenated block copolymer can be obtained by hydrogenating the block copolymer obtained by the above method in the presence of a hydrogenation catalyst in an inert solvent.

  Specific examples of the (hydrogenated) block copolymer include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (hydrogenated SBS), SEPS (hydrogenated SIS) and the like. be able to. In the present invention, a particularly preferred (hydrogenated) block copolymer includes a polymer block A mainly composed of styrene, isoprene mainly and 70 to 100% by weight of isoprene has a 1,4-microstructure, A hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and comprising a polymer block B in which at least 90% of the aliphatic double bonds based on the isoprene are hydrogenated. More preferably, 90 to 100% by weight of isoprene is the hydrogenated block copolymer having a 1,4-microstructure.

Component (b): Essential component Non-aromatic rubber softeners include non-aromatic mineral oils or liquid or low molecular weight synthetic softeners. The mineral oil softener generally used for rubber is a mixture of aromatic rings, naphthene rings, and paraffin chains, and the number of carbon atoms in the paraffin chain accounts for 50% or more of the total carbon number. Are classified as paraffinic, those having 30 to 40% of naphthenic ring carbon are called naphthenic, and those having 30% or more of aromatic carbon are called aromatic.

  The mineral oil rubber softeners used as component (b) of the present invention are paraffinic and naphthenic in the above categories. Aromatic softeners are not preferred because the component (a) becomes soluble by use of the aromatic softener, inhibits the crosslinking reaction, and cannot improve the physical properties of the resulting composition. In particular, the component (b) of the present invention is preferably a paraffin-based one, and a paraffin-based one having a small aromatic ring component is particularly suitable.

  These non-aromatic rubber softeners have a dynamic viscosity at 37.8 ° C of 20 to 500 cst, a pour point of -10 to -15 ° C, and a flash point (COC) of 170 to 300 ° C. Is preferred. Moreover, a thing with a weight average molecular weight of 100-2,000 is preferable.

  The amount of component (b) is 20 parts by weight or more, preferably 40 parts by weight or more, more preferably 80 parts by weight or more, particularly preferably 100 parts by weight or more, with respect to 100 parts by weight of component (a). 300 parts by weight or less, preferably 200 parts by weight or less, more preferably 170 parts by weight or less. If the amount exceeds 300 parts by weight, the softening agent is likely to be bled out, and the final product may become sticky, and the mechanical properties are also lowered. Moreover, if it is less than 40 weight part, the softness | flexibility of the composition obtained will be lost.

Component (c): Essential component Examples of the flame retardant used in the present invention include a phosphorus flame retardant, a halogen flame retardant, and an inorganic flame retardant.

Examples of phosphorus flame retardants include the following compounds:
Non-halogen phosphates such as aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate;
Halogen-containing phosphates such as tris (halopropyl) phosphate, tris (haloethyl) phosphate;
Inorganic phosphates such as ammonium polyphosphate;
Nitrogen-containing phosphorus compounds such as chlorinated phosphonitrile derivatives;
Polymerizable phosphorus compounds such as vinyl phosphonates, allyl phosphonates; and red phosphorus flame retardants coated on red phosphorus and red phosphorus surfaces.

  Halogen flame retardants include chlorine and bromine. Examples of chlorine include chlorinated paraffin and chlorinated polyethylene perchloropentacyclodecane. Examples of bromine include hexabromobenzene and decabromodiphenyl oxide. , Tetrabromobisphenol A, and hexabromocyclododecane.

  Inorganic flame retardants include halogen-containing and non-halogen-based. Examples of the halogen-containing system include ammonium bromide. Examples of non-halogen compounds include metal compounds such as metal oxides, metal hydroxides, and metal salts. For example, antimony trioxide, barium metamonate, zirconium oxide, aluminum hydroxide, magnesium hydroxide, dosonite, calcium aluminate, dihydrated gypsum, calcium hydroxide, zinc borate, barium metaborate, borax, kaolin clay , Calcium carbonate, molybdenum compound, ammonium aluminum hydroxycarbonate, ferrocene, tin compound and the like.

  In addition to the flame retardant described above, the addition of a silicone compound improves the flame retardancy. Examples of the silicone compound include silicone oil, silicone rubber, and silicone resin. Silicone oil, silicone resin, or resin copolymerized with silicone is preferably used in combination with the flame retardant.

  Moreover, when using ammonium polyphosphate as a flame retardant, a flame retardant effect will improve if a nitrogen-containing compound is used together. Examples of such nitrogen-containing compounds include triazine derivatives, tris (2-bidoxyethyl) isocyanurate, tris (2,3-epoxypropyl) isocyanurate, pentaerythritol, melamine cyanurate, benzoguanamine, melamine phosphate, and melamine. It is done. A structure containing oxygen is particularly preferable.

  The above flame retardants may be used alone or in combination.

  As the component (c), a combination of metal hydroxide and red phosphorus or ammonium polyphosphate combined with a nitrogen-containing compound is preferable.

  The amount of component (c) is 95 parts by weight or more, preferably 100 parts by weight or more, and 600 parts by weight or less, preferably 500 parts by weight or less based on 100 parts by weight of component (a). If the amount exceeds 600 parts by weight, the resulting composition becomes hard and the properties as an elastomer cannot be obtained. Moreover, if it is less than 95 weight part, the flame retardance performance of the obtained composition is not recognized.

Component (d): Optional component The peroxide cross-linked olefin resin and / or copolymer rubber containing the same in the present invention undergoes a cross-linking reaction mainly by heat treatment in the presence of peroxide, and its fluidity. Use the one that decreases. Examples of the olefin resin include high-density polyethylene (low-pressure polyethylene), low-density polyethylene (high-pressure polyethylene), linear low-density polyethylene (ethylene and a small amount, preferably 1 to 10 mol% of butene-1, hexene-1). , Copolymers with α-olefins such as octene-1), polyethylene having a polymer density in the range of 0.88 to 0.94 g / cm ³ , such as ultra-low density polyethylene, or ethylene / propylene copolymer rubber, An elastic body of an indefinite random copolymer mainly composed of olefin, such as ethylene / propylene / non-conjugated diene copolymer rubber. Among these, polyethylene or ethylene / propylene copolymer rubber is preferable, and among them, linear low density polyethylene is particularly preferable in that an appropriate cross-linked structure can be obtained.
For example, when the component (d) is rubber, the Mooney viscosity and ML _{L1 + 4} (100 ° C.) are preferably 10 to 120, more preferably 40 to 100. When one having a Mooney viscosity of less than 10 is used, the rubber properties of the resulting elastomer composition tend to be inferior. Further, if a material exceeding 120 is used, the molding processability deteriorates, and in particular, the appearance of the molded product tends to deteriorate. The ethylene content in the copolymer is suitably 5 to 50% by weight. Preferably it is 6-20 weight%, More preferably, it is 10-15 weight%. When the ethylene content is less than 5% by weight, the flexibility of the resulting elastomer composition is insufficient, and when it is more than 50% by weight, the mechanical strength tends to decrease.

  The weight average of the peroxide cross-linked olefin resin and / or copolymer rubber containing the same used is preferably in the range of 50,000 to 1,000,000, more preferably 70,000 to 500,000. When a peroxide cross-linked olefin resin having a weight average molecular weight of less than 50,000 and / or a copolymer rubber containing the same is used, the resulting elastomer composition tends to have inferior rubber properties. In addition, if a polymer having a weight average molecular weight exceeding 1,000,000 is used, molding processability is deteriorated, and in particular, the appearance of the molded product tends to be deteriorated.

  When component (d) is used, it is used in an amount of 150 parts by weight or less, preferably 100 parts by weight or less, based on 100 parts by weight of component (a). When the amount of component (d) exceeds 150 parts by weight, the flexibility of the resulting elastomer composition is lowered and the molding processability is also deteriorated. Although the lower limit in the case of using is not specifically limited, Usually, it is 5 weight part or more. A preferred blending amount is 30 to 100 parts by weight.

Component (e): Essential component The compounding of the peroxide-decomposable olefin resin and / or copolymer rubber containing the same has the effect of improving the rubber dispersion of the resulting composition and improving the appearance of the molded product. Have.

The peroxide-decomposable olefin resin suitable as the component (e) of the present invention has a rrrr / l-mmmm of 20% or more in the pentad fraction by ¹³ C-nuclear magnetic resonance absorption method, and a differential scanning calorimetry method. The melting peak temperature (Tm) determined by (DSC) is 150 ° C. or higher and the melting enthalpy (ΔHm) is 100 J / g or lower. Preferably, Tm is in the range of 150 ° C. to 167 ° C. and ΔHm is in the range of 25 mJ / mg to 83 mJ / mg. The degree of crystallinity can be estimated from Tm and ΔHm. When Tm and ΔHm are outside the above ranges, rubber elasticity at 100 ° C. or higher of the resulting elastomer composition is hardly improved.

Examples of the peroxide-decomposable olefin resin and / or copolymer rubber containing the same include the following.
(1) Isotactic polypropylene or a copolymer of propylene and other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like. The MFR (ASTM-D-1238, L condition, 230 ° C.) of this resin can be 0.1 to 800 g / 10 min. In particular, when used for electric wire applications, it is preferably 0.1 to 10 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes, and still more preferably 0.1 to 3 g / 10 minutes.
(2) Well-flowing block, random, homotype polypropylene, such as isotactic polypropylene, or propylene and other small amounts of α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, etc. And a copolymer. The MFR of this resin is preferably 5 to 200 g / 10 minutes, more preferably 8 to 150 g / 10 minutes, and still more preferably 10 to 100 g / 10 minutes.

  The above (1) is suitable for blending before heat treatment (before crosslinking) in the presence of an organic peroxide when the resin composition of the present invention is produced as a crosslinked product, (2) It is suitable for blending after heat treatment (after crosslinking) in the presence of organic peroxide. Preferably, as the component (e), a resin selected from the above (1) and a resin selected from the above (2) are used in combination, and before and after the heat treatment in the presence of the organic peroxide, respectively. Blend.

  When blended before the heat treatment in the presence of an organic peroxide, that is, before the crosslinking reaction, if the MFR of the peroxide-decomposable olefin resin is less than 0.1 g / 10 minutes, the moldability of the resulting elastomer is lowered, If the MFR exceeds 10 g / 10 min, the rubber elasticity of the resulting elastomer composition deteriorates, which is not preferable.

  On the other hand, when blended after heat treatment in the presence of an organic peroxide, that is, after a crosslinking reaction, if the MFR of the peroxide-decomposable olefin resin is less than 5 g / 10 min, the moldability of the resulting elastomer is lowered, and the MFR Is more than 200 g / 10 minutes, the rubber elasticity of the resulting elastomer composition deteriorates, which is not preferable.

  In addition to the above, as the component (e), the number average molecular weight (Mn) is 25,000 or more, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 7 or less. A peroxide-decomposable olefin resin comprising a boiling heptane-soluble polypropylene and a boiling heptane-insoluble polypropylene having a melt index of 0.1 to 4 g / 10 min; a boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more; A peroxide-decomposable olefin resin comprising boiling heptane-insoluble polypropylene having an intrinsic viscosity [η] of 0.5 to 9.0 dl / g can also be used.

  Component (e) is 10 parts by weight or more, preferably 20 parts by weight or more, more preferably 25 parts by weight or more, and 150 parts by weight or less, preferably 100 parts by weight or less, relative to 100 parts by weight of component (a). More preferably, it is used in an amount of 80 parts by weight or less. If the amount is less than 10 parts by weight, the moldability deteriorates. If the amount exceeds 150 parts by weight, the resulting elastomer composition has too high hardness and loses flexibility, and a rubber-like product cannot be obtained.

Component (f): Optional component An inorganic filler can be blended as required. In addition to the effect of improving some physical properties such as compression set of molded articles, the inorganic filler has an economic advantage due to an increase in the amount. Any inorganic filler commonly used in the field can be used, such as calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, carbon black, etc. Can be mentioned. Of these, calcium carbonate or talc is particularly preferred.

  When component (f) is used, it is used in an amount of 150 parts by weight or less, preferably 100 parts by weight or less, based on 100 parts by weight of component (a). When the amount exceeds 150 parts by weight, the mechanical strength of the resulting elastomer composition is remarkably lowered, the hardness is increased, the flexibility is lost, and a rubber-like product cannot be obtained. Moreover, the lower limit in the case of using is although it does not specifically limit, Usually, it is 5 weight part or more.

  The resin composition of the present invention can be a crosslinked product or a non-crosslinked product.

  The resin composition of the present invention may contain a residue thereof when an organic peroxide and a crosslinking aid are used in the production stage.

  In addition to the above components, the composition of the present invention may be a polymer or copolymer (for example, a polyester polymer or copolymer, a polyurethane polymer or copolymer, a polyamide polymer or copolymer, depending on the application). And a polymethylpentene polymer or copolymer may be used, but there is no particular limitation). In addition to these, it is also possible to contain various anti-blocking agents, sealability improvers, heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, crystal nucleating agents, colorants and the like.

  Next, a method for producing the above-described composition of the present invention will be described. The manufacturing method is not particularly limited. Any conventional melt-kneading technique and apparatus (single- or twin-screw extruder, roll, Banbury mixer, various kneaders, etc.) can be used.

  As a kneading method, it is preferable to use a twin screw extruder or Banbury mixer having an L / D of 47 or more because all the steps can be performed continuously. Further, for example, when kneading with a twin screw extruder, if the number of revolutions of the screw is 80 to 250 rpm, preferably 80 to 100 rpm, each component can be dispersed well and the physical properties can be obtained. it can.

  The example of the manufacturing method of the composition of this invention is described below.

Manufacturing method 1 (Batch kneading)
The total amount of component (a), component (b), component (c) and component (e), and, if component (d), the total amount of component (d), and optionally an organic peroxide and a crosslinking aid, In some cases, various additives such as an antioxidant, a light stabilizer, a colorant, and the component (f) are further melt-kneaded together. The kneading temperature is preferably 160 to 240 ° C. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, etc. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders are used. By this step, a composition in which each component is uniformly dispersed can be obtained.
In this production method, when an organic peroxide and a crosslinking aid are used, a crosslinked resin composition is obtained, and when not used, a non-crosslinked resin composition is obtained.

  Examples of the organic peroxide usable in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2, 5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate Tert-butyl peroxyisopropyl carbonate, Examples thereof include diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

  Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of odor, colorability, and scorch stability. (Tert-Butylperoxy) hexyne-3 is most preferred.

  The amount of peroxide added is preferably in the range of 0.1 to 3.0 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the total of components (a) to (f) when the peroxide is added. The amount is 2.5 parts by weight, particularly preferably 1.0 to 2.5 parts by weight. If it is less than 0.1 part by weight, it is difficult to obtain the required crosslinking. When the amount exceeds 3.0 parts by weight, the crosslinking proceeds too much, and the dispersion of the crosslinked product becomes worse.

  The crosslinking aid can be blended during the partial crosslinking treatment with an organic peroxide, and a monomer having an ethylenically unsaturated group is preferred. For example, polyfunctional vinyl monomers such as divinylbenzene, triallyl cyanurate, or polyfunctional vinyl monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate. Mention may be made of functional methacrylate monomers. By such a compound, a uniform and efficient crosslinking reaction can be expected.

  In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has a good compatibility with the peroxide-crosslinked olefin polymer rubber (d), and has a peroxide solubilizing action. It is most preferable because it provides a crosslinked thermoplastic elastomer having a balance between hardness and rubber elasticity, which acts as a dispersing aid for peroxide and has a uniform and effective crosslinking effect by heat treatment.

  The amount of the crosslinking aid used in the present invention is preferably in the range of 0.1 to 10 parts by weight, more preferably 1.10 parts by weight with respect to 100 parts by weight of the total of components (a) to (f) at the time of addition. 0 to 8.0 parts by weight, particularly preferably 2.0 to 6.0 parts by weight. The addition amount of the crosslinking aid is preferably an amount that is about 2 to 2.5 times the addition amount of the peroxide. If the amount is less than 0.1 parts by weight, it is difficult to obtain the required crosslinking, and if the amount exceeds 10 parts by weight, the crosslinking proceeds too much, and the dispersion of the crosslinked product tends to deteriorate.

  Antioxidants that are optionally used include, for example, 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like, phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are preferred.

  The addition amount of the antioxidant is preferably in the range of 3.0 parts by weight or less, more preferably 1.0 part by weight or less, with respect to 100 parts by weight of the total of components (a) to (f) at the time of addition. .

Production method 2 (crosslinking reaction)
In the first step, first, the total amount of component (a), component (b) and component (c), and at least part of component (e), and at least part of component (d) if there is component (d) In some cases, various additives such as an antioxidant, a light stabilizer, a colorant and the component (f) are further melt-kneaded in advance. The kneading temperature is preferably 160 to 240 ° C. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, etc. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders are used. By this step, a composition in which each component is uniformly dispersed can be obtained.

  In the second step, a peroxide and, if desired, a crosslinking aid are added to the composition obtained in the first step, and further kneaded under heating to cause crosslinking. The temperature at this time is preferably 180 to 240 ° C. Thus, it is particularly preferable that the components (a) to (e) are melt-kneaded in advance to cause micro dispersion, and then an organic peroxide is added to cause crosslinking, thereby causing particularly preferable physical properties. This step can be generally performed by a kneading method using a twin screw extruder, a Banbury mixer, or the like.

  About the said 1st and 2nd process, it is set as a single process, and it is also possible to mix and knead | mix each component.

  In the third step, the remaining amount of each component is added to the crosslinked composition obtained in the second step and kneaded. The kneading temperature is preferably 180 to 240 ° C. The kneading can be generally performed using a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders. In this step, the dispersion of each component further proceeds and at the same time the reaction is completed.

Production method 3 (Crosslinking reaction)
In the first step, first, the total amount of component (a) and component (b), at least part of component (c), and at least part of component (e), and component (d) if present In some cases, various additives such as an antioxidant, a light stabilizer and a colorant and component (f) are previously melt-kneaded. The kneading temperature is preferably 160 to 240 ° C. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, etc. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders are used. By this step, a composition in which each component is uniformly dispersed can be obtained.

  In the second step, a peroxide and, if desired, a crosslinking aid are added to the composition obtained in the first step, and further kneaded under heating to cause crosslinking. The temperature at this time is preferably 180 to 240 ° C. Thus, it is particularly preferable that the components (a) to (e) are melt-kneaded in advance to cause micro dispersion, and then an organic peroxide is added to cause crosslinking, thereby causing particularly preferable physical properties. This step can be generally performed by a kneading method using a twin screw extruder, a Banbury mixer, or the like. About the said 1st and 2nd process, it is set as a single process, and it is also possible to mix and knead | mix each component.

  In the third step, the remaining amount of each component is added to the crosslinked composition obtained in the second step and kneaded. The kneading temperature is preferably 180 to 240 ° C. The kneading can be generally performed using a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders. In this step, the dispersion of each component further proceeds and at the same time, the reaction is completed.

Production Method 4 (Crosslinking Reaction)
In the first step, first, the total amount of component (a) and component (b), and at least a part of component (e), and at least a part of component (d) if there is component (d), optionally further Various additives such as an antioxidant, a light stabilizer, a colorant and the component (f) are melt kneaded in advance. The kneading temperature is preferably 160 to 240 ° C. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, etc. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders are used. By this step, a composition in which each component is uniformly dispersed can be obtained.

  In the second step, an organic peroxide, a crosslinking aid, and the like are added to the composition obtained in the first step as desired, and further kneaded under heating to cause crosslinking. The temperature at this time is preferably 180 to 240 ° C. In this way, components (a), (b) and component (e), and optionally (d) are preliminarily melt-kneaded to produce micro dispersion, and then organic peroxide is added to cause crosslinking. Particularly favorable physical properties are brought about. This step can be generally performed by a kneading method using a twin screw extruder, a Banbury mixer, or the like. About the said 1st and 2nd process, it is set as a single process, and it is also possible to mix and knead | mix each component.

  In the third step, the total amount of component (c) and the remaining amount of other components are added to the crosslinked composition obtained in the second step and kneaded. The kneading temperature is preferably 180 to 240 ° C. The kneading can be generally performed using a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders. In this step, the dispersion of each component further proceeds and at the same time the reaction is completed.

  In the above-described production methods 2 to 4, the composition to be produced is a crosslinked product. The method for producing such a crosslinked product is preferably carried out as follows.

  In the case of blending a thermoplastic polyester elastomer, the antioxidant is preferably added in the first step in order to prevent hydrolysis.

  In the first step, the kneading temperature is desirably set so that each component is completely melted and easily mixed. In the second step, it is desirable to set the temperature so that a shearing force is applied to the organic peroxide and each component and the reaction proceeds uniformly. In the third step, it is desirable to set the temperature so that the reaction is completed simultaneously with the mixing of the components.

  Component (a) must be blended in the first step or the second step at the latest. Thereby, a part of component (a) produces a crosslinking reaction, and as a result, the effect that the dispersibility of each component becomes favorable arises.

  The component (b) is preferably blended in the first step. Component (b) can be blended in the third step (after heat treatment in the presence of organic peroxide), but blending in the third step is not preferable because it causes bleeding out.

  Component (c) can be blended in the first step in the first step (the production method 2), but an appropriate amount is blended in the first step for the purpose of adjusting processing characteristics, fluidity, mechanical strength, dispersibility, and the like. The remaining amount can be blended in the second or third step (the above production method 3). Moreover, when a component (c) and an organic peroxide react, it is preferable to mix | blend whole quantity by the 3rd process (the said manufacturing method 4).

  When component (d) is used, the entire amount can be blended in the first step, but an appropriate amount is blended in the first step for the purpose of adjusting processing characteristics, fluidity, mechanical strength, etc. It can also be blended in the second or third step. In the latter case, the composition obtained by partially crosslinking in the presence of the organic peroxide and a part of the component (d) blended in the second or third step are compatible with each other and microdispersed in the composition. This is preferable because it has an effect of improving physical properties such as mechanical strength of the composition. In particular, it is preferable to blend an appropriate amount in the first step and the remaining amount in the third step. Preferably at least half of the amount of component (d) used, in particular 3 parts by weight or more, is blended (in the first or second step) before the heat treatment in the presence of peroxide. The remainder is blended after the heat treatment (in the third step), whereby various physical properties can be adjusted as described later.

  Component (e) is preferably blended in an appropriate amount in the first step and the remaining amount in the third step. Thereby, a partially crosslinked composition in the presence of an organic peroxide and a part of the component (e) blended in the third step are compatible and microdispersed in the composition, and the processing characteristics of the resulting elastomer composition, It has the effect of improving physical properties such as fluidity and mechanical strength. At least a portion, preferably at least 3 parts by weight of component (e) is subjected to a heat treatment in the presence of an organic peroxide (ie formulated before or during heat treatment) and the remainder of component (e), preferably at least It is desirable that 3 parts by weight, more preferably at least 5 parts by weight are blended after the heat treatment. By adding component (e) in this way, each component is uniformly dispersed, so that there is no stickiness on the surface of the molded product and moldability is improved. Since the ratio of the amount (X) to be blended before the crosslinking reaction of the component (e) and the amount (Y) to be blended after the crosslinking reaction is X <Y, a resin having superior rubber elasticity can be obtained. preferable. The addition ratios X and Y can be determined by respective final molding methods such as injection molding and extrusion molding.

  When using a component (f), it can mix | blend in any one of a 1st process and a 3rd process, or both processes.

The degree of crosslinking of the flame retardant thermoplastic elastomer composition obtained by crosslinking in this way can be represented by a gel fraction and a dynamic elastic modulus. The gel fraction can be expressed as the ratio of the weight of the residual solid to 1 g of the sample after 1 g of the sample is wrapped in a 100 mesh wire net and extracted in boiling xylene using a Soxhlet extractor for 10 hours. The dynamic elastic modulus can be expressed by a storage elastic modulus of melt viscoelasticity using a parallel plate. In the present invention, the preferable degree of crosslinking is 30 to 45% by weight, particularly 35 to 45% by weight in gel fraction, and 10 ⁵ to 10 ⁷ Pa in storage elastic modulus. Below this range, the resulting flame retardant thermoplastic elastomer composition has poor high temperature compression set and oil resistance. If this range is exceeded, the moldability deteriorates and the tensile properties deteriorate.

  The flame-retardant thermoplastic elastomer composition obtained in this way is more uniformly microdispersed than the components obtained by the prior art, so compression set, tensile strength, flame-retardant effect The composition is stable and has good physical properties.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to this.

The evaluation methods used in Examples and Comparative Examples were as follows.
1) Hardness In accordance with JIS K 6301 or JIS K 6050, a 6.3 mm thick press sheet was used as a test piece. The hardness after 15 seconds was measured.
2) Tensile strength In accordance with JIS K 6301, a 1 mm thick press sheet was used as a test piece by punching it into a No. 3 type with a dumbbell. The tensile speed was 500 mm / min.
3) Tensile elongation In accordance with JIS K 6301, the test piece was a 1 mm thick press sheet punched into a No. 3 shape with a dumbbell. The tensile speed was 500 mm / min.
4) 100% modulus In accordance with JIS K 6301, the test piece was a 1 mm thick press sheet punched into No. 3 with a dumbbell and used. The tensile speed was 500 mm / min.
5) Oil resistance In accordance with JIS K 6301, a 1 mm-thick press sheet was used as a test piece by punching it into a No. 3 type with a dumbbell. Using ASTM No. 2 oil, the tensile strength residual ratio and elongation residual ratio at 70 ° C. for 4 hours were measured. The case of 85% or more was marked with ◎, the case of 75% or more and less than 85% was marked with ○, the case of 60% or more and less than 75% was marked with Δ, and the case of less than 60% was marked with ×.
6) Extrudability In a single-screw extruder, when extrusion is performed under conditions of a temperature of 180 ° C. and a rotation speed of 30 rpm, there is no delamination or deformation, and there is no fish eye or undulation that significantly deteriorates the appearance. The case where there was little drawdown and the shape retention property was good was marked with ◎.
7) Heat deformation The heat denaturation rate was measured according to JIS K 6723.
8) Cold resistance Measured according to JIS K 6723.
9) Volume resistivity Measured according to JIS K 6723.
10) Oxygen index It measured based on JISK7201.
11) Generation | occurrence | production of corrosive gas It measured based on JCS (Japan Electric Wire Industry Standard) C53.
12) Dielectric constant and dielectric loss tangent Measured according to JIS K 6760.

As each component, the following were used.
Component (a): Hydrogenated block copolymer, Kuraray Co., Ltd., Septon 4077 (styrene content: 30% by weight, isoprene content: 70% by weight, microstructure: 1,4-microstructure, number average molecular weight: 260,000, weight average molecular weight: 320,000, molecular weight distribution: 1.23, hydrogenation rate: 90% or more)
Component (b): Non-aromatic rubber softener Diana Process Oil PW-90 (Type: Paraffinic oil, Weight average molecular weight: 540, Aromatic component content: 0.1% or less), Idemitsu Kosan Co., Ltd. (C): Flame retardant (c-1) Kisuma 5A (magnesium hydroxide), manufactured by Kyowa Chemical Industry Co., Ltd. (c-2) SAYTEX 102 (halogen: decabromodiphenyl oxide, bromine content: 83%, melting point: 304- 309 ° C., decomposition temperature: 350 ° C., ethyl (c-3) antimony trioxide, Mikuni Seiki Co., Ltd. (c-4) no backwell ST100 (type: red phosphorus), phosphorus chemical industry (c- 5) Hostafram AP462 (ammonium polyphosphate, outer shell: melamine / formaldehyde resin, inside: ammonium polyphosphate), manufactured by Clariant Japan (c-6) (Tris (2-hydroxyethyl) isocyanurate), Nissan Chemical Co., Ltd. (c-7) BY27-001 (propylene / silicone graft copolymer, silicone component 50%), Toray Dow Silicone Co., Ltd. component (d) : Peroxide-crosslinked olefin resin (d-1) Engagement EG8150 (ethylene-octene copolymer, density: 0.868 g / cm ³ , melt index (measurement temperature 190 ° C., measurement load 2.16 kg): 0.5 g / 10 minutes), Dow Chemical Japan (d-2) CA3002 (linear low density polyethylene, density: 0.925 g / cm ³ , melt index (measurement temperature 190 ° C., measurement load 2.16 kg): 2 5 g / 10 min), Sumitomo Chemical Co., Ltd. component (e): peroxide-decomposable olefin resin (e-1) CJ700 Polypropylene homopolymer, crystallinity: Tm 166 ° C., ΔHm 82 mJ / mg, melt index (measuring temperature 230 ° C., measuring load 2.16 kg): 8 g / 10 min), Mitsui Chemicals (e-2) PN610 (Polypropylene, density 0.9 g / cm ³ , melt index (measuring temperature 230 ° C., measuring load 2.16 kg): 0.5 g / 10 min), Toxo Corporation component (f): inorganic filler NS400 (calcium carbonate) JA13R (talc) manufactured by Nitto Flour Chemical Co., Ltd. Satinton SP-33 (calcined clay) manufactured by Asada Milling Co., Ltd. Organic peroxide manufactured by Tsuchiya Kaolin Kogyo Co., Ltd .:
Perhexa 25B (2,5-dimethyl-2,5-di (t-butylperoxy) -hexane) manufactured by NOF Corporation
Crosslinking aid:
Shin Nakamura Chemical Co., Ltd., NK ester 3G (triethylene glycol dimethacrylate)
Other:
DOP (di-2-ethylhexyl phthalate, plasticizer), Mitsubishi Chemical Corporation SH200 1000CS (silicone oil, viscosity 1000 CS), Toray Dow Corning DC4-7081 (silicone resin powder), Toray Dow Corning P-1300 (Polyvinyl chloride resin, average polymerization degree 1300), Shin-Etsu Chemical Co., Ltd. EEA A710 (ethylene / ethyl acrylate copolymer), Mitsui / DuPont.

Examples 1 to 5 (Crosslinking reaction)
The composition was manufactured in three stages. First, the total amount of each component other than the component (e) shown in Table 1 and 20 parts by weight of the component (e) were melt-kneaded (first step), and then the organic peroxide and A crosslinking aid was added and melt-kneaded (second step), and the remainder of component (e) was added from the middle of the extruder and melt-kneaded (third step). Using a twin screw extruder (L / D = 47), melt kneading was performed at a screw rotation speed of 100 rpm, and the melt kneading temperature of each step was as follows: First step: 230 to 240 ° C., 2nd process: 180-240 degreeC, 3rd process: 200-220 degreeC.

About the obtained resin composition, the above-mentioned test was done and the result is shown in Table 1.
Comparative Example 1 (Non-crosslinking reaction)
The components shown in Table 1 were kneaded together to produce a composition. Using a twin screw extruder (L / D = 47), melt kneading was performed under the conditions of a screw rotation speed of 100 rpm and a melt kneading temperature of 180 to 240 ° C. About the obtained resin composition, the above-mentioned test was done and the result is shown in Table 1.

Comparative Examples 2-3 (Crosslinking reaction)
The composition was manufactured in three stages. First, the total amount of each component other than the component (e) shown in Table 1 and 20 parts by weight of the component (e) were melt-kneaded (first step), and then the organic peroxide and A crosslinking aid was added and melt-kneaded (second step), and the remainder of component (e) was added from the middle of the extruder and melt-kneaded (third step). Using a twin screw extruder (L / D = 47), melt kneading was performed at a screw rotation speed of 100 rpm, and the melt kneading temperature of each step was as follows: First step: 230 to 240 ° C., 2nd process: 180-240 degreeC, 3rd process: 200-220 degreeC.
About the obtained resin composition, the above-mentioned test was done and the result is shown in Table 1.

Comparative Example 4 (Non-crosslinking reaction)
The components shown in Table 1 were kneaded together to produce a composition. Using an 8-inch open roll, the mixture was kneaded at a kneading temperature of 170 ° C. for 5 minutes.
About the obtained resin composition, the above-mentioned test was done and the result is shown in Table 1.

Reference Examples 1-2 and Comparative Example 5 (Crosslinking reaction)
The composition was manufactured in three stages. First, the total amount of each component other than the component (e) shown in Table 2 and 20 parts by weight of the component (e) were melt-kneaded (first step), and then the organic peroxide and A crosslinking aid was added and melt-kneaded (second step), and the remainder of component (e) was added from the middle of the extruder and melt-kneaded (third step). Using a twin screw extruder (L / D = 47), melt kneading was performed at a screw rotation speed of 100 rpm, and the melt kneading temperature of each step was as follows: First step: 230 to 240 ° C., 2nd process: 180-240 degreeC, 3rd process: 200-220 degreeC.
The obtained resin composition was subjected to the above test, and the results are shown in Table 2.

Reference Example 3 (Crosslinking reaction)
The composition was manufactured in three stages. First, the total amount of each component other than component (c) and component (e) shown in Table 2 and 20 parts by weight of component (e) were melt-kneaded (first step), and then in the middle of the extruder The organic peroxide and the crosslinking aid are added and melt-kneaded (second step), and the whole amount of the component (c) and the remainder of the component (e) are added and melt-kneaded from the middle of the extruder (third step). ). Using a twin screw extruder (L / D = 47), melt kneading was performed at a screw rotation speed of 100 rpm, and the melt kneading temperature of each step was as follows: First step: 230 to 240 ° C., 2nd process: 180-240 degreeC, 3rd process: 200-220 degreeC.
The obtained resin composition was subjected to the above test, and the results are shown in Table 2.

Reference Examples 4 and 5 (non-crosslinking reaction)
Each component shown in Table 3 was melt-kneaded at once. Using a twin screw extruder (L / D = 47), melt kneading was performed at a kneading temperature of 180 to 240 ° C. and a screw rotation speed of 100 rpm.

  The obtained resin composition was tested as described above, and the results are shown in Table 3.

  The resin composition of the present invention is excellent in flame retardancy, tensile properties and molding processability, does not whiten even when bent, and does not require a post-crosslinking step when being processed into an electric wire. Therefore, it is useful in automobile parts, home appliance parts, electric wire coverings, and the like.

Claims (14)

(A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them. 100 parts by weight of a block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide,
(D) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide-decomposable olefin resin and / or copolymer rubber 10 containing the same. A flame-retardant thermoplastic elastomer resin composition for covering electric wires, comprising ~ 150 parts by weight. The flame retardant thermoplastic elastomer resin composition according to claim 1, further comprising (f) 0 to 150 parts by weight of an inorganic filler. The flame retardant thermoplastic elastomer resin composition according to claim 1 or 2, wherein the component (c) flame retardant further contains red phosphorus. The flame retardant thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein the component (c) flame retardant further comprises a silicone compound. The flame retardant thermoplastic elastomer resin composition according to any one of claims 1 to 4, wherein the resin composition is a crosslinked product. The flame retardant thermoplastic elastomer resin composition according to any one of claims 1 to 4, wherein the resin composition is a non-crosslinked product. (A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them. 100 parts by weight of a block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide,
(D) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide-decomposable olefin resin and / or copolymer rubber 10 containing the same. It is a manufacturing method of the flame-retardant thermoplastic elastomer resin composition for electric wire coating | cover containing -150 weight part, Comprising: The whole quantity of a component (a), a component (b) and a component (c), and a component (e) At least a portion, and if there is component (d), at least a portion of component (d) is crosslinked by heat treatment in the presence of an organic peroxide, and then the remainder of the crosslinked product and component (e), In addition, a method for producing a flame-retardant thermoplastic elastomer resin composition for coating an electric wire, characterized in that if there is a balance of component (d), the remainder of component (d) is blended and melt-kneaded. Furthermore, (f) 0-150 weight part of inorganic fillers are mix | blended in arbitrary steps. Claims wherein at least 3 parts by weight of component (e) is blended before or during heat treatment in the presence of organic peroxide and at least 3 parts by weight is blended after heat treatment in the presence of organic peroxide Item 9. The production method according to Item 7 or 8. The production method according to any one of claims 7 to 9, wherein at least half of the component (d) is blended before or during heat treatment in the presence of an organic peroxide. The production method according to any one of claims 7 to 10, wherein the crosslinking is performed in the presence of a crosslinking aid which is a monomer having an ethylenically unsaturated group. (A) a block copolymer consisting of at least two polymer blocks A mainly made from vinyl aromatic compounds and at least one polymer block B mainly made from conjugated diene compounds, and / or hydrogenating them. 100 parts by weight of a block copolymer obtained by
(B) 20 to 300 parts by weight of a non-aromatic rubber softener,
(C) 100 to 600 parts by weight of a flame retardant containing a metal hydroxide, (d) 0 to 150 parts by weight of a peroxide-crosslinked olefin resin and / or copolymer rubber containing the same, and (e) a peroxide. A method for producing a flame retardant thermoplastic elastomer resin composition for wire coating, comprising 10 to 150 parts by weight of a decomposable olefin resin and / or copolymer rubber containing the same, comprising: component (a), component ( b), the total amount of component (c) and component (e), and if there is component (d), the total amount of component (d) is melt-kneaded all at once, and the flame retardancy for covering wires A method for producing a thermoplastic elastomer resin composition. Furthermore, (f) 0-150 weight part of inorganic fillers are mix | blended, The method of Claim 12. The method according to claim 12 or 13, wherein the melt-kneading is performed in the presence of an organic peroxide and a crosslinking aid.