JP2010159363A - Thermoplastic polymer composition - Google Patents

Abstract

A polyphenylene ether resin / styrene block copolymer / flame retardant composition that maintains flame retardancy and heat resistance, and can significantly improve flexibility and wear resistance. A thermoplastic polymer composition having improved properties is also provided.
A thermoplastic polymer composition comprising (I) a resin component, (II) a rubber component, and (III) a flame retardant component, wherein (I) the resin component is (a) a polyphenylene ether resin. And (II) a rubber component and (b) a block copolymer having a polymer block A mainly composed of α-methylstyrene units and a polymer block B mainly composed of conjugated diene units and / or hydrogen thereof Including the additive, the mass ratio [(I) / ((I) + (II))] is 0.03 to 0.8, and the mass ratio [(III) / ((I) + (II) + (III))] is 0.01 to 0.67, and is a thermoplastic polymer composition.
[Selection figure] None

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic polymer composition, and more specifically, a thermoplastic polymer that maintains flame retardancy and heat resistance, and can significantly improve flexibility and wear resistance. Relates to the composition.

Conventionally, polyphenylene ether resin / styrene block copolymer / flame retardant composition is excellent in flame retardancy and heat resistance as described in Patent Documents 1 to 4, -Although widely used as a covering material for communication cables, etc., in recent years, more excellent flexibility and wear resistance have been demanded.
However, by adding a softening agent, a styrene block copolymer or the like to the composition to increase the rubber component, the softening can be achieved if a large amount of the rubber component is not added even if the rubber component is added. In addition, if the rubber component content is increased until it can be softened to the required level, the flame retardancy, heat resistance, mechanical properties, wear resistance, etc. are greatly reduced. Actually, it is difficult to obtain a composition excellent in all of flammability, heat resistance, mechanical properties and wear resistance.
On the other hand, Patent Document 5 contains an α-methylstyrene block copolymer and / or a hydrogenated product thereof, and is excellent in the balance of flexibility and moldability, particularly excellent in heat resistance, and in a high temperature atmosphere. A thermoplastic polymer composition is disclosed that provides a shaped body suitable for use.
This composition gives a molded article having an excellent balance of physical properties as described above, but no polyphenylene ether resin is used.

Japanese Patent Laid-Open No. 11-185532 JP 2003-16853 A JP 2005-89700 A JP 2006-299235 A JP 2004-91530 A

  The present invention has been made under such circumstances, and is a polyphenylene ether resin / styrene block copolymer / flame retardant composition, which maintains flame retardancy and heat resistance, and is remarkably An object of the present invention is to provide a thermoplastic polymer composition having improved flexibility and improved wear resistance.

As a result of intensive research in order to achieve the above object, the present inventors have identified a block copolymer having a polymer block mainly composed of α-methylstyrene units as a styrene-based block copolymer. It has been found that the purpose can be achieved by using the ratio. The present invention has been completed based on such findings.
That is, the present invention
A thermoplastic polymer composition comprising (I) a resin component, (II) a rubber component, and (III) a flame retardant component,
The (I) resin component contains (a) a polyphenylene ether resin, and (II) the rubber component contains (b) a polymer block A mainly composed of α-methylstyrene units and a conjugated diene unit. A block copolymer having a polymer block B and / or a hydrogenated product thereof, and a mass ratio of (I) resin component to (I) resin component and (II) total mass of rubber component [(I) / ((I) + (II))] is 0.03 to 0.8, and the mass ratio of (III) flame retardant component to the total mass of (I) resin component and (II) rubber component [( III) / ((I) + (II) + (III))] is 0.01 to 0.67, and a thermoplastic polymer composition is provided.

  According to the present invention, it is a polyphenylene ether resin / styrene block copolymer / flame retardant composition, which can significantly improve flexibility while maintaining flame retardancy and heat resistance. Further, it is possible to provide a thermoplastic polymer composition having improved wear resistance.

  The thermoplastic polymer composition of the present invention (hereinafter sometimes simply referred to as “polymer composition”) includes (I) a resin component, (II) a rubber component, and (III) a flame retardant component as essential components. It is a polymer composition. Hereinafter, each component will be described.

[(I) Resin component]
The (I) resin component contained in the polymer composition of the present invention includes (a) a polyphenylene ether-based resin, and may further include (e) a styrene-based resin as necessary.
((A) polyphenylene ether resin)
In the present invention, the (a) polyphenylene ether-based resin used as the (I) resin component is not particularly limited, and conventionally known ones can be used. For example, a polymer represented by the following general formula (1) can be used.

(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. , M is an integer representing the degree of polymerization.)
The polymer represented by the general formula (1) may be a homopolymer or a copolymer in which two or more are combined. Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrogen atom, chlorine atom, bromine atom, iodine atom, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl. , Cyano, methoxy, ethoxy, phenoxy, nitro and the like.

A preferable polyphenylene ether resin is that R ¹ and R ² in the above formula (1) are alkyl groups, particularly alkyl groups having 1 to 4 carbon atoms, and R ³ and R ⁴ are hydrogen atoms or carbon atoms having 1 to ⁴ carbon atoms. 4 is a polymer that is an alkyl group. m 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 Etc. Among them, a particularly preferable polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether.

Examples of the polyphenylene ether copolymer include a copolymer partially containing an alkyl 3-substituted phenol, for example, a 2,3,6-trimethylphenol unit, 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. Examples of polar groups include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters, acid azides, sulfone groups, nitrile groups, cyano groups, isocyanate esters, amino groups, imide groups, hydroxyl groups, and epoxy groups. , An oxazoline group, a thiol group, and the like. The molecular weight of the polyphenylene ether resin used in the present invention is preferably a number average molecular weight of 1,000 to 100,000, and more preferably in the range of 6,000 to 60,000 in consideration of the balance of various physical properties.
Such a polyphenylene ether resin is used for imparting heat resistance, flame retardancy, abrasion resistance, and the like to the polymer composition of the present invention.

((E) Styrenic resin)
In the resin component (I), the (e) styrene resin used in combination with the (a) polyphenylene ether resin as necessary has an effect of improving moldability, etc. in the polymer composition of the present invention. Used for the purpose of granting. As this (e) styrene resin, either a styrene polymer produced by normal radical polymerization or a styrene polymer having a syndiotactic structure may be used. A rubber-modified styrene resin is also preferably used.
Examples of the styrene polymer produced by normal radical polymerization include a homopolymer of a styrene compound or a copolymer of 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, and the like. 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 the case of exhibiting better chemical resistance. The syndiotactic structure has a three-dimensional structure in which phenyl groups or substituted phenyl groups are alternately positioned in opposite directions with respect to the main chain formed from carbon-carbon bonds, and the tacticity is isotope carbon. Quantified by the nuclear magnetic resonance method ( ^13C -NMR method). ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of consecutive constitutional 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 with a dyad ratio 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 (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoate), a mixture thereof, or a copolymer containing these as a main component. Is included.

Here, examples of 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 obtained by using, for example, a styrenic monomer (the above styrenic monomer) in 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 polymers) can be produced by polymerizing (see, for example, JP-A Nos. 62-104818 and 63-268709), or commercially available ones can also be used. it can.

  In the (I) resin component, the content ratio of the (a) polyphenylene ether resin and (e) styrene resin is in the range of 0.01 to 2.0 in terms of mass ratio [(e) / (a)]. It is preferable that it exists in. If this mass ratio [(e) / (a)] is 0.01 or more, sufficient effect of improving moldability can be exhibited, and if it is 2.0 or less, the heat resistance and flame retardancy are lowered. Can be suppressed. The mass ratio [(e) / (a)] is more preferably 0.02 to 1.0, and still more preferably 0.05 to 0.5.

[(II) Rubber component]
The rubber component (II) contained in the polymer composition of the present invention contains (b) a block copolymer and / or a hydrogenated product thereof, and, if necessary, (c) a rubber softener or (D) A thermoplastic elastomer other than the component (b) can be included.
((B) Block copolymer and / or hydrogenated product thereof)
In the present invention, (II) the block copolymer and / or hydrogenated product thereof used as the rubber component (II) is mainly composed of a polymer block A mainly composed of α-methylstyrene units and a conjugated diene unit. And a block copolymer having a polymer block B and / or a hydrogenated product thereof.
The block copolymer of component (b) and / or a hydrogenated product thereof is used to give the polymer composition of the present invention remarkably flexibility while maintaining flame retardancy and heat resistance. .

<Polymer block A>
The polymer block A constituting the component (b) mainly comprises α-methylstyrene units. The content of α-methylstyrene in the polymer block A is preferably 50% by mass or more and 70% by mass or more from the viewpoint of heat resistance and mechanical strength of the obtained thermoplastic polymer composition. More preferably, it is more preferably 90% by mass or more.
The polymer block A may be copolymerized with other monomers within a range that does not impair the object of the present invention, usually within a range of 50% by mass or less. If it is a body, there is no limitation. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2- Aromatic vinyl compounds such as ethyl-4-benzylstyrene and 4- (phenylbutyl) styrene; Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are preferred, especially styrene. P-methylstyrene is preferred. The form in the case of copolymerizing another monomer with the polymer block A may be random or tapered.

The weight average molecular weight of the polymer block A is usually in the range of 1,000 to 50,000, preferably in the range of 2,000 to 40,000, and more preferably in the range of 3,000 to 35,000. When the weight average molecular weight of the polymer block A is less than 1,000, the resulting thermoplastic polymer composition may be inferior in wear resistance and mechanical strength, whereas when the weight average molecular weight exceeds 50,000. (B) The block copolymer may have an excessively high melt viscosity, resulting in poor processability. In addition, the weight average molecular weight as used in this specification is the molecular weight of polystyrene conversion calculated | required by the gel permeation chromatography (GPC) measurement.
(B) The content of the polymer block A in the block copolymer is preferably from 5 to 70 mass%, more preferably from 10 to 60 mass%, further preferably from 20 to 50 mass%, particularly preferably from 25 to 40 mass%. preferable. When the content of the polymer block A is less than 5% by mass, the resulting thermoplastic polymer composition may be inferior in wear resistance and mechanical strength, whereas when it exceeds 70% by mass, b) When the melt viscosity of the block copolymer becomes too high and the processability is lowered, the thermoplastic polymer composition becomes poor in flexibility, and when a rubber softener described later is used in combination. , Bleeding tends to occur.

<Polymer block B>
The polymer block B constituting the component (b) is mainly composed of conjugated diene units. Examples of the conjugated diene compound that forms the conjugated diene unit include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. A conjugated diene compound can be used individually or in combination of 2 or more types. Among these, 1,3-butadiene, isoprene, or a mixture of 1,3-butadiene and isoprene is preferable. When two or more types are used in combination, any of random, block, and tapered shapes may be used.
Further, the polymer block B is within the range not impairing the object of the present invention, usually 30% by mass or less, preferably 10% by mass or less, and other anionic polymerizable monomers other than the conjugated diene compound. The body may be copolymerized. Examples of the other copolymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and the like can be given. An aromatic vinyl compound can be used individually or in combination of 2 or more types. The form in the case of copolymerizing the conjugated diene compound and the aromatic vinyl compound may be either random or tapered.

(B) The content of the polymer block B in the block copolymer is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, still more preferably 50 to 80% by mass, and particularly preferably 60 to 75% by mass. preferable. When the content of the polymer block B is less than 30% by mass, the melt viscosity of the (b) block copolymer tends to be too high, and the processability tends to be lowered. On the other hand, when the content exceeds 95% by mass, In this case, the wear resistance and mechanical strength may be inferior.
The weight average molecular weight of the polymer block B is usually 10,000 to 499,000, preferably in the range of 20,000 to 320,000, and more preferably in the range of 30,000 to 300,000. When the weight average molecular weight of the polymer block B is less than 10,000, the resulting thermoplastic polymer composition may be inferior in heat resistance, and when the weight average molecular weight exceeds 499,000, (b) The melt viscosity of the coalescence becomes too high, and the processability may be inferior.

<Binding mode of polymer block A and polymer block B>
(B) The bonding mode of the polymer block A and the polymer block B in the block copolymer may be linear, branched, radial, or any combination thereof. For example, when the polymer block A is represented by A and the polymer block B is represented by B, an AB diblock copolymer, an ABA type triblock copolymer, an ABBA type, Tetrablock copolymer, (AB) nX type copolymer (X represents a coupling agent residue, and n represents an integer of 3 or more). These block copolymers can be used singly or in combination of two or more. Among these, an ABA type triblock copolymer or a mixture of an AB type triblock copolymer and an AB type diblock copolymer is preferable.
Here, in the present specification, when the same type of polymer block is linearly bonded via a divalent coupling agent or the like, the entire bonded polymer block is handled as one polymer block. It is. Accordingly, including the above examples, the polymer block that should be expressed strictly as YXY (X represents a coupling agent residue) must be distinguished from the single polymer block Y in particular. Except for some cases, Y is displayed as a whole. In the present specification, this type of polymer block containing a coupling agent residue is handled as described above, so that, for example, it contains a coupling agent residue, and strictly speaking, YZXXZY ( A block copolymer to be represented as X represents a coupling agent residue is represented as YZY, and is treated as an example of a triblock copolymer.
Further, the block copolymer (b) used in the present invention is copolymerized with a polymer block C composed of other monomers such as methyl methacrylate and styrene within a range not to impair the purpose of the present invention. Also good. In this case, the structure of the block copolymer includes an ABC type triblock copolymer, an ABCA type tetrablock copolymer, and an ABCA type tetrablock copolymer. Examples include coalescence.
Furthermore, it is preferable that the (b) block copolymer is hydrogenated from the viewpoint of improving heat resistance and weather resistance. The proportion of hydrogenation is not particularly limited, but at least (b) 30% or more of the carbon-carbon double bonds based on the conjugated diene unit in the block copolymer are preferably hydrogenated, More preferably, 50% or more is hydrogenated, more preferably 80% or more is hydrogenated, and particularly preferably 90% or more is hydrogenated.
(B) The block copolymer contains a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain or at the molecular end unless the purpose of the present invention is impaired. It may be.

<(B) Production of block copolymer and / or hydrogenated product thereof>
"polymerization"
The block copolymer can be produced by an anionic polymerization method, and the following specific synthesis examples are shown.
(1) After polymerization of a conjugated diene compound using a dianionic initiator in a tetrahydrofuran solvent, α-methylstyrene is sequentially polymerized under a temperature condition of −78 ° C. to obtain an ABA type block copolymer. Method (see Macromolecules, Vol. 2, pages 453-458 (1969)).
(2) After bulk polymerization of α-methylstyrene using an anionic initiator, conjugated dienes are sequentially polymerized, and then a coupling reaction is performed with a coupling agent such as tetrachlorosilane, and (AB) nX A method for obtaining a mold block copolymer (see Kautsch. Gummi, Kunstst., 37, 377-379 (1984); Polym. Bull., 12, 71-77 (1984)).
(3) In a nonpolar solvent, an organolithium compound is used as a polymerization initiator, and in the presence of a polar compound having a concentration of 0.1 to 10% by mass, at a temperature of −30 to 30 ° C., a concentration of 5 to 50% by mass. A method of polymerizing α-methylstyrene, polymerizing a conjugated diene to the resulting living polymer, and then adding a coupling agent to obtain an ABA block copolymer.
(4) In a nonpolar solvent, an organolithium compound is used as a polymerization initiator, and in the presence of a polar compound having a concentration of 0.1 to 10% by mass, at a temperature of −30 to 30 ° C., a concentration of 5 to 50% by mass. α-methylstyrene is polymerized, the resulting living polymer is polymerized with a conjugated diene compound, and the resulting α-methylstyrene polymer block and conjugated diene polymer block block copolymer living polymer other than α-methylstyrene A method for obtaining an ABC type block copolymer by polymerizing the anionic polymerizable monomer.
Among the above methods, the methods (3) and (4) are preferable, and the method (3) is more preferable.

Examples of the organic lithium compound used as a polymerization initiator in the above method include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and tetraethylenedilithium. The dilithium compound etc. are mentioned.
The solvent used in the polymerization of α-methylstyrene is a nonpolar solvent, for example, an aliphatic hydrocarbon such as cyclohexane, methylcyclohexane, n-hexane, n-pentane, an aromatic hydrocarbon such as benzene, toluene, xylene, etc. Is mentioned.
The polar compound used in the polymerization of α-methylstyrene is a compound that does not have a functional group (hydroxyl group, carbonyl group, etc.) that reacts with anionic species and has a hetero atom such as an oxygen atom or a nitrogen atom in the molecule. Examples thereof include dimethyl ether, diethyl ether, monoglyme, N, N, N ′, N′-tetramethylethylenediamine, triethylamine, N-methylmorpholine, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and the like.
The concentration of the polar compound in the reaction system is such that when α-methylstyrene is polymerized at a high conversion rate and the subsequent conjugated diene compound is polymerized, the amount of 1,4-bond in the conjugated diene polymer block is controlled. From the viewpoint, it is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 3% by mass.

The α-methylstyrene concentration in the reaction system is preferably in the range of 5 to 50% by mass from the viewpoint of the viscosity of the reaction solution in the latter stage of polymerization by polymerizing α-methylstyrene at a high conversion rate. A range of 40% by mass is more preferred.
The above conversion rate means the ratio of unpolymerized α-methylstyrene converted to a block copolymer by polymerization, and in the present invention, the degree is preferably 70% or more, and 85% More preferably.
The temperature conditions during the polymerization of α-methylstyrene are the ceiling temperature of α-methylstyrene (the temperature when the polymerization reaction reaches an equilibrium state and does not substantially proceed), the polymerization rate of α-methylstyrene, the living property, etc. From the point of -30-30 degreeC is preferable, More preferably, it is -20-10 degreeC, More preferably, it is -15-0 degreeC. By setting the polymerization temperature to 30 ° C. or less, α-methylstyrene can be polymerized at a high conversion rate, and the ratio of the living polymer to be generated is small, so that the homopoly α- Suppressing the mixing of methylstyrene, physical properties are not impaired, and by setting the polymerization temperature to −30 ° C. or higher, the reaction solution can be stirred without increasing the viscosity in the latter stage of polymerization of α-methylstyrene, and in a low temperature state This is economically preferable because it does not increase the cost required to maintain the temperature.

In the above method, as long as the characteristics of the α-methylstyrene polymer block are not impaired, another vinyl aromatic compound may coexist at the time of polymerization of α-methylstyrene, and this may be copolymerized with α-methylstyrene. . Examples of the vinyl aromatic compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. A vinyl aromatic compound can be used individually or in combination of 2 or more types.
Living poly α-methylstyryl lithium is produced by polymerization of α-methylstyrene using organolithium as a polymerization initiator, and this is then polymerized with a conjugated diene compound. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and these compounds are used alone or in combination. Two or more kinds can be used in combination. Among these, a preferable conjugated diene compound is 1,3-butadiene or isoprene.

The conjugated diene compound is subjected to polymerization by being added to the reaction system. The method for adding the conjugated diene compound to the reaction system is not particularly limited, and the conjugated diene compound may be added directly to the living poly α-methylstyryllithium solution or diluted with a solvent.
The method for diluting a conjugated diene compound in a solvent is to add the conjugated diene compound and then dilute with the solvent, or simultaneously add the conjugated diene compound and the solvent, or dilute with the solvent and then the conjugated diene compound. May be added. Suitably, 1 to 100 molar equivalents, preferably 5 to 50 molar equivalents of the conjugated diene compound is added to the living poly α-methylstyryl lithium, and the living active terminal is modified, and then diluted with a solvent. Then, the method of introducing the remaining conjugated diene compound and performing the polymerization reaction at a temperature exceeding 30 ° C., preferably 40 to 80 ° C., is recommended.
In changing the active terminal of the living poly α-methylstyryl lithium, instead of the conjugated diene compound, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene Vinyl aromatic compounds such as 1,1-diphenylethylene may be used.
Examples of the solvent that can be used for dilution include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. .
The block copolymer (b) thus obtained is coagulated by pouring the polymerization reaction solution into methanol or the like, and then heated or dried under reduced pressure, or the polymerization reaction solution is poured into boiling water, and the solvent is used as a co-polymer. It can be obtained by heating or vacuum drying after so-called steam stripping which is removed by boiling.

《Hydrogenation》
The block polymer (b) composed of an α-methylstyrene polymer block and a conjugated diene polymer block has excellent heat resistance and weather resistance, and therefore, carbon-based on the conjugated diene unit in the block copolymer— It is preferable that at least a part (70% or more) of the carbon double bond is hydrogenated.

For example, a polyfunctional coupling agent is added to a living polymer of a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block obtained by copolymerizing a conjugated diene with living poly α-methylstyryl lithium. By reacting, a triblock or radial teleblock type (b) block copolymer can be produced.
The block copolymer in this case is a mixture containing diblock, triblock, and radial teleblock block copolymers at an arbitrary ratio, which is obtained by adjusting the amount of the polyfunctional coupling agent used. May be. Multifunctional coupling agents include phenyl benzoate, methyl benzoate, ethyl benzoate, methyl acetate, ethyl acetate, methyl pivalate, ethyl pivalate, phenyl pivalate, α, α'-dichloro-o-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-p-xylene, bis (chloromethyl) ether, dibromomethane, diiodomethane, dimethyl phthalate, dichlorodimethylsilane, dichlorodiphenylsilane, trichloromethylsilane, Examples thereof include tetrachlorosilane and divinylbenzene.

A triblock or radial teleblock type (b) block copolymer obtained by reacting a living polymer of a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block with a polyfunctional coupling agent When hydrogenating the coalescence, an active hydrogen compound such as alcohols, carboxylic acids or water is added as necessary to stop the coupling reaction, and then water is added in an inert organic solvent according to a known method. By hydrogenating in the presence of a hydrogenation catalyst, a hydrogenated (b) block copolymer can be obtained.
Also, in the case of hydrogenating the block copolymer (b) consisting of an α-methylstyrene polymer block and a conjugated diene polymer block, an alcohol is used after polymerizing the conjugated diene compound with living poly α-methylstyryl lithium. The polymerization reaction was stopped by adding active hydrogen compounds such as carboxylic acids, carboxylic acids and water, followed by hydrogenation in the presence of a hydrogenation catalyst in an inert organic solvent according to a known method. ) It can be a block copolymer.

  An anionically polymerizable monomer is polymerized into an unhydrogenated block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block, and a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block. A polyfunctional coupling agent to a living polymer of a non-hydrogenated ABC type triblock copolymer obtained by the process or a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block The unhydrogenated triblock or radial teleblock type block copolymer obtained by reacting (both included in the block copolymer (b) used in the present invention) was used for the production thereof. It can be directly used for hydrogenation without replacing the solvent.

The hydrogenation reaction is made of Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a carrier such as carbon, alumina, diatomaceous earth, or the like; Group 8 metal such as nickel or cobalt Ziegler catalyst comprising a combination of an organometallic compound and an organoaluminum compound such as triethylaluminum or triisobutylaluminum, or an organolithium compound; a bis (cyclopentadienyl) compound of a transition metal such as titanium, zirconium or hafnium and lithium; In the presence of a hydrogenation catalyst such as a metallocene catalyst comprising a combination of organometallic compounds such as sodium, potassium, aluminum, zinc or magnesium, the reaction is carried out under conditions of a reaction temperature of 20 to 100 ° C. and a hydrogen pressure of 0.1 to 10 MPa. be able to.
The unhydrogenated block copolymer is desirably hydrogenated until 70% or more, particularly preferably 90% or more, of the carbon-carbon double bonds based on the conjugated diene units in the conjugated diene polymer block are saturated. Thereby, the weather resistance of the block copolymer can be enhanced. Hydrogenation rate of carbon-carbon double bond in conjugated diene polymer block in hydrogenated block copolymer is determined by iodine titration method, infrared spectroscopic spectrum measurement, nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) It can be calculated using an analysis means such as measurement.

  The 1,4-bond amount of the conjugated diene polymer block B of the (b) unhydrogenated or hydrogenated block copolymer (α-methylstyrene block copolymer) produced by the above method is 20 mol% or more. Preferably, it is in the range of 30 to 95 mol%, more preferably in the range of 35 to 80 mol%. When the amount of 1,4-bond is less than 20 mol%, the Tg of the rubber part composed of conjugated diene units is increased, and the flexibility and rubber elasticity of the resulting thermoplastic polymer composition tend to be inferior.

<Properties of (b) Block Copolymer and / or Hydrogenated Product>
In the thermoplastic polymer composition of the present invention, the weight average molecular weight of the block copolymer and / or its hydrogenated product used as component (b) is preferably in the range of 30,000 to 500,000, The range of 3,000 to 300,000 is more preferred. (B) When the number average molecular weight of the block copolymer and / or its hydrogenated product is less than 30,000, the resulting thermoplastic polymer composition tends to have poor mechanical strength, while the number average molecular weight is 500, When it exceeds 000, the melt viscosity of (b) the block copolymer and / or its hydrogenated product becomes too high, and the processability may be inferior.

  As the (b) block copolymer in the present composition, those obtained by the above method are preferably used. In particular, in a nonpolar solvent, an organolithium compound is used as a polymerization initiator, and in the presence of a polar compound having a concentration of 0.1 to 10% by mass, an α- of 5 to 50% by mass at a temperature of −30 to 30 ° C. When polymerizing methylstyrene and then polymerizing the conjugated diene compound, first, 1 to 100 molar equivalents of the conjugated diene compound is polymerized with respect to the living poly α-methylstyryl lithium to form the polymer block B1, and then the reaction system is It is desirable that the block copolymer is obtained by polymerizing by adding a conjugated diene compound at a temperature exceeding 30 ° C. to form the polymer block B2, from the viewpoint of excellent low-temperature characteristics. That is, in this case, the polymer block B includes the polymer block B1 and the polymer block B2.

The block copolymer (b) is not limited to a linear or branched structure as its structure, but among them, a block copolymer having at least one (A-B1-B2) structure is preferable. B1-B2-B2-B1-A type copolymer, A-B1-B2-B2-B1-A type copolymer and A-B1-B2 type copolymer mixture, (A-B1-B2) pX Type copolymer (X represents a coupling agent residue, p is an integer of 2 or more), (A-B1-B2) mixture of pX type copolymer and A-B1-B2 type copolymer Etc. Among these, from the viewpoint of wear resistance and mechanical properties, (A-B1-B2) pX type copolymer, or (A-B1-B2) pX type copolymer and A-B1-B2 type copolymer And a mixture of (A-b1-b2) ₂ X-type copolymer or (A-b1-b2) ₂ X-type copolymer and A-b1-b2 type copolymer is particularly preferred.
The weight average molecular weight of the polymer block B1 in the block copolymer (b) is preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and 1,4 of the polymer block b1. -The amount of bonds is preferably less than 30 mol%. Further, the weight average molecular weight of the polymer block B2 in the block copolymer is preferably 10,000 to 498,000, more preferably 20,000 to 300,000, and 1,4- of the polymer block B2. The bonding amount is preferably 30 mol% or more, more preferably 35 to 95 mol%, still more preferably 40 to 80 mol%.

((C) Rubber softener)
In the (II) rubber component, the (b) block copolymer and / or hydrogenated product thereof is used in combination with the (b) block copolymer and / or the hydrogenated product thereof as needed. Further, it is used for imparting flexibility. The rubber softener is preferably a non-aromatic one from the viewpoint of imparting flexibility, and can be appropriately selected from conventionally known ones.
Examples of rubber softeners include paraffinic process oil, naphthenic process oil, aromatic process oil, ethylene and α-olefin oligomers, liquid paraffin, polybutene, low molecular weight polybutadiene, low molecular weight polyisoprene, and hydrogenated low molecular weight polybutadiene. , Hydrogenated low molecular weight polyisoprene, vegetable oil and the like. Among these, paraffinic process oil, ethylene and α-olefin oligomers, and liquid paraffin are preferable, and paraffinic process oil is particularly preferable. Examples of the paraffinic process oil include “Diana Process Oil” series, which is commercially available from Idemitsu Kosan Co., Ltd.
The rubber softeners can be used alone or in combination of two or more.
In the rubber component (II), (b) the mass ratio [(c) / (b)] of the block copolymer and / or its hydrogenated product to the (c) rubber softener is 0.01. It is preferable that it is -3.0. When this mass ratio is 0.01 or more, the softening effect is satisfactorily exhibited. On the other hand, when it is 3.0 or less, flame retardancy and bleeding of rubber softener can be suppressed. The mass ratio [(c) / (b)] is more preferably 0.05 to 1.5, and still more preferably 0.1 to 1.0.

((D) thermoplastic elastomer)
In the rubber component (II), the (b) block copolymer and / or the hydrogenated product thereof is used together as necessary. (D) The thermoplastic elastomer is molded into the polymer composition of the present invention. It is used for imparting a property improving effect. This (d) thermoplastic elastomer is a thermoplastic elastomer other than the component (b) described above, for example, a polymer block C mainly composed of vinyl aromatic compound units and a polymer block D mainly composed of conjugated diene units. And / or a hydrogenated product thereof may be used.

<Polymer block C>
(D) A block copolymer having a polymer block C mainly composed of vinyl aromatic compound units and a polymer block D mainly composed of conjugated diene units as a thermoplastic elastomer (hereinafter referred to as (d) block copolymer) And / or hydrogenated product thereof, the polymer block C constituting the (d) block copolymer is mainly composed of aromatic vinyl compound units other than α-methylstyrene units. .
Examples of the aromatic vinyl compound unit other than the α-methylstyrene unit constituting the polymer block C include styrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene, p. -Propylstyrene, pt-butylstyrene, p-cyclohexylstyrene, p-dodecylstyrene, 2-ethyl-4-benzylstyrene, p- (phenylbutyl) styrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene And units based on methoxystyrene, indene and the like, and may have one or more of these units. Of these, units based on styrene are preferred.

  The polymer block C may have a small amount of structural units based on other polymerizable monomers as necessary, together with the structural units based on the aromatic vinyl compound other than α-methylstyrene. In that case, the proportion of the structural units based on the other polymerizable monomers is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total mass of the polymer block C. Examples of other polymerizable monomers in that case include methacrylic acid esters, acrylic acid esters, 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. The bonding form of the units based on these other polymerizable monomers may be any form such as random or tapered.

<Polymer block D>
The polymer block D constituting the (d) block copolymer is mainly composed of conjugated diene units. Examples of the conjugated diene unit constituting the polymer block D include units based on isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like. The polymer block D may be composed of only one kind of units based on these conjugated diene compounds or may be composed of two or more kinds, among which units based on butadiene, isoprene, or a mixture of butadiene and isoprene. It is preferable that it is comprised from these. When the polymer block D has structural units based on two or more kinds of conjugated diene compounds, the bonding form thereof may be random, block, tapered, or a combination of two or more thereof. it can.

Further, the polymer block D is within the range not impairing the object of the present invention, usually 30% by mass or less, preferably 10% by mass or less, and other anionic polymerizable monomers other than the conjugated diene compound. The body may be copolymerized. Examples of the other copolymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and the like can be given. An aromatic vinyl compound can be used individually or in combination of 2 or more types. The form in the case of copolymerizing the conjugated diene compound and the aromatic vinyl compound may be either random or tapered.
In addition, in the block copolymer (d), the polymer block D is hydrogenated (hydrogenated) in part or all of the carbon-carbon double bonds in the polymer block D from the viewpoint of weather resistance, heat resistance, and the like. It is preferable that In this case, the hydrogenation rate of the polymer block D is preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 95 mol% or more.
(D) The hydrogenation rate of the polymer block D in the block copolymer is determined based on the content of the carbon-carbon double bond in the polymer block D by the iodine value measurement method, infrared spectroscopy, nuclear magnetic resonance method, etc. And can be obtained from the measured value.

The polymer block D is preferably the following polymer block from the viewpoints of weather resistance, heat resistance and the like of the thermoplastic polymer composition of the present invention.
(I) A hydrogenated polyisoprene block obtained by hydrogenating a part or all of carbon-carbon double bonds based on isoprene units of a polyisoprene block comprising isoprene units.
(Ii) A hydrogenated polybutadiene block in which a part or all of carbon-carbon double bonds based on butadiene units of a polybutadiene block comprising butadiene units are hydrogenated.
(Iii) A mixture of isoprene and butadiene in which some or all of the carbon-carbon double bonds based on the isoprene unit and butadiene unit of the copolymer block consisting of a mixture of isoprene and butadiene comprising isoprene units and butadiene units are hydrogenated. A copolymer block consisting of

In the above (i) hydrogenated polyisoprene block, the unit derived from isoprene is a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ ) = before hydrogenation. CH—CH ₂ —; 1,4-bonded isoprene unit], isopropenylethylene group [—CH (C (CH ₃ ) ═CH ₂ ) —CH ₂ —; 3,4-bonded isoprene unit] and 1- It comprises at least one group selected from the group consisting of a methyl-1-vinylethylene group [—C (CH ₃ ) (CH═CH ₂ ) —CH ₂ —; 1,2-bonded isoprene unit]; The ratio of each unit is not particularly limited.
In the above (ii) hydrogenated polybutadiene block, before the hydrogenation, 70 to 10 mol%, particularly 65 to 20 mol% of the butadiene unit is a 2-butene-1,4-diyl group (—CH ₂ —CH _2). ═CH—CH ₂ —; 1,4-bonded butadiene unit), and 30 to 90 mol%, particularly 35 to 80 mol% is a vinylethylene group [—CH (CH═CH ₂ ) —CH ₂ —; 2-bonded butadiene unit] is preferable. When the 1,4-bond amount in the polybutadiene block is in the above-described range of 70 to 10 mol%, rubber elasticity is improved.

In the copolymer block consisting of the mixture of (iii) isoprene and butadiene, before the hydrogenation, the units derived from isoprene are 2-methyl-2-butene-1,4-diyl group, isopropenylethylene group and Units derived from 1-methyl-1-vinylethylene group and derived from butadiene are composed of 2-butene-1,4-diyl group and vinylethylene group, and the ratio of each unit is not particularly limited. In a copolymer block composed of a mixture of isoprene and butadiene, the arrangement of isoprene units and butadiene units may be random, block, or tapered.
In the case of a copolymer block composed of a mixture of isoprene and butadiene, the molar ratio of isoprene units: butadiene units is preferably 10:90 to 90:10 from the viewpoint of improving rubber elasticity, and 30:70 to 70: 30 is more preferable.

<Properties of (d) Block Copolymer>
When the polymer block C is represented by C and the polymer block D is represented by D, (d) the block copolymer is a diblock copolymer represented by CD, C-D-C, D-C-D. , C-D-C-D, C-D-C-D-C, (C-D) _q (q represents an integer of 3 or more), (C-D) _r -C (r represents an integer of 2 or more), (DC) _s -D (s represents an integer of 2 or more), (CD) _t -X (t is an integer of 3 or more, X Is a hydrogenated product of various multi-block copolymers represented by, for example, a coupling agent residue, and any of them may be used. Among them, the (d) block copolymer is a hydrogenated product of a triblock copolymer represented by C-D-C, in particular, so that the production stability of the block copolymer and the thermoplastic weight obtained can be obtained. It is preferable from the viewpoint of the flexibility of the combined composition.

  In this composition, the weight average molecular weight of the block copolymer used as the thermoplastic elastomer of the component (d) and its hydrogenated product is preferably in the range of 30,000 to 500,000. If this weight average molecular weight is in the above range, the resulting composition can be excellent in fluidity (molding processability). This number weight average molecular weight is more preferably 40,000 to 300,000.

<(D) Production of hydrogenated block copolymer>
"polymerization"
(D) The manufacturing method of a block copolymer is not limited at all, For example, it can manufacture by performing well-known polymerization methods, such as ion polymerization methods, such as anionic polymerization and cationic polymerization, and radical polymerization method. For example, in the case of the anionic polymerization method, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an organic solvent inert to a polymerization reaction such as n-hexane and cyclohexane using an alkyl lithium compound as an initiator to block copolymerization. Form a coalescence.

《Hydrogenation》
The hydrogenation reaction of the (d) block copolymer obtained above is performed, for example, by reacting the (d) block copolymer in a saturated hydrocarbon solvent such as cyclohexane in the presence of a catalyst, usually at a reaction temperature. Can be carried out under the conditions of a hydrogen pressure of 0.1 to 10 MPa in a range of 20 to 100 ° C., and a hydrogenated product of the (d) block copolymer can be obtained.
As a catalyst for this hydrogenation reaction, Raney nickel; heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth; Ziegler-type catalyst consisting of a combination of an organometallic compound composed of a Group 10 metal and an organoaluminum compound such as triethylaluminum or triisobutylaluminum, or an organolithium compound; Enyl) compounds and metallocene catalysts composed of a combination of lithium, sodium, potassium, aluminum, zinc, magnesium and other organic metal compounds.

  In the rubber component (II) used in the polymer composition of the present invention, the mass ratio [(d) / (b) block copolymer and / or hydrogenated product thereof to (d) thermoplastic elastomer described above] (B)] is preferably 0.01 to 5.0. When the mass ratio [(d) / (b)] is 0.01 or more, a good moldability improving effect is exhibited. On the other hand, when the mass ratio is 5.0 or less, flame retardancy, wear resistance, mechanical strength, and heat resistance are exhibited. Deterioration can be suppressed. The mass ratio [(d) / (b)] is more preferably 0.05 to 3.0, and still more preferably 0.1 to 1.5.

[(III) Flame retardant component]
The (III) flame retardant component contained in the polymer composition of the present invention is preferably a non-halogen flame retardant from the viewpoint of environmental hygiene during combustion. For example, magnesium hydroxide, aluminum hydroxide, hydrated silicic acid Examples thereof include metal hydrates having a hydroxyl group or crystal water such as aluminum, hydrated magnesium silicate and hydrotalcite, phosphoric acid compounds such as polyphosphate amines and polyphosphate esters, and silicon compounds. Among these, a phosphoric acid compound is preferable from the viewpoint of processability and lightness, and a phosphate ester flame retardant is particularly preferable.
(Phosphate ester flame retardant)
Examples of phosphate ester flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Examples thereof include dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, and compounds obtained by substituting these with various substituents. Moreover, the condensed phosphate ester flame retardant represented by the following general formula (2) can also be preferably used.

(In formula, Ar < ¹ > -Ar < ⁴ > shows a phenyl group, a tolyl group, or a xylyl group each independently, and u is an integer of 1-10. When u is two or more, several Ar < ⁴ > is respectively the same. R ⁵ represents a 1,4-phenylene group, a 1,3-phenylene group, a 4,4′-biphenylene group, or a 2,2-propylidenebisphenylene group.
In the present invention, the (III) flame retardant component may be used alone or in combination of two or more.

[Content Ratio of Each Component in Polymer Composition]
It shows below about the content rate of each component in the thermoplastic polymer composition of this invention.
The mass ratio [(I) / ((I) + (II))] of (I) resin component to the total mass of (I) resin component and (II) rubber component is 0.03 to 0.8. It is necessary, and it is preferably 0.10 to 0.65, and more preferably 0.15 to 0.55. If the mass ratio [(I) / ((I) + (II))] is less than 0.03, heat resistance and flame retardancy cannot be obtained, while if it exceeds 0.8, flexibility is lowered.
Further, the mass ratio [(III) / ((I) + (II) + (III))] of (III) flame retardant component to the total mass of (I) resin component and (II) rubber component is 0.01. It needs to be -0.67, Preferably it is 0.05-0.54, More preferably, it is 0.1-0.49. If the mass ratio [(III) / ((I) + (II) + (III))] is less than 0.01, flame retardancy cannot be obtained, while if it exceeds 0.67, flexibility and mechanical strength are reduced. To do.

[Other optional ingredients]
In the thermoplastic polymer composition of the present invention, as an optional component other than the component (c), the component (d), and the component (e), as long as it does not impair the properties of the composition, other components can be used. Polymers, inorganic fillers, crosslinking agents, antioxidants, light stabilizers, UV absorbers, antistatic agents, lubricants, colorants, antibacterial agents, foaming agents, tackifying resins, electromagnetic wave sealing agents, heavy metal inertness An agent and the like can be appropriately contained.
(Other polymers)
Examples of the other polymer include polyolefin resins; polyamide 6, polyamide 6 · 6, polyamide 6 · 10, polyamide 11, polyamide 12, polyamide 6 · 12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide. Polyamide resins such as xylene group-containing polyamides; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyoxymethylene homopolymers, polyoxymethylene copolymers, etc. Polyoxymethylene resin; Polycarbonate resin; Ethylene / propylene copolymer rubber (EPM), Ethylene / propylene / non-conjugated diene copolymer rubber (EPDM); Styrene / butadiene copolymer Combined rubber, styrene / isoprene copolymer rubber or hydrogenated product thereof or modified product thereof; natural rubber; synthetic isoprene rubber, liquid polyisoprene rubber and hydrogenated product or modified product thereof; chloroprene rubber; acrylic rubber; butyl rubber; Examples thereof include butadiene rubber; epichlorohydrin rubber; silicone rubber; fluoro rubber; chlorosulfonated polyethylene; urethane rubber; polyurethane elastomer; polyamide elastomer; polyester elastomer;
In addition, when other polymers are contained, the content is preferably within a range in which the mechanical properties of the obtained thermoplastic polymer composition are not impaired, and the total amount of the (I) component and the (II) component is 100 mass. It is preferable that it is 200 mass parts or less with respect to a part.

(Inorganic filler)
Examples of inorganic fillers include calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate, mica, glass fiber, whisker, carbon fiber, magnesium carbonate, glass bead powder, glass hollow sphere powder, resin hollow Examples thereof include spherical powder, metal powder, kaolin, graphite, molybdenum disulfide, zinc oxide, and the like, and one or more of these can be contained. When the inorganic filler is contained, the content thereof is preferably within a range that does not impair the object of the present invention. Generally, the total amount of the (I) component and the (II) component is 100 parts by mass. On the other hand, it is preferably 50 parts by mass or less.

(Crosslinking agent)
The composition may contain a crosslinking agent as necessary and can be used after crosslinking.
Examples of the cross-linking agent include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (T-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t-butylcumyl peroxide Such as organic peroxides It is below. In that case, you may use a crosslinking adjuvant together.

[Preparation of Thermoplastic Polymer Composition]
As a method for preparing the thermoplastic polymer composition of the present invention, a method used for preparing a normal thermoplastic resin composition or a thermoplastic elastomer composition can be employed. Specifically, using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll, various kneaders, the components (I), (II), (III), and as necessary It can prepare by melt-kneading the mixture which consists of various additive components used according to it.
The thermoplastic polymer composition of the present invention thus prepared maintains flame retardancy and heat resistance, and has greatly improved flexibility. Sheet, film, tube, hollow molded body, mold It can be formed into a molded body and other various molded bodies and used for various applications.
As the molding method, conventionally known methods such as extrusion molding, injection molding, hollow molding, compression molding, press molding, calendar molding, etc. can be employed. Moreover, it can also be compounded with other members, for example, polymer members such as polyethylene, polypropylene, olefin elastomers, ABS resins, polyamides, metal, wood, cloth, etc., by a two-color molding method.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition, the physical property evaluation in each example was performed by the method shown below.
(1) Breaking strength, breaking elongation A sheet having a thickness of 2 mm was obtained by press-molding the thermoplastic polymer compositions obtained in Examples and Comparative Examples at 260 ° C. A dumbbell No. 5 type test piece conforming to JIS K 6251 was punched out from this sheet, and a tensile test was performed under a temperature condition of 23 ° C. and a tensile speed condition of 500 mm / min to measure the breaking strength and breaking elongation. .
(2) Shore hardness D
According to ASTM-D-2240, Shore hardness (D type) was measured at a measurement temperature of 23 ° C. using a 6 mm thickness test piece.
(3) Vicat softening point temperature In accordance with JIS K 7206, the Vicat softening point temperature under a 9.8 N load was measured.
(4) DIN Wear Amount According to JIS K 6264, a DIN wear amount at a wear distance of 40 m was measured under a 10N load.
(5) Flame retardancy A 1.6 mm thick vertical flammability test was conducted according to UL-94.

<Production Example 1 (Production of hydrogenated product of (b) block copolymer)>
(I) 90.9 g of α-methylstyrene, 138 g of cyclohexane, 15.2 g of methylcyclohexane and 3.1 g of tetrahydrofuran were charged into a pressure-resistant vessel equipped with a stirrer purged with nitrogen. To this mixed solution, 9.4 ml of sec-butyllithium (1.3 M cyclohexane solution) was added and polymerized at −10 ° C. for 3 hours. When the weight average molecular weight of poly α-methylstyrene (polymer block A) 3 hours after the start of polymerization was measured by GPC, it was 6,600 in terms of polystyrene, and the polymerization conversion rate of α-methylstyrene was 89%. It was. Next, 23 g of butadiene was added to the reaction mixture and stirred at −10 ° C. for 30 minutes to polymerize the polymer block B1, and then 930 g of cyclohexane was added. At this time, the polymerization conversion rate of α-methylstyrene was 89%, and the weight average molecular weight (Mw) of the polybutadiene block (polymer block B1) was 3,700, which was determined from ¹ H-NMR measurement. 4- Bond amount was 19%.
(Ii) Next, 141.3 g of butadiene was further added to the reaction solution, and a polymerization reaction was performed at 50 ° C. for 2 hours. The Mw of the polybutadiene block (polymer block B2) of the block copolymer (structure: A-B1-B2) obtained by sampling at this time is 29,800, and 1,4 determined from ¹ H-NMR measurement. -The binding amount was 60%.
(Iii) Subsequently, 12.2 ml of dichlorodimethylsilane (0.5 M toluene solution) was added to this polymerization reaction solution, and the mixture was stirred at 50 ° C. for 1 hour, and polyα-methylstyrene-polybutadiene-polyα-methylstyrene. A triblock copolymer was obtained. The coupling efficiency at this time was determined by the coupling body (poly α-methylstyrene-polybutadiene-polyα-methylstyrene triblock copolymer: A-B1-B2-X-B2-B1-A; Area ratio of UV absorption in GPC of ring agent residue (representing —Si (Me ₂ ) —) and unreacted block copolymer (poly α-methylstyrene-polybutadiene block copolymer: A-B1-B2) It was 94% when calculated from. As a result of ¹ H-NMR analysis, the polymer block A content in the poly α-methylstyrene-polybutadiene-polyα-methylstyrene triblock copolymer was 33%, and the entire polymer block B (ie, The 1,4-bond amount of the polymer block B1 and the polymer block B2) was 56%.
(Iv) A Ziegler-based hydrogenation catalyst formed from nickel octylate and triethylaluminum was added to the polymerization reaction solution obtained above in a hydrogen atmosphere, and hydrogen pressure was 0.8 MPa at 80 ° C. for 5 hours. The addition reaction was performed to obtain a hydrogenated product of poly α-methylstyrene-polybutadiene-α-polymethylstyrene triblock copolymer. As a result of GPC measurement of the obtained block copolymer, the main components are poly α-methylstyrene-polybutadiene-polyα-methylstyrene triblock copolymer having Mw = 80,000 and Mw / Mn = 1.01. From the area ratio of UV (254 nm) absorption in GPC, it was found that 94% of the coupling body was contained. Further, ¹ H-NMR measurement hydrogenation rate of the polymer block B composed of polymer block B1 and the polymer block B2 was 99%.

Examples 1-4 and Comparative Examples 1-4
Each component shown in Table 1 is mixed in advance using a Henschel mixer according to the formulation shown in Table 1, and supplied to a twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at 260 ° C. After kneading, it was extruded into strands and cut to prepare a pellet-shaped thermoplastic polymer composition. Next, from the obtained thermoplastic polymer composition, using a press molding machine, a predetermined molded body was produced under conditions of a molding temperature of 260 ° C., a molding pressure of 10 MPa, and a molding time of 3 minutes, and physical properties were evaluated. . The results are shown in Table 1.

In addition, the detail of the component shown in Table 1 is as follows.
1) PPE: poly (2,6-dimethyl-1,4-phenylene ether); manufactured by Asahi Kasei Chemicals Corporation, “P402”
2) PS: Polystyrene resin; manufactured by PS Japan, “Polystyrene 685”
3) (b) αMeSEBαMeS: hydrogenated product of polyα-methylstyrene-polybutadiene-polyα-methylstyrene triblock copolymer obtained in Production Example 1; α-methylstyrene unit content = 33% by mass, MFR = 15 g / 10 min (230 ° C., 5 kg load)
4) (c) Rubber softener: Paraffin-based process oil; Idemitsu Kosan Co., Ltd., trade name “Diana Process PW-90”, kinematic viscosity 95.54 mm ² / s (40 ° C.)
5) (d-1) SEBS: hydrogenated product of polystyrene-polybutadiene-polystyrene triblock copolymer; “G1650” manufactured by Kraton Polymer Co., Ltd., styrene unit content = 29 mass%, MFR = −g / 10 minutes ( (Does not flow) (230 ° C, 5kg load)
6) (d-2) SEBS: hydrogenated product of polystyrene-polybutadiene-polystyrene triblock copolymer; “G1652” manufactured by Kraton Polymer Co., Ltd., styrene unit content = 29 mass%, MFR = 10 g / 10 min (230 ℃, 5kg load)
7) Phosphorus flame retardant: condensed phosphate ester flame retardant; manufactured by Daihachi Chemical Co., Ltd., “CR7338”

  As can be seen from Table 1, the thermoplastic polymer compositions of the examples maintained heat resistance and flame retardancy, and were excellent in flexibility and improved in wear resistance, and were well balanced. Has physical properties.

  The thermoplastic polymer composition of the present invention maintains flame retardancy and heat resistance, and has greatly improved flexibility. Strands, sheets, films, tubes, hollow molded products, molded products, and other various types It can be formed into a molded body and used for various applications.

Claims (5)

A thermoplastic polymer composition comprising (I) a resin component, (II) a rubber component, and (III) a flame retardant component,
The (I) resin component contains (a) a polyphenylene ether resin, and (II) the rubber component contains (b) a polymer block A mainly composed of α-methylstyrene units and a conjugated diene unit. A block copolymer having a polymer block B and / or a hydrogenated product thereof, and a mass ratio of (I) resin component to (I) resin component and (II) total mass of rubber component [(I) / ((I) + (II))] is 0.03 to 0.8, and the mass ratio of (III) flame retardant component to the total mass of (I) resin component and (II) rubber component [( III) / ((I) + (II) + (III))] is 0.01 to 0.67.   (II) The rubber component further includes (c) a rubber softener, (b) a mass ratio of the block copolymer and / or a hydrogenated product thereof to (c) the rubber softener [(c) / ( The thermoplastic polymer composition according to claim 1, wherein b)] is 0.01 to 3.0.   (II) The rubber component further includes (d) a thermoplastic elastomer other than the component (b), and (b) a mass ratio of the block copolymer and / or a hydrogenated product thereof to (d) the thermoplastic elastomer [ (D) / (b)] is 0.01-5.0, The thermoplastic polymer composition of Claim 1 or 2.   (D) The thermoplastic elastomer is a block copolymer having a polymer block C mainly composed of vinyl aromatic compound units and a polymer block D mainly composed of conjugated diene units and / or a hydrogenated product thereof. Item 4. The thermoplastic polymer composition according to Item 3.   (I) The resin component further includes (e) a styrene resin, and the mass ratio [(e) / (a)] of (a) polyphenylene ether resin and (e) styrene resin is 0.01-2. The thermoplastic polymer composition according to any one of claims 1 to 4, which is 0.0.