JP2006225477A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonhalogen flame-retardant composition excellent in flexibility, mar resistance, abrasion resistance, and moldability and to provide an electric wire-coating material using the same. <P>SOLUTION: The flame-retardant resin composition comprises 15 to below 45 pts.wt. (a) polyphenylene ether resin, 0 to 30 pts.wt. (b) styrene-based polymer, 10 to 60 pts.wt. (c) hydrogenated copolymer obtained by hydrogenating a random copolymer comprising conjugated diene monomer units and vinylaromatic monomer units, and 3 to 40 pts.wt. phosphorus-based flame retardant (d), provided that component (a)+component (b)+component (c)+component (d)=100 pts.wt. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a flame retardant resin composition comprising a polyphenylene ether resin, a styrene polymer, a specific hydrogenated copolymer, and a phosphorus flame retardant, and an electric wire covering material thereof. More specifically, the present invention relates to a copolymer block obtained by hydrogenating a random copolymer comprising a polyphenylene ether resin, a styrene polymer, a conjugated diene monomer unit and a vinyl aromatic monomer unit. The present invention relates to a hydrogenated copolymer containing a flame retardant resin composition and a flame retardant resin composition mainly composed of a phosphorus-based flame retardant. The flame retardant resin composition of the present invention is excellent in flexibility, various mechanical properties, heat deformation resistance, scratch resistance, abrasion resistance characteristics, and moldability, and includes wire and cable coating materials. It can be suitably used for applications where soft vinyl chloride resin is used.

In general, a soft vinyl chloride resin having excellent flame retardancy is used as a coating material for electric wires such as home appliance parts and automobile parts. Soft vinyl chloride resin is flexible and has excellent mechanical properties such as tensile strength. However, since it contains a large amount of chlorine in the molecule, there is concern about environmental impact, and its alternative material has recently been demanded. .
In recent years, non-vinyl chloride resin-based flame retardant materials have been studied mainly in olefin resins, and some flame-retardant resin compositions in which hydrated metal oxides are blended with olefin resins such as polyethylene have been put into practical use. Has been. However, in the flame retardant resin composition, a large amount of hydrated metal hydroxide is added in order to ensure the flame retardant properties required for the wire coating material and the like. As a result, the flame retardant resin composition The current wire covering material has a high specific gravity and does not reach the performance of the vinyl chloride resin system in terms of flexibility, mechanical properties, moldability, and the like.

  On the other hand, the polyphenylene ether resin is an amorphous thermoplastic resin having a high softening point, has balanced mechanical properties and excellent electrical properties, and is easily flame retardant with phosphorus flame retardants. Since it is a resin, it is expected as a resin for covering electric wires. However, the polyphenylene ether resin alone is insufficient in flexibility and cold resistance and cannot be used for electric wire coating for home appliances. Therefore, an attempt to improve the disadvantages of the polyphenylene ether resin. Has been done. For example, for the purpose of improving the flexibility and cold resistance of polyphenylene ether-based resins, improvement studies using relatively compatible styrene-based elastomers are being conducted.

  Although a composition comprising a styrene-olefin-styrene block copolymer and a hydrated metal oxide is disclosed in a polyphenylene ether resin, a large amount of hydrated metal oxide is used when used as a wire covering material for home appliances. Formulation is necessary, and as a result, various physical properties and moldability are poor (see, for example, Patent Document 1 and Patent Document 2). In addition, an attempt to impart flexibility and the like to a polyphenylene ether resin by using a commercially available hydrogenated type block polymer of styrene-butadiene-styrene is also disclosed. In this case, a phosphorus flame retardant is used as a flame retardant. Because it is used, problems such as hydrated metal oxide addition systems do not occur, but a large amount of hydrogenated type block polymer is added to improve flexibility, and the wear and scratching properties of the resin composition, etc. There is a problem in that productivity becomes poor due to frequent occurrence of scorching and scorching during molding. (For example, refer to Patent Documents 3, 4, and 5.)

Japanese Patent Laid-Open No. 03-199256 Japanese Patent Laid-Open No. 03-273055 Japanese Patent Laid-Open No. 04-248870 Japanese Patent Application Laid-Open No. 07-150030 JP 2004-161929 A

  The present invention eliminates the above-mentioned drawbacks of the prior art, and is a flame retardant resin excellent in mechanical properties such as flexibility and tensile strength, heat deformation resistance, abrasion resistance, scratch resistance, and moldability. It aims at providing a composition and its electric wire coating | covering material.

  In order to solve the above-mentioned problems, the present inventors have conducted various researches, and as a result, a random comprising a polyphenylene ether resin, a styrene polymer, a conjugated diene monomer unit and a vinyl aromatic monomer unit. A hydrogenated copolymer containing a copolymer block obtained by hydrogenating a copolymer, and a flame retardant composition mainly composed of a phosphorus flame retardant have mechanical properties such as flexibility and tensile strength, The present inventors have found that it becomes a flame retardant resin composition excellent in heat deformation resistance, abrasion resistance, scratch resistance and moldability and suitable for wire coating, and has completed the present invention.

That is, the present invention
1. (A) 15 parts by weight to less than 45 parts by weight of a polyphenylene ether resin, (b) 0 to 30 parts by weight of a styrene polymer, (c) a conjugated diene monomer unit and a vinyl aromatic monomer unit. Component (a) + component comprising 10 to 60 parts by weight of a hydrogenated copolymer containing a copolymer block obtained by hydrogenating a random copolymer and 3 to 40 parts by weight of (d) a phosphorus flame retardant (B) flame retardant resin composition in which component (c) + component (d) = 100 parts by weight,

2. The hydrogenated copolymer (c) is obtained by hydrogenating a polymer block (A) comprising a vinyl aromatic monomer unit and a polymer block comprising a conjugated diene monomer unit having a vinyl bond content of less than 30%. At least 1 obtained by hydrogenating the resulting hydrogenated polymer block (C) and a random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit and having a vinyl bond content of less than 40%. A hydrogenated copolymer (c) comprising one hydrogenated copolymer block (B) or water having at least two polymer blocks (A) and at least one hydrogenated copolymer block (B) The flame retardant resin composition according to 1 above, which is a hydrogenated copolymer (c) that is a hydrogenated copolymer (c) and has the following characteristics (1) to (6):
(1) The content of the vinyl aromatic monomer unit is more than 40% by weight and less than 95% by weight with respect to the weight of the hydrogenated copolymer;
(2) The content of the polymer block (A) is 0 to 60% by weight with respect to the weight of the hydrogenated copolymer,
(3) The weight average molecular weight is 30,000 to 1,000,000,
(4) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more,
(5) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or more and less than 0 ° C., and (6) the In the case where the hydrogenated copolymer (c) does not have the hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, the temperature is -20 to 80 ° C. There is substantially no crystallization peak due to the at least one hydrogenated copolymer block (B) in the range.

3. The hydrogenated copolymer (c) includes at least one of the hydrogenated polymer block (C), the hydrogenated copolymer block (B) and the polymer block (A), and has the following characteristics (7 And flame retardant resin composition according to 1 above, further comprising:
(7) The content of the hydrogenated polymer block (C) is 10 to 50% by weight and the content of the hydrogenated copolymer block (B) is 30 to 90% by weight based on the weight of the hydrogenated copolymer. %, And the content of the polymer block (A) is 0 to 40% by weight,
(8) The content of the vinyl aromatic monomer unit is more than 40% by weight and less than 90% by weight with respect to the weight of the hydrogenated copolymer.

4). In the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer (c), a crystallization peak due to the at least one hydrogenated copolymer block (B) is in the range of −20 to 80 ° C. The flame retardant resin composition according to the above item 3, which is a hydrogenated copolymer that is substantially absent,
5. The hydrogenated copolymer (c) comprises at least two polymer blocks (A) and at least one hydrogenated copolymer block (B), and has the following properties (9) and (10): The flame retardant resin composition according to the above 1, further comprising:
(9) The content of the vinyl aromatic monomer unit is more than 40% by weight and not more than 60% by weight with respect to the weight of the hydrogenated copolymer,
(10) The content of at least two polymer blocks (A) is 5 to 60% by weight based on the weight of the hydrogenated copolymer.

6). The flame retardant resin composition according to any one of 1 to 5 above, wherein the phosphorus flame retardant (d) is at least one selected from the group consisting of red phosphorus, an organic phosphate compound, a phosphazene compound, and a phosphoramide compound. object,
7). (A) 25-40 parts by weight of a polyphenylene ether resin, (b) 5-15 parts by weight of a styrene polymer, (c) a random copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit. Comprising 30 to 55 parts by weight of a hydrogenated copolymer containing a copolymer block obtained by hydrogenating and (d) 12 to 25 parts by weight of a phosphorus-based flame retardant, component (a) + component (b) + The flame retardant resin composition according to any one of 1 to 6 above, wherein component (c) + component (d) = 100 weight,
8). Any one of 1 to 7 above, wherein 1 to 30 parts by weight of the component (e) polyolefin resin is added to 100 parts by weight of the component (a) + component (b) + component (c) + component (d) = 100 parts by weight. Flame retardant resin composition,
9. An electric wire and cable covering material comprising the flame retardant resin composition according to any one of 1 to 8 above,
It is.

  The flame retardant resin composition of the present invention has excellent flame retardancy, and is excellent in mechanical properties such as flexibility and tensile strength, heat distortion resistance, wear resistance, scratch resistance, moldability and the like. Utilizing this characteristic, various electric wires. It can be used in a wide range of applications where a soft vinyl chloride resin such as a cable covering material is used.

Hereinafter, the present invention will be described in detail.
Polyphenylene ether resin (component (a))
In the present invention, known polyphenylene ether resins as component (a) can be used. That is, the polyphenylene ether resin is, for example, the following general formula (I):

(Wherein R ¹ , R ² , R ³ And R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group or a nitro group, and n is an integer representing the degree of polymerization). It is a general term for the polymers shown, and may be a single polymer represented by the above general formula or a copolymer in which two or more are combined.
R ¹ , R ² Specific examples of R ³ and R ⁴ include chlorine atom, bromine atom, iodine atom, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy And groups such as nitro.

A preferred polyphenylene ether resin is R ¹ in the above formula (I). And R ² Is an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ are polymers each having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is usually preferably 50 or more.
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2-methyl-6- 6). Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-) 6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6 -Dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenyle) ) Ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable.

Examples of the polyphenylene ether copolymer include a copolymer partially containing an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the polyphenylene ether repeating unit. Further, copolymers obtained by grafting styrene compounds to these polyphenylene ether resins may be used. Examples of the styrene compound-grafted polyphenylene ether include a copolymer obtained by graft polymerization of styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like as the styrene compound to the polyphenylene ether resin.
The polyphenylene ether resin may be modified with a modifier having a polar group. For example, acid halide, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, thiol Groups and the like.

  The molecular weight of the component (a) polyphenylene ether resin in the present invention is preferably a number average molecular weight of 1000 to 100,000, and more preferably in the range of 6000 to 60000 in consideration of the balance of various physical properties. The component (a) polyphenylene ether resin in the present invention is blended in an amount of 15 to 45 parts by weight, preferably 25 to 40 parts by weight in 100 parts by weight of the flame retardant resin composition of the present invention. When the blending amount of the polyphenylene ether-based resin is less than 15 parts by weight, the flame retardancy is insufficient, and when it exceeds 45 parts by weight, the flexibility of the flame retardant resin composition is insufficient.

Styrene polymer (component (b))
As the component (b) styrene polymer in the present invention, either a styrene polymer produced by ordinary radical polymerization or a styrene polymer having a syndiotactic structure may be used.
Examples of the styrene polymer produced by normal radical polymerization include those containing a homopolymer of a styrene compound or a monomer copolymerizable with the styrene compound. Examples of the styrene compound include alkyl-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o -Halogenated styrene such as chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, tribromostyrene, etc., among these, styrene, α -Methylstyrene is preferred. Examples of monomers copolymerizable with styrene compounds include vinyl cyanide such as acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride. An acid etc. are mentioned, Among these, acrylonitrile is preferable.

In the present invention, a styrenic polymer having a syndiotactic structure may be used in order to develop better chemical resistance. The syndiotactic structure is a structure in which phenyl groups or substituted phenyl groups are alternately located in opposite directions with respect to the main chain formed from carbon-carbon bonds, and the tacticity is isotope carbon. Quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method). ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of consecutive structural units, for example, a dyad for two, a triad for three, a pentad for five. . In the present invention, syndiotactic polystyrene is usually a styrenic polymer having a syndiotacticity of 75% or more, preferably 85% or more, or a racemic pentad ratio of 30% or more, preferably 50% or more. It is. The styrenic polymer is polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinyl benzoate), a mixture thereof, or a copolymer based on these. Is included.

Here, examples of the poly (alkyl styrene) include poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), and the like. , Poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), and further styrene and p-methylstyrene. Mention may be made of copolymers. Such syndiotactic polystyrene is produced by using, for example, a styrenic monomer (the above styrenic monomer) in the presence of an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst. (Monomers corresponding to the polymer) can be produced by polymerization (for example, Japanese Patent Application Laid-Open Nos. 62-104818 and 63-268709), and commercially available products can also be used. .
The component (b) styrenic polymer in the present invention can be blended in an amount of 0 to 30 parts by weight, preferably 5 to 15 parts by weight, in 100 parts by weight of the flame retardant resin composition. When the compounding amount of the component (b) styrene polymer exceeds 30 parts by weight, flame retardancy and mechanical strength are lowered.

Hydrogenated copolymer (component (c))
The component (c) hydrogenated copolymer in the present invention contains a copolymer block obtained by hydrogenating a random copolymer composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. It is a hydrogenated copolymer. The flame retardant resin composition using the component (c) hydrogenated copolymer in the present invention is a flame retardant resin composition using an ordinary styrene elastomer (for example, styrene-b-ethylene / butylene-styrene). When compared with, it is excellent in terms of fluidity, wear resistance, scratch resistance and the like. This difference in performance is presumed to be due to the effect of the hydrogenated segment of the non-hydrogenated random copolymer block. Moreover, in the electric wire covering molding using the flame retardant resin composition of the present invention, there is an effect that the occurrence frequency of scum and scorch is low compared with the case where a conventional styrene-based elastomer is blended.

  The name of each monomer unit constituting the polymer is in accordance with the name of the monomer from which the monomer unit is derived. For example, “vinyl aromatic monomer unit” means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is substituted ethylene derived from a substituted vinyl group. It is a molecular structure in which the two carbons of the group are binding sites. The term “conjugated diene monomer unit” means a structural unit of a polymer produced as a result of polymerizing a monomer, conjugated diene, and its structure is the same as that of an olefin derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.

  The component (c) hydrogenated copolymer in the present invention is a non-hydrogenated random copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit (hereinafter often referred to as “base non-hydrogenated copolymer”). And a copolymer obtained by hydrogenation. The component (c) hydrogenated copolymer in the present invention is obtained by hydrogenating a polymer block (A) composed of vinyl aromatic monomer units and a non-hydrogenated polymer block composed of conjugated diene monomer units. At least one polymer block selected from the group consisting of the hydrogenated polymer block (C) obtained in the above, and a non-hydrogenated random copolymer consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit You may include the at least 1 hydrogenated copolymer block (B) obtained by hydrogenating a unification block. However, the vinyl bond amount of the non-hydrogenated polymer block composed of conjugated diene monomer units is preferably less than 30%, and the non-hydrogenated random copolymer weight composed of conjugated diene monomer units and vinyl aromatic monomer units. The vinyl bond content of the combined block is preferably less than 40%.

The polymer block (A) and the hydrogenated polymer block (C) serve as physical cross-linking points and are therefore referred to as “constrained phase”. On the other hand, the hydrogenated copolymer block (B) is referred to as “unconstrained phase”.
The component (c) hydrogenated copolymer in the present invention preferably has two or more polymer blocks which are constrained phases. When the hydrogenated copolymer (c) in the present invention does not have a hydrogenated polymer block (C), the hydrogenated copolymer (c) may have at least two polymer blocks (A). preferable. In the case where the component (c) hydrogenated copolymer used in the present invention has two or more polymer blocks that are a constrained phase, the mechanical strength of the hydrogenated copolymer is excellent.

  When the component (c) hydrogenated copolymer in the present invention does not have the hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, −20 It is preferable that the crystallization peak due to the hydrogenated copolymer block (B) is substantially absent in the range of ˜80 ° C. Here, “the crystallization peak due to the hydrogenated copolymer block (B) is not substantially present in the range of −20 to 80 ° C.” means that the hydrogenated copolymer block (B) in this temperature range. The peak due to crystallization does not appear or the peak due to crystallization is observed, but the crystallization peak heat due to the crystallization is preferably less than 3 J / g, more preferably less than 2 J / g, Preferably it means less than 1 J / g, particularly preferably no crystallization peak heat.

When the component (c) hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), the hydrogenated copolymer is in the range of −20 to 80 ° C. in the differential scanning calorimetry (DSC) chart. It is not required that the crystallization peak due to the polymer block (B) is substantially absent. However, even in the case of having the hydrogenated polymer block (C), in the above differential scanning calorimetry (DSC) chart, the crystallization peak caused by the hydrogenated copolymer block (B) in the range of −20 to 80 ° C. Is preferably substantially absent.
The hydrogenated copolymer having substantially no crystallization peak due to the hydrogenated polymer block (B) in the range of -20 to 80 ° C. in the differential scanning calorimetry (DSC) chart has good flexibility. In the present invention, it is preferable. A hydrogenated copolymer having substantially no crystallization peak due to the hydrogenated copolymer block (B) in the range of −20 to 80 ° C. as described above is a vinyl bond amount adjusting agent or A non-hydrogenated copolymer obtained by conducting a polymerization reaction under the conditions described later using a regulator as described later for adjusting the random copolymerizability between the conjugated diene and the vinyl aromatic compound Obtained by hydrogenation.

In the case of having a hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart, regarding the crystallization peak due to the hydrogenated polymer block (C), the crystallization peak temperature is 30 ° C. or higher, preferably It preferably has a crystallization peak in the temperature range of 45 to 100 ° C, more preferably 50 to 90 ° C. The crystallization peak heat quantity is preferably 3 J / g or more, preferably 6 J / g or more, and more preferably 10 J / g or more.
The crystallization peak temperature and the crystallization peak calorie can be measured using a differential scanning calorimeter.

  The content of the vinyl aromatic monomer unit in the component (c) hydrogenated copolymer in the present invention is preferably more than 40% by weight and less than 95% by weight with respect to the hydrogenated copolymer. The hydrogenated copolymer of the present invention preferably has a vinyl aromatic monomer unit content in the above range, and exhibits excellent performance in flexibility, low temperature characteristics, and the like. From the viewpoint of flexibility and low temperature characteristics, the content of the vinyl aromatic monomer unit is more preferably more than 40% by weight and 80% by weight or less, particularly preferably more than 45% by weight and 70% by weight or less, most preferably. Is more than 45% by weight and 60% by weight or less. In particular, when the hydrogenated copolymer does not have the hydrogenated polymer block (C), the content of the vinyl aromatic monomer unit is preferably more than 40% by weight and 90% by weight or less, more preferably 45%. More than 85% by weight, more preferably more than 50% by weight and 80% by weight or less.

The content of vinyl aromatic monomer units in the hydrogenated copolymer is almost equal to the content of vinyl aromatic monomer units in the base non-hydrogenated copolymer. The content rate with respect to an addition copolymer is calculated | required as a content rate with respect to a base non-hydrogenation copolymer. The content of the vinyl aromatic monomer unit with respect to the hydrogenated copolymer is measured using an ultraviolet spectrophotometer using the base non-hydrogenated copolymer as a specimen.
In the component (c) hydrogenated copolymer in the present invention, the content of the polymer block (A) is preferably in the range of 0 to 60% by weight based on the hydrogenated copolymer. The hydrogenated copolymer of the present invention has excellent flexibility and low temperature characteristics because the content of the polymer block (A) is in the above range. From the viewpoint of low temperature characteristics, the content of the polymer block (A) is more preferably 5 to 60% by weight, particularly preferably 8 to 50% by weight, and most preferably 10 to 40% by weight.

  In the present invention, the content of the polymer block (A) with respect to the hydrogenated copolymer is substantially equal to the content of the polymer block (A) with respect to the base non-hydrogenated copolymer. The content rate with respect to a hydrogenated copolymer is calculated | required as a content rate with respect to the base non-hydrogenated copolymer of a polymer block (A). Specifically, a method of oxidizing and decomposing a base non-hydrogenated copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 ( 1946), and the weight of the vinyl aromatic polymer block component determined by the method described below (hereinafter often referred to as “osmium tetroxide decomposition method”) (however, the vinyl aromatic polymer component having an average degree of polymerization of about 30 or less is It is obtained from the following equation using

Content (% by weight) of vinyl aromatic polymer block (A) = (weight of vinyl aromatic polymer block (A) in base non-hydrogenated copolymer / weight of base non-hydrogenated copolymer) × 100.
In addition, when directly measuring the content rate with respect to the hydrogenated copolymer of a polymer block (A), it can carry out using a hydrogenated copolymer as a test substance using a nuclear magnetic resonance apparatus (NMR) (Y Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as “NMR method”).
The content of the polymer block (A) determined by the osmium tetroxide decomposition method (referred to as “Os value”) and the content of the polymer block (A) determined by the NMR method (“Ns value”) Are referred to as correlations. As a result of investigations using various copolymers by the present inventors, it was found that the relationship is expressed by the following formula.
Os value = −0.012 (Ns value) 2 + 1.8 Ns value) −13.0

Therefore, in the present invention, when the content (Ns value) of the polymer block (A) with respect to the hydrogenated copolymer is determined by the NMR method, the Ns value is converted into an Os value based on the above formula.
The content of the hydrogenated copolymer block (B) in the component (c) hydrogenated copolymer of the present invention is not particularly limited. However, when the hydrogenated copolymer of the present invention does not have the hydrogenated polymer block (C), the content of the hydrogenated copolymer block (B) is water from the viewpoint of flexibility and low temperature characteristics. Preferably it is 30 to 95 weight% with respect to an additive copolymer, More preferably, it is 40 to 92 weight%, Most preferably, it is 50 to 90 weight%. On the other hand, when the hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), the content of the hydrogenated copolymer block (B) is preferably 30 to 90% by weight, more preferably It is 40 to 88% by weight, particularly preferably 50 to 86% by weight.

  As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. Content of a hydrogenated copolymer block (B) is calculated | required from the addition amount of the conjugated diene monomer and vinyl aromatic monomer unit at the time of manufacturing the said non-hydrogenated random copolymer block. The content of the hydrogenated copolymer block (B) with respect to the hydrogenated copolymer is substantially equal to the content of the non-hydrogenated random copolymer block with respect to the base non-hydrogenated copolymer. The content of the polymer block (B) with respect to the hydrogenated copolymer is determined as the content of the non-hydrogenated random copolymer block with respect to the base non-hydrogenated copolymer.

The content of the hydrogenated polymer block (C) in the component (c) hydrogenated copolymer in the present invention is not particularly limited. However, from the viewpoint of flexibility and low-temperature characteristics, the content of the hydrogenated polymer block (C) is preferably 0 to 50% by weight, more preferably 10 to 50% by weight, further based on the hydrogenated copolymer. It is preferably 12 to 45% by weight, particularly preferably 15 to 40% by weight.
As described above, the hydrogenated polymer block (C) is obtained by hydrogenating a non-hydrogenated polymer block composed of conjugated diene monomer units. Content of a hydrogenated polymer block (C) is calculated | required from the addition amount of the conjugated diene monomer at the time of manufacturing the said non-hydrogenated polymer block. In addition, since the content rate with respect to the hydrogenated copolymer of the hydrogenated polymer block (C) is substantially equal to the content rate of the non-hydrogenated polymer block with respect to the base non-hydrogenated copolymer, the hydrogenated polymer block ( The content of C) with respect to the hydrogenated copolymer is determined as the content of the non-hydrogenated polymer block with respect to the base non-hydrogenated copolymer.

  The weight average molecular weight of the component (c) hydrogenated copolymer in the present invention is preferably 30,000 to 1,000,000. The component (c) hydrogenated copolymer in the present invention has an excellent balance between mechanical strength and moldability because the weight average molecular weight is in the above range. From the viewpoint of the balance between mechanical strength, impact absorbability and moldability, the weight average molecular weight of the hydrogenated copolymer of the present invention is more preferably 50,000 to 800,000, still more preferably 100,000 to 500,000. Particularly preferred is 150,000 to 400,000. In particular, when the component (c) hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), the weight average molecular weight is preferably more than 100,000 and more than 1,000,000 from the viewpoint of molding processability. Hereinafter, it is more preferably 120,000 to 800,000, particularly preferably 140,000 to 500,000.

  The molecular weight distribution (Mw / Mn) (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated copolymer of the component (c) in the present invention is preferably 10 or less, more preferably 1 .01 to 8, particularly preferably 1.1 to 5. When emphasizing molding processability, it is preferably 1.3 to 5, more preferably 1.5 to 5, even more preferably 1.6 to 4.5, and particularly preferably 1.8 to 4. Since the weight average molecular weight of the hydrogenated copolymer is substantially equal to the weight average molecular weight of the base non-hydrogenated copolymer, the weight average molecular weight of the hydrogenated copolymer is determined as the weight average molecular weight of the base non-hydrogenated copolymer. The weight average molecular weight of the base non-hydrogenated copolymer is determined by gel permeation chromatography (GPC) using a calibration curve obtained for a commercially available standard monodisperse polystyrene having a known molecular weight. The number average molecular weight of the hydrogenated copolymer is determined in the same manner. The molecular weight distribution is obtained by calculation as a ratio of the weight average molecular weight to the number average molecular weight.

As noted above, component (c) hydrogenated copolymer of the present invention is a non-hydrogenated copolymer comprising a conjugated diene monomer unit and a vinyl aromatic compound monomer unit (ie, a base non-hydrogenated copolymer). Polymer) is obtained by hydrogenation. The hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated copolymer of the invention is preferably 75 to 100%. From the viewpoint of thermal stability, the hydrogenation rate is more preferably 80 to 100%, still more preferably 85 to 100%, and particularly preferably 90 to 100%.
The hydrogenation rate of the double bond of the vinyl aromatic monomer unit in the component (c) hydrogenated copolymer in the present invention is not particularly limited, but the hydrogenation rate is preferably 50% or less, Preferably it is 30% or less, particularly preferably 20% or less.

The hydrogenation rate in the hydrogenated copolymer can be measured using a nuclear magnetic resonance apparatus.
The component (c) hydrogenated copolymer in the present invention has a loss tangent (tan δ) peak in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, preferably from −40 ° C. to less than 0 ° C. More preferably, it is at least one in the range of −35 to −12 ° C., more preferably −30 to −14 ° C. The loss tangent peak existing in the range of −40 ° C. or higher and lower than 0 ° C. is a hydrogenated copolymer block (B) (non-hydrogenated consisting of a conjugated diene monomer unit, a vinyl aromatic compound and a monomer unit. This is a peak resulting from a hydrogenated polymer block obtained by hydrogenating a random copolymer block. The presence of at least one loss tangent peak in the range of −40 ° C. or more and less than 0 ° C. is also preferable from the viewpoint of the balance between the low temperature characteristics, the flexibility, the wear resistance, and the scratch resistance of the hydrogenated copolymer. In the present invention, the loss tangent peak due to the polymer block (A) is not particularly limited, but the loss tangent peak due to the polymer block (A) usually exceeds 80 ° C. , Within a temperature range of 150 ° C. or less.

The loss tangent (tan δ) peak in the dynamic viscoelastic spectrum is measured at a frequency of 10 Hz using a viscoelasticity analyzer.
As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. The weight ratio of the conjugated diene monomer unit / vinyl aromatic monomer unit in the non-hydrogenated random copolymer is not particularly limited. However, considering that at least one peak of loss tangent exists in the range of −40 ° C. or higher and lower than 0 ° C. as described above, the weight ratio of conjugated diene monomer unit / vinyl aromatic monomer unit is It is recommended that the ratio be 50/50 to 90/10, more preferably 53/47 to 80/20, and particularly preferably 56/44 to 75/25.

  As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. The microstructure of the conjugated diene monomer unit in the non-hydrogenated random copolymer (ratio of cis, trans, vinyl) can be arbitrarily changed by using a polar compound described later. In the present invention, the vinyl bond amount of the conjugated diene monomer unit in the non-hydrogenated random copolymer block composed of the conjugated diene monomer unit and the vinyl aromatic monomer unit may be less than 40%. preferable. {Hereafter, the total amount of 1,2-vinyl bond and 3,4-vinyl bond (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bond) is simply vinyl bond. It is called quantity. }. From the viewpoint of handleability (blocking resistance), the vinyl bond content is preferably 5 to 35%, more preferably 8 to 30%, and still more preferably 10 to 25%.

As described above, the hydrogenated polymer block (C) is obtained by hydrogenating a non-hydrogenated polymer block composed of a conjugated diene monomer unit and having a vinyl bond content of less than 30%. The amount of vinyl bonds in the non-hydrogenated polymer block is preferably 8 to 25%, more preferably 10 to 25%, and particularly preferably 12 to 20% from the viewpoint of handleability (anti-blocking).
The vinyl bond amount is measured using an infrared spectrophotometer using the base non-hydrogenated copolymer as a specimen.
The structure of the component (c) hydrogenated copolymer in the present invention is not particularly limited, and any structure can be used. As an embodiment of the component (c) hydrogenated copolymer in the present invention, at least one hydrogenated polymer block (C), at least one hydrogenated copolymer block (B), and optionally at least Examples of the hydrogenated copolymer include one polymer block (A). Examples of such a hydrogenated copolymer include those having a structure represented by the following formula.

(C-B) _n , C- (B-C) _n , B- (C-B) _n ,
[(C-B) _n ] _m- X, [(BC) _n- B] _m- X,
[(C-B) _n- C] _m- X,
C- (B-A) _n , C- (A-B) _n ,
C- (A-B-A) _n , C- (B-A-B) _n ,
A-C- (B-A) _n , A-C- (A-B) _n ,
A-C- (BA) _n -B, [(ABC) _n ] _m -X,
[A- (B-C) _n ] _m- X, [(AB) _n- C] _m- X,
[(ABA) _n -C] _m -X,
[(B-A-B) _n- C] _m- X, [(C-B-A) _n ] _m- X,
[C- (BA) _n ] _m- X,
[C- (ABA) _n ] _m -X,
[C- (BAB) _n ] _m -X

  Further, as another embodiment of the component (c) hydrogenated copolymer in the present invention, it includes at least two polymer blocks (A) and at least one hydrogenated copolymer block (B). Examples of such hydrogenated copolymers include those having a structure represented by the following formula.

(AB) _{n + 1} , A- (BA) _n ,
B- (A-B) _{n + 1} ,
[(AB) _n ] _m- X, [(BA) _n- B] _m- X,
[(AB) _n- A] _m- X, [(BA) _{n + 1} ] _m- X.
In the above formula, each A independently represents a polymer block composed of vinyl aromatic monomer units. Each B represents a hydrogenated copolymer block obtained by hydrogenating a non-hydrogenated random copolymer consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit. Each C independently represents a hydrogenated polymer block obtained by hydrogenating a non-hydrogenated polymer block composed of a conjugated diene monomer unit and having a vinyl bond content of less than 30%. The boundary of each block does not necessarily have to be clearly distinguished. The vinyl aromatic monomer units in the hydrogenated copolymer block B obtained by hydrogenating the non-hydrogenated random copolymer may be distributed uniformly or in a tapered shape. Good.

  Further, the hydrogenated copolymer block B may have a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or a plurality of portions where the vinyl aromatic monomer units are distributed in a tapered shape. In the hydrogenated copolymer block B, a plurality of segments having different vinyl aromatic monomer unit contents may exist. Each n is independently an integer of 1 or more, preferably an integer of 1 to 5. Each m is independently an integer of 2 or more, preferably an integer of 2 to 11. Each X independently represents a residue of a coupling agent or a residue of a polyfunctional initiator. As the coupling agent, a bifunctional or higher functional coupling agent described later can be used. As a polyfunctional initiator, a reaction product of diisopropenylbenzene and sec-butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene, or the like can be used.

The component (c) hydrogenated copolymer in the present invention may be any mixture having the structure represented by the above formula. The hydrogenated copolymer includes a hydrogenated copolymer having a structure represented by the above formula, a polymer composed of vinyl aromatic monomer units, a copolymer having an AB structure, and B- It may be a mixture with at least one polymer selected from the group consisting of copolymers having an AB structure.
As described above, the component (c) hydrogenated copolymer of the present invention has a loss tangent (tan δ) peak of −40 ° C. or higher in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, It is preferable that at least one peak is present in the range of less than 0 ° C., and the loss tangent peak present in the above range is the hydrogenated copolymer block (B) (conjugated diene monomer unit, vinyl aromatic compound and monomer This is a peak resulting from a hydrogenated copolymer block obtained by hydrogenating a non-hydrogenated random copolymer block comprising body units. Outside the above range, a loss tangent (tan δ) peak may or may not exist. For example, the component (c) hydrogenated copolymer of the present invention may contain a polymer block having a peak outside the above range.

  As an example of such a polymer block, a non-hydrogenated copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit (provided that the content of the vinyl aromatic monomer unit is 50% by weight) Obtained by hydrogenating a hydrogenated copolymer block obtained by hydrogenating a non-hydrogenated polymer block comprising a conjugated diene monomer unit having a vinyl bond content of 30% or more. Examples thereof include hydrogenated polymer blocks. However, when the hydrogenated copolymer contains these polymer blocks, in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, -20 to 80 ° C, preferably -50 to 100 It is recommended that there is substantially no crystallization peak in the range of ° C.

In addition, as the component (c) hydrogenated copolymer in the present invention, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or higher and lower than 0 ° C., and the range of −10 to 80 ° C. The hydrogenated copolymer present in at least one of them is preferable in that the flexibility and low temperature characteristics, which are one of the characteristics of the present invention, are low in temperature. In such a hydrogenated copolymer, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or more and less than −10 ° C., and the range of −10 to 15 ° C. and over 15 ° C. Particularly preferred are hydrogenated copolymers each present in the range of at most 1 ° C. or less.
In the present invention, a conjugated diene is a diolefin having a pair of conjugated double bonds. Examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (ie, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are particularly preferred. These may be used alone or in combination of two or more.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- p-aminoethylstyrene may be mentioned. These may be used alone or in combination of two or more.
As described above, the component (c) hydrogenated copolymer in the present invention is obtained by hydrogenating a non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit. There is no limitation in particular about the manufacturing method of this non-hydrogenated copolymer, A well-known method can be used. For example, it can be produced by anionic living polymerization using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of hydrocarbon solvents include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic carbonization such as cyclohexane, cycloheptane, and methylcycloheptane Hydrogens; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

  Examples of the polymerization initiator include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic aminoalkali metal compounds having anionic polymerization activity with respect to conjugated dienes and vinyl aromatic compounds. Examples of the alkali metal include lithium, sodium, and potassium. Examples of suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and compounds containing at least one lithium in one molecule (monolithium compounds, dilithium compounds, trilithium compounds, Lithium compounds, tetralithium compounds, etc.). Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec- A reaction product of butyllithium, a reaction product of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene can be used. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

In the present invention, when an organic alkali metal compound is used as a polymerization initiator and a conjugated diene monomer and a vinyl aromatic monomer are copolymerized, a vinyl bond resulting from a conjugated diene monomer unit incorporated in the polymer ( In order to adjust the amount of 1,2 vinyl bond or 3,4 vinyl bond) or the random copolymerization of conjugated diene and vinyl aromatic compound, a tertiary amine compound or ether compound is added as a regulator. be able to.
Examples of tertiary amine compounds are those of formula R1 R2 R3 N (wherein R1, R2 and R3 are each independently a hydrocarbon group having 1 to 20 carbon atoms or a tertiary amino group) The compound represented by these is mentioned. Specifically, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine Etc.

  Examples of ether compounds include linear ether compounds and cyclic ether compounds. Examples of linear ether compounds include dimethyl ether, diethyl ether, diphenyl ether; ethylene glycol dialkyl ether compounds such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether And dialkyl ether compounds of diethylene glycol. Examples of cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and furfuryl alcohol. Of these alkyl ethers.

  In the present invention, the method of copolymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organic alkali metal compound as a polymerization initiator may be batch polymerization or continuous polymerization, and a combination thereof. There may be. In particular, continuous polymerization is recommended for adjusting the molecular weight distribution to a preferable range in terms of moldability. The polymerization temperature is usually 0 to 180 ° C, preferably 30 to 150 ° C. The time required for the polymerization varies depending on other conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a pressure range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, care must be taken so that impurities (water, oxygen, carbon dioxide, etc.) that inactivate the catalyst and living polymer do not enter the polymerization system.

In the present invention, when the polymerization is completed, a coupling reaction may be performed using a bifunctional or higher functional coupling agent. There are no particular limitations on the bifunctional or higher functional coupling agent, and known coupling agents can be used. Examples of the bifunctional coupling agent include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. Examples of trifunctional or higher polyfunctional coupling agents include trihydric or higher polyalcohols; polyhydric epoxy compounds such as epoxidized soybean oil and diglycidyl bisphenol A; formula R _4-n SiX _n (where each R is Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a halogen atom, and n represents 3 or 4), for example, methylsilyl trichloride , T _- butylsilyl trichloride, silicon tetrachloride, and bromides thereof; Formula R _4-n SnX _n (where each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, and each X represents Each independently represents a halogen atom, and n represents 3 or 4, for example, methyltin trichloride, t-butyltin trichloride, tin tetrachloride, etc. Of the polyvalent halogen compounds. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used as a polyfunctional coupling agent.

By hydrogenating the non-hydrogenated copolymer produced by the above method, the component (c) hydrogenated copolymer in the present invention is obtained. There is no limitation in particular in a hydrogenation catalyst, A well-known hydrogenation catalyst can be used. Examples of the hydrogenation catalyst include the following.
(1) A supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth,
(2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt together with a reducing agent such as organoaluminum, and (3) Ti, Ru, Rh, Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Zr.

Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841 (corresponding to US Pat. No. 4,501,857), Japanese Patent Publication No. Hydrogenation catalysts described in Japanese Patent No. 37970 (corresponding to US Pat. No. 4,673,714), Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041 can be used. Examples of preferred hydrogenation catalysts include titanocene compounds and mixtures of titanocene compounds and reducible organometallic compounds.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds. Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction for producing the component (c) hydrogenated copolymer in the present invention is usually carried out in a temperature range of 0 to 200 ° C, preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is usually 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used in any of batch processes, continuous processes, and combinations thereof.
A hydrogenated copolymer solution is obtained by the above hydrogenation reaction. If necessary, catalyst residues are removed from the hydrogenated copolymer solution, and the hydrogenated copolymer is separated from the solution. An example of a method for separating the solvent is a method in which a polar solvent that is a poor solvent for the hydrogenated copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer; Examples thereof include a method in which the solvent is removed by steam stripping and recovered by stirring in hot water under stirring; and a method in which the solvent is distilled off by directly heating the polymer solution.
The component (c) hydrogenated copolymer in the present invention is blended in an amount of 10 to 60 parts by weight, preferably 30 to 55 parts by weight, in 100 parts by weight of the flame retardant resin composition of the present invention. When the blending amount of the component (c) is less than 10 parts by weight in 100 parts by weight of the flame retardant resin composition, flexibility and cold resistance are insufficient, while when it exceeds 60 parts by weight, flame retardancy is exhibited. Neither is desirable because it is insufficient.

Phosphorus flame retardant (component (d))
Examples of the component (d) phosphorus-based flame retardant in the present invention include red phosphorus, an organic phosphate compound, a phosphazene compound, and a phosphoramide compound.
Specific examples of the organic phosphate compound include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl-bis (3,5,5'-tri-methyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl-hexyl di (p-tolyl) phosphate, bis- (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) p-tolyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethyl hex Le diphenyl phosphate.

Also, bisphenol A / bis (diphenyl phosphate), diphenyl- (3-hydroxyphenyl) phosphate, bisphenol A / bis (dicresyl phosphate), resorcin / bis (diphenyl phosphate), resorcin / bis (dixylenyl phosphate), 2 -Naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate, di (2-naphthyl) phenyl phosphate, etc. are mentioned. Among them, for example, a phosphoric ester compound (Daihachi Chemical Co., Ltd., CR741) mainly composed of triphenyl phosphate (Daihachi Chemical Co., Ltd.), bisphenol A-bis (diphenyl phosphate), resorcin-bis (Di Phosphoric acid ester compounds mainly composed of xylenyl phosphate. Resorcins such as (Daihachi Chemical Co., Ltd., PX200) and phosphate ester compounds of bisphenol A are preferred in terms of volatility and heat resistance.
The phosphazene compound has a cyclic structure and a linear structure represented by the general formula (I), and a cyclic structure compound is preferable, and a 6-membered ring and an 8-membered phenoxyphosphazene compound having n = 3 and 4 are preferable. Particularly preferred.

(Here, R independently represents an aliphatic group or an aromatic group having 1 to 20 carbon atoms, and n is an integer of 3 or more.)
Further, these compounds may be cross-linked by a cross-linking group selected from the group consisting of a phenylene group, a biphenylene group and the following group.

(Wherein X _{is, -C (CH 3) 2 -} , - SO 2 -, - S-, or -O- shown.)

  The phosphazene compound represented by the general formula (I) is a known compound, for example, “Ino-rganic Polymers” by James E. Mark, Harry R. Allcock, Robert West, “Pretice-Hall International, Inc., 1992, p61-”. It is described in p140. Synthesis examples for obtaining these phosphazene compounds are disclosed in JP-B-3-73590, JP-A-9-71708, JP-A-9-183864, JP-A-11-181429, and the like. For example, in the synthesis of non-crosslinked cyclic phenoxyphosphazene compounds, R. According to the method described by Allcock, “Phosphorus-Nitrogen Compounds”, Academic Press, (1972), dichlorophosphazene oligomer (mixture of 62% trimer and 38% tetramer) 1.0 unit mole (115. After adding a toluene solution of sodium phenolate to 580 g of 20% chlorobenzene solution containing 9 g) under stirring, the mixture is reacted at 110 ° C. for 4 hours, and after purification, an uncrosslinked cyclic phenoxyphosphazene compound is obtained.

Since the phosphazene compound has a higher phosphorus content in the compound than a normal phosphate ester compound, a sufficient amount of flame retardancy can be ensured even with a small amount of addition, and as a result, a decrease in physical properties of the flame retardant resin composition can be suppressed. The phosphorus-based flame retardant in the present invention is a particularly preferable compound.
The component (d) phosphorus flame retardant in the present invention is blended in an amount of 3 to 40 parts by weight, preferably 12 to 25 parts by weight, in 100 parts by weight of the flame retardant resin composition of the present invention. When the blending amount of the component (d) is less than 3 parts by weight in 100 parts by weight of the flame-retardant resin composition, the flame retardancy is insufficient. , Both of which are not preferable.
If necessary, the flame retardant resin composition of the present invention may contain an anti-drip agent as a flame retardant aid. This anti-drip agent is an additive having a function of suppressing drip (dripping) during combustion, and a known one can be used. The anti-drip agent is added in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the flame retardant resin composition. In the present invention, a polyphenylene ether resin typified by polytetrafluoroethylene (PTFE) or the like that forms a fibril structure is particularly suitable because it has a high drip suppression effect. A resin composition containing such an anti-drip agent is particularly excellent in flame retardancy.

  Among such polytetrafluoroethylenes (PTFE), those having excellent dispersibility, for example, those obtained by emulsifying and dispersing PTFE in a solution such as water, acrylic ester resins, methacrylic ester resins, styrene-acrylonitrile A product obtained by encapsulating PTFE with a copolymer resin or the like is preferable because it gives a molded article made of a modified PPE resin a good surface appearance. In the case where PTFE is emulsified and dispersed in a solution such as water, there is no particular limitation. Specific examples of such commercially available PTFE include Teflon (registered trademark) 30J (trademark, Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-2C (trademark, Daikin Chemical Industries, Ltd.), Aflon AD1 (Trademark, Asahi Glass Co., Ltd.). Such polytetrafluoroethylene can also be produced by a known method (see US Pat. No. 2,393,967). Specifically, using a free radical catalyst such as sodium peroxydisulfate, potassium or ammonium, in an aqueous solvent at a pressure of 0.7 to 7 MPa, 0 to 200 ° C., preferably 20 to 100. Polytetrafluoroethylene can be obtained as a white solid by polymerizing tetrafluoroethylene under the temperature condition of ° C.

Such polytetrafluoroethylene has a molecular weight of 100,000 or more, preferably about 200,000 to 3,000,000. For this reason, the drip at the time of combustion is suppressed in the resin composition containing polytetrafluoroethylene. Furthermore, when polytetrafluoroethylene and a silicone resin are used in combination, drip can be further suppressed and combustion time can be shortened as compared with the case where only polytetrafluoroethylene is added.
In the flame-retardant resin composition of the present invention, a known thermoplastic resin may be further blended as necessary. Examples of the thermoplastic resin include block copolymer resins of conjugated dienes and vinyl aromatics and their hydrogenated products (however, different from the component (c) of the present invention), styrene resins such as polystyrene and rubber-modified styrene resins. , Polyamide resins, polyester resins, polycarbonate resins, polyolefins and the like. In particular, since polyolefin has an effect of improving the solvent resistance and heat distortion resistance of the flame retardant resin composition, about 1 to 30 parts by weight may be added to 100 parts by weight of the flame retardant resin composition.

The additive is not particularly limited as long as it is generally blended with a rubbery polymer or the like. Examples of the additive include those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.). Specific examples include pigments such as iron oxides; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide; mold release agents; organic polysiloxanes, hindered phenolic antioxidants Agents, antioxidants such as phosphorus heat stabilizers; hindered amine light stabilizers; benzotriazole ultraviolet absorbers, non-phosphorous flame retardants, flame retardant aids, antistatic agents, organic fibers, glass fibers, carbon fibers And reinforcing agents such as metal whiskers, coloring agents, and the like. These additives may be used in combination of two or more.
The method for producing the flame-retardant resin composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general blender such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, or a multi-screw extruder can be used.
The flame-retardant resin composition of the present invention can be used in various applications that require flame retardancy. For example, it can be suitably used for coating materials such as home appliance parts and automobile parts, coating materials such as power cables, communication cables, and power transmission cables, and building materials.

Hereinafter, the present invention will be specifically described with reference examples, examples and comparative examples, but the present invention is not limited to these examples.
(1) Component (a) Polyphenylene ether-based resin (PPE-1): Poly (2,6-dimethyl-1,4-phenylene ether powder (P402, Asahi Kasei Chemicals Corporation)
(2) Component (b) Styrene polymer (PS-1): Homopolystyrene 685 (PS Japan Co., Ltd.)
(3) Component (c) Hydrogenated copolymer (3.1) Preparation of hydrogenated copolymer The characteristics of the hydrogenated copolymer were measured by the following method.

(3.1-1) Styrene content The content of the styrene monomer unit with respect to the hydrogenated copolymer was measured with an ultraviolet spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) using the base non-hydrogenated copolymer as a specimen. It measured using. The content of the styrene monomer unit with respect to the hydrogenated copolymer was determined as the content of the styrene monomer unit with respect to the base non-hydrogenated copolymer.
In addition, when using a hydrogenated copolymer as a test substance, it measured using the nuclear magnetic resonance apparatus (Germany BRUKER company make, DPX-400).
(3.1-2) Styrene polymer block content (Os value)
The styrene polymer block content of the non-hydrogenated copolymer is M. Kolthoff, etal. , J .; Polym. Sci. 1, 429 (1946). For the decomposition of the non-hydrogenated copolymer, a 0.1 g / 125 ml tertiary butanol solution of osmic acid was used. The styrene polymer block content obtained here is referred to as “Os value”.

  In the case of measuring the styrene polymer block content of the hydrogenated copolymer, a nuclear magnetic resonance apparatus (JMN-270WB; manufactured by JEOL Ltd.) was used. Measurement was performed according to the method described in Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Specifically, 1H-NMR was measured using a sample obtained by dissolving 30 mg of a hydrogenated copolymer in 1 g of deuterated chloroform. The styrene polymer block content (Ns value) of the hydrogenated copolymer obtained by NMR measurement is the total integrated value, the integrated value of chemical shift 6.9 to 6.3 ppm, and the chemical shift 7.5 to 6.9 ppm. The Ns value is converted into an Os value. The calculation method is shown below.

Block styrene (St) strength = (6.9 to 6.3 ppm) integrated value / 2
Random styrene (St) strength = (7.5-6.9 ppm) integrated value-3 (block St strength)
Ethylene / Butylene (EB) Strength = Total Integrated Value-3 {(Block St Strength) + (Random St Strength)} / 8
Styrene polymer block content obtained by NMR measurement (Ns value) = 104 (block St intensity) / [104 {(block St intensity) + (random St intensity)} + 56 (EB intensity)]
Os value = −0.012 (Ns value) 2 + 1.8 (Ns value) −13.0

(3.1-3) Vinyl Bond Amount The vinyl bond amount of the polymer block in the base non-hydrogenated copolymer was measured using an infrared spectrophotometer (FT / IR-230; manufactured by JASCO Corporation). The vinyl bond amount of the conjugated diene polymer block which is a homopolymer block was calculated by the Morero method. The vinyl bond amount of the conjugated diene / styrene copolymer block, which is a copolymer block, was calculated by the Hampton method.
In addition, when measuring the amount of vinyl bonds using a hydrogenated copolymer, it measured using the nuclear magnetic resonance apparatus (DPX-400; German BRUKER company make).
(3.1-4) Weight average molecular weight and molecular weight distribution Since the weight average molecular weight of the hydrogenated copolymer is almost equal to the weight average molecular weight of the base non-hydrogenated copolymer, the weight average molecular weight of the hydrogenated copolymer is the base. Obtained as the weight average molecular weight of the non-hydrogenated copolymer. The weight average molecular weight of the base non-hydrogenated copolymer was measured by GPC (using an apparatus manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and the temperature was measured at 35 ° C. The weight average molecular weight was calculated | required from the GPC chromatogram using the calibration curve created using the commercially available standard monodisperse polystyrene type gel with known molecular weight.
The number average molecular weight was determined from the GPC chromatogram.
The molecular weight distribution is determined as a ratio of the obtained weight average molecular weight (Mw) to the obtained number average molecular weight (Mn).

(3.1-5) Hydrogenation rate of double bond of conjugated diene monomer unit The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (DPX-400; manufactured by BRUKER, Germany).
(3.1-6) Peak temperature of loss tangent (tan δ) The loss tangent (tan δ) was determined by measuring a viscoelastic spectrum using a viscoelasticity measuring and analyzing apparatus (model DVE-V4; manufactured by Rheology Co., Ltd.). The measurement frequency is 10 Hz.

(3.2.) Preparation of hydrogenation catalyst The hydrogenation catalyst used in the hydrogenation reaction was produced as follows.
<Preparation of hydrogenation catalyst>
A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, 40 mmol of bis (η-cyclopentadienyl) -di-p-tolyl titanium and a molecular weight of about 1,2-polybutadiene (1,1) After dissolving 150 g of 2-vinyl bond (about 85%), a cyclohexane solution containing 60 mmol of n-butyllithium was added and allowed to react at room temperature for 5 minutes, immediately adding 40 mmol of n-butanol and stirring. As a result, a hydrogenation catalyst was obtained.

(3.3.) Preparation of component (c) hydrogenated copolymer <Polymer 1>
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.
After 10 parts by weight of cyclohexane was charged into the reactor and adjusted to a temperature of 70 ° C., n-butyllithium was 0.076% by weight based on the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by weight of styrene as a monomer (monomer A concentration of 22% by weight) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C.

Next, a cyclohexane solution (monomer concentration of 22% by weight) containing 48 parts by weight of butadiene and 36 parts by weight of styrene was continuously fed to the reactor at a constant rate over 60 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution further containing 8 parts by weight of styrene (monomer concentration: 22% by weight) was added over 3 minutes and reacted for 30 minutes while adjusting the reaction temperature to about 70 ° C. to obtain a copolymer. The resulting copolymer had a styrene content of 52% by weight, a styrene polymer block content of 16% by weight, a vinyl bond content of the butadiene portion of 21% by weight, a weight average molecular weight of 16,000, and a molecular weight. The distribution was 1.2. Next, 100 weight ppm of the hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated block copolymer was obtained. The hydrogenation rate was 99%, and the peak temperature of tan δ (loss tangent) was −15 ° C. As a result of DSC measurement, there was no crystallization peak.

<Polymer 2>
A hydrogenated copolymer similar to polymer 1 was obtained by changing the amount of monomers and the like supplied to the reactor. The obtained results are shown in Table 1.
<Comparative polymer>
As a conventional type styrene elastomer, G1652 grade of styrene- (ethylene butylene) -styrene type (SEBS type) was used (Clayton, USA). The structural results of the polymer are shown in Table 1.

(4) Component (d) Phosphorus flame retardant ・ Triphenyl phosphate (TPP); Daihachi Chemical Co., Ltd.
Cyclic phenoxyphosphazene (FR-1): The acid value obtained by washing and refining the phenoxyphosphazene compound obtained by reacting sodium phenolate with a mixture of 6-membered and 8-membered chlorophosphazene and sodium phenolate. About 0.1 cyclic phenoxyphosphazene

[Examples 1 and 2 and Comparative Example 1]
Each component was charged in the ratio shown in Table 2, and melt-mixed at a kneading temperature of 280 ° C. and a rotational speed of 280 rpm using a 30 mmφ twin screw extruder to prepare pellets. A press plate having a thickness of 2 mm was prepared using this pellet. Using the pellets thus obtained, a covered electric wire having a copper wire of 1.2 mm and an outer diameter of 2 mm was produced at a temperature of 280 [deg.] C. and a linear velocity of 100 m / hour. The following items were evaluated.
(A) Hardness According to JIS K6253, a value after 10 seconds was measured with a durometer type A using a 2 mm flat plate.
(A) Tensile strength and elongation In accordance with JIS K6251, a test piece was cut from a 2 mm flat plate, and the tensile strength and elongation at break were measured. The tensile speed was 500 mm / min and the measurement temperature was 23 ° C.
(C) Scratch resistance Pencil hardness was measured using a 2 mm press plate in accordance with the pencil scratch test of JIS K5400. The load was 300 g. It was judged that the higher the hardness, the better the scratch resistance.

(D) Abrasion resistance characteristics The Gakusei abrasion test was used. Using a 2 mm pressed flat plate, friction material: Kanakin No. 3 cotton cloth Load: 500 gg Friction surface: R shape The volume change after rubbing 10,000 times with a width of 19.5 mm was measured. The smaller this value, the better the wear characteristics.
(E) MFR (index of moldability)
Based on JISK7210, the melt flow index was evaluated under the conditions of 230 ° C. and a load of 2.16 kg.
(F) Meani (formability)
Wire covering molding was performed, and visual evaluation of the degree of occurrence of a crack on the die was performed. As a guide for evaluation, it was determined as follows.
When the surface of the coating material is roughed by a mess in less than 1 hour ×
When the surface of the coating material is roughened in 1 to 5 hours
When the coating surface has not been disturbed for more than 5 hours ○

(G) Flame retardancy A VW-1 flammability test according to UL1581 was performed using the prepared coated wire (copper wire 1.2 mm, outer diameter 2 mm).
(H) Heat deformation resistance Measured according to JIS K6723. A test piece having a thickness of 2.0 mm was loaded with a load of 1 kg / cm ² at 75 ° C. and left for 1 hour. After the test, the test piece was taken out and further left at room temperature for 24 hours. Thereafter, the deformation rate was measured.
(I) Cold resistance The coated electric wire was left in a freezer at −25 ° C. for 4 hours, and then the electric wire was wound around a copper bar of 8 mmφ to confirm the breakage.

[Example 1]
The obtained flame retardant resin composition is excellent in various mechanical performances, and ensures a sufficient level of flame retardancy even in a covered electric wire.

[Example 2]
The obtained flame retardant resin composition is excellent in various mechanical performances, and ensures a sufficient level of flame retardancy even in a covered electric wire. In particular, phosphazene flame retardants can ensure flame retardancy in a small amount.

[Example 3]
The obtained flame retardant resin composition is excellent in various mechanical performances, and ensures a sufficient level of flame retardancy even in a covered electric wire. In particular, compared with conventional wire coating materials, it has low hardness and excellent mechanical property balance.

[Comparative Example 1]
A conventional flame-retardant resin composition using a styrene-based elastomer has poor scratch resistance, wear resistance, and flame retardancy. If it consists of such a flame-retardant resin composition, a coating | covering material will be easily damaged when wiring an electric wire, and the surface will be shaved if it rubs repeatedly. Further, even during the molding, the dies were generated in the extruder die in a short time, the frequency of disassembly and cleaning was increased, and the productivity was not satisfactory.

  The flame retardant resin composition of the present invention has excellent flame retardancy and is excellent in mechanical properties such as flexibility and tensile strength, heat distortion resistance, wear resistance, and moldability. Taking advantage of this characteristic, it can be suitably used for various applications where flame retardancy is required and for various applications where soft vinyl chloride resin is used. Specifically, it can be suitably used for coating materials such as home appliance parts and automobile parts, coating materials such as power cables, communication cables, and power transmission cables, and building materials.

Claims (9)

  (A) 15 parts by weight to less than 45 parts by weight of a polyphenylene ether resin, (b) 0 to 30 parts by weight of a styrene polymer, (c) a conjugated diene monomer unit and a vinyl aromatic monomer unit. Component (a) + component comprising 10 to 60 parts by weight of a hydrogenated copolymer containing a copolymer block obtained by hydrogenating a random copolymer and 3 to 40 parts by weight of (d) a phosphorus flame retardant Flame retardant resin composition in which (b) + component (c) + component (d) = 100 parts by weight. The hydrogenated copolymer (c) is obtained by hydrogenating a polymer block (A) comprising a vinyl aromatic monomer unit and a polymer block comprising a conjugated diene monomer unit having a vinyl bond content of less than 30%. At least 1 obtained by hydrogenating the resulting hydrogenated polymer block (C) and a random copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit and having a vinyl bond content of less than 40%. A hydrogenated copolymer (c) comprising one hydrogenated copolymer block (B) or water having at least two polymer blocks (A) and at least one hydrogenated copolymer block (B) The flame retardant resin composition according to claim 1, which is a hydrogenated copolymer (c) which is a hydrogenated copolymer (c) and has the following characteristics (1) to (6).
(1) The content of the vinyl aromatic monomer unit is more than 40% by weight and less than 95% by weight with respect to the weight of the hydrogenated copolymer;
(2) The content of the polymer block (A) is 0 to 60% by weight with respect to the weight of the hydrogenated copolymer,
(3) The weight average molecular weight is 30,000 to 1,000,000,
(4) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more,
(5) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or more and less than 0 ° C., and (6) the In the case where the hydrogenated copolymer (c) does not have the hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, the temperature is -20 to 80 ° C. There is substantially no crystallization peak due to the at least one hydrogenated copolymer block (B) in the range. The hydrogenated copolymer (c) includes at least one of the hydrogenated polymer block (C), the hydrogenated copolymer block (B) and the polymer block (A), and has the following characteristics (7 The flame retardant resin composition according to claim 1, further comprising:
(7) The content of the hydrogenated polymer block (C) is 10 to 50% by weight and the content of the hydrogenated copolymer block (B) is 30 to 90% by weight based on the weight of the hydrogenated copolymer. %, And the content of the polymer block (A) is 0 to 40% by weight,
(8) The content of the vinyl aromatic monomer unit is more than 40% by weight and less than 90% by weight with respect to the weight of the hydrogenated copolymer.   In the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer (c), a crystallization peak due to the at least one hydrogenated copolymer block (B) is in the range of −20 to 80 ° C. The flame retardant resin composition according to claim 3, wherein the flame retardant resin composition is substantially a hydrogenated copolymer. The hydrogenated copolymer (c) comprises at least two polymer blocks (A) and at least one hydrogenated copolymer block (B), and has the following properties (9) and (10): The flame retardant resin composition according to claim 1, further comprising:
(9) The content of the vinyl aromatic monomer unit is more than 40% by weight and not more than 60% by weight with respect to the weight of the hydrogenated copolymer,
(10) The content of at least two polymer blocks (A) is 5 to 60% by weight based on the weight of the hydrogenated copolymer.   The flame retardant resin according to any one of claims 1 to 5, wherein the phosphorus-based flame retardant (d) is at least one selected from the group consisting of red phosphorus, an organic phosphate compound, a phosphazene compound, and a phosphoramide compound. Composition.   (A) 25-40 parts by weight of a polyphenylene ether resin, (b) 5-15 parts by weight of a styrene polymer, (c) a random copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit. Comprising 30 to 55 parts by weight of a hydrogenated copolymer containing a copolymer block obtained by hydrogenating and (d) 12 to 25 parts by weight of a phosphorus-based flame retardant, component (a) + component (b) + The flame retardant resin composition according to claim 1, wherein component (c) + component (d) = 100 weight.   Component (a) + component (b) + component (c) + component (d) = 100 weight part WHEREIN: 1-30 weight part of component (e) polyolefin resin is added in any one of Claims 1-7 The flame retardant resin composition described   The coating material of the electric wire and cable which consist of a flame-retardant resin composition in any one of Claims 1-8.