JP5047549B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a composition excellent in gas barrier properties, hygiene, compression set properties, vibration damping properties, and mechanical properties, and a medical drug stopper, a beverage cap liner, and a vibration damping material using the composition.

  Conventionally, as a polymer material having elasticity, a material obtained by blending a rubber such as natural rubber or synthetic rubber with a crosslinking agent or a reinforcing agent and crosslinking under high temperature and high pressure has been widely used. However, such rubbers require a process of crosslinking and molding for a long time under high temperature and pressure, and are inferior in processability. In addition, since the crosslinked rubber does not exhibit thermoplasticity, it cannot be recycled as with a thermoplastic resin. Therefore, in recent years, it has been possible to easily produce molded products using general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding as well as general thermoplastic resins, and recycling molding. Various possible thermoplastic elastomers have been developed. As such thermoplastic elastomers, there are various types of polymers such as olefins, urethanes, esters, styrenes, vinyl chlorides, etc., which are also commercially available.

  Of these, olefin-based thermoplastic elastomers are excellent in heat resistance, cold resistance, weather resistance, and the like. Olefin-based thermoplastic elastomers include a crosslinked type and a non-crosslinked type. Non-crosslinked thermoplastic elastomers do not involve a crosslinking reaction, and therefore have little variation in quality and are inexpensive to manufacture. On the other hand, the cross-linked thermoplastic elastomer is excellent in terms of tensile strength, elongation at break, rubber properties (for example, permanent elongation, compression set) and heat resistance (see Non-Patent Document 1 and Patent Documents 1 to 9).

  However, non-crosslinked thermoplastic elastomers are not necessarily sufficient in tensile strength, elongation at break, rubbery properties (permanent elongation, compression set, etc.), heat resistance, and low temperature characteristics. Cross-linked thermoplastic elastomers also improve the compression set by increasing the degree of cross-linking, resulting in a decrease in flexibility, heat resistance, tensile strength at break, elongation at break, or cross-linking agent on the composition surface, softening Agent bleeding occurs.

  Thus, it is difficult to obtain a thermoplastic composition having an excellent balance of physical properties, and it can be easily molded by a hot press or the like like a conventional thermoplastic resin, and has an excellent balance of physical properties. Development of thermoplastic elastomer compositions is desired.

Japanese Patent Publication No.53-21021 Japanese Patent Publication No.55-18448 Japanese Patent Publication No.56-15741 Japanese Patent Publication No. 56-15742 Japanese Examined Patent Publication No. 58-46138 Japanese Patent Publication No.58-56575 Japanese Patent Publication No.59-30376 Japanese Patent Publication No.62-938 Japanese Examined Patent Publication No. 62-59139 Rubber Chemistry and Technology, A.R. Y. Coran et al., 53 (1980), 141 pages

  In view of the above-mentioned problems of the prior art, the object of the present invention is not only excellent in flexibility, rubbery characteristics, and vibration damping properties, but also exhibits particularly good compression set characteristics, hygiene, gas barrier properties, An object of the present invention is to provide a thermoplastic elastomer composition excellent in balance of molding processability, hardness-tensile strength and elongation property.

  As a result of intensive studies, the present inventors have completed the present invention.

That is, the present invention contains at least two or more selected from the following three types of resin compositions (A), (B) and (C), and (b), (d) and (e) It is related with the thermoplastic elastomer composition whose total amount is 10-300 weight part with respect to 100 weight part of (a) component.
(A): (a) Resin composition obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal with (b) a hydrosilyl group-containing compound during melt kneading with (b) polypropylene resin (B): (a (C) Resin composition obtained by dynamically crosslinking an isobutylene polymer having an alkenyl group at the terminal during the melt-kneading with (d) a polyethylene resin (c) a hydrosilyl group-containing compound (C): (a) An alkenyl group at the terminal (C) hydrosilylation during melt kneading of (e) a polymer block (I) mainly composed of an aromatic vinyl compound and an isobutylene block copolymer comprising the isobutylene polymer block (II) Resin composition dynamically cross-linked with group-containing compound As a preferred embodiment, (D) liquid polybutene is further alkenyl group (a) terminal It is related with the thermoplastic elastomer composition containing 1-500 weight part with respect to the isobutylene type polymer which has this.

A preferred embodiment relates to a thermoplastic elastomer composition having an oxygen permeability coefficient (JIS K 7126A method) of 15 × 10 ⁻¹⁶ mol × m / m ² × s × Pa or less.

  The present invention also relates to a medical drug stopper, a beverage cap liner, and a vibration damping material comprising the thermoplastic elastomer.

  The composition according to the present invention can be easily molded by a general technique such as hot pressing as in the case of a conventional thermoplastic resin. In addition, the composition according to the present invention is not only rich in flexibility and rubber elasticity, but also exhibits particularly good gas barrier properties, hygiene, compression set properties, vibration damping properties, and excellent balance of hardness-tensile strength and elongation properties. ing. For this reason, it can be suitably used for various applications such as sealing materials such as medical drug stoppers and cap liners for beverages, vibration damping materials, vibration proof materials, automobile interior materials, cushion materials, and the like.

The thermoplastic elastomer composition of the present invention contains at least two or more of the following three types of resin compositions (A), (B), and (C), and (b), (d), and (e). The total amount of components is a thermoplastic elastomer composition containing 10 to 300 parts by weight per 100 parts by weight of component (a).
(A): (a) Resin composition obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal with (b) a hydrosilyl group-containing compound during melt kneading with (b) polypropylene resin (B): (a (C) Resin composition obtained by dynamically crosslinking an isobutylene polymer having an alkenyl group at the terminal during the melt-kneading with (d) a polyethylene resin (c) a hydrosilyl group-containing compound (C): (a) An alkenyl group at the terminal (C) hydrosilylation during melt kneading of (e) a polymer block (I) mainly composed of an aromatic vinyl compound and an isobutylene block copolymer comprising the isobutylene polymer block (II) Resin composition dynamically crosslinked with group-containing compound

  The isobutylene polymer (a) of the present invention refers to a block in which isobutylene accounts for 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. The monomer component other than isobutylene of the isobutylene polymer (a) is not particularly limited as long as it is a monomer component capable of cationic polymerization, but aromatic vinyls, aliphatic olefins, isoprene, butadiene, divinylbenzene, etc. And monomers such as dienes, vinyl ethers and β-pinene. These may be used alone or in combination of two or more.

  The number average molecular weight of the isobutylene polymer (a) is not particularly limited, but is preferably 1,000 to 500,000, particularly preferably 5,000 to 200,000. When the number average molecular weight is less than 1,000, mechanical properties and the like are not sufficiently exhibited, and when it exceeds 500,000, the moldability and the like are greatly deteriorated.

  The alkenyl group of the present invention is not particularly limited as long as it is a group containing a carbon-carbon double bond active for the crosslinking reaction of component (a) for achieving the object of the present invention. Specific examples include aliphatic unsaturated hydrocarbon groups such as vinyl group, allyl group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group. And cyclic unsaturated hydrocarbon groups such as

  As a method for introducing an alkenyl group into the terminal of the isobutylene polymer of the present invention (a method for producing the polymer (a)), it is disclosed in JP-A-3-152164 and JP-A-7-304909. Examples thereof include a method of introducing an unsaturated group into a polymer by reacting a polymer having a functional group such as a hydroxyl group with a compound having an unsaturated group. In order to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with alkenylphenyl ether, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols, etc. And a method of performing the above-mentioned alkenyl group introduction reaction after introducing a hydroxyl group by performing a Friedel-Crafts reaction. Further, as disclosed in U.S. Pat. No. 4,316,973, JP-A 63-105005, and JP-A 4-288309, an unsaturated group can be introduced during the polymerization of the monomer. Among these, those in which an allyl group is introduced at the terminal by a substitution reaction of allyltrimethylsilane and chlorine are preferable from the viewpoint of certainty.

  The amount of the alkenyl group at the terminal of the isobutylene polymer (a) of the present invention can be arbitrarily selected depending on the required properties. From the viewpoint of the properties after crosslinking, at least 0.2 alkenyl groups per molecule. A polymer having a terminal group is preferred. If the number is less than 0.2, the improvement effect due to crosslinking may not be sufficiently obtained.

  In the present invention, the isobutylene polymer constituting the resin composition (A), (B), (C) is the same as long as it is an isobutylene polymer having an alkenyl group at the terminal. It may be different or different. That is, the molecular weight and the monomer component constituting the polymer may be different.

  The hydrosilyl group-containing compound (c) of the present invention is used to obtain a crosslinked product of an isobutylene polymer (a) having an alkenyl group introduced at the terminal. In the present invention, the hydrosilyl group-containing compounds constituting the resin compositions (A), (B), and (C) may be the same or different as long as they are hydrosilyl group-containing compounds. It may be.

There is no restriction | limiting in particular as a hydrosilyl group containing compound, Various things can be used. That is, a linear polysiloxane represented by the general formula (I) or (II);
_{^{R 1 3 SiO- [Si (R}} 1) 2 O] a - [Si (H) (R 2) O] b - [Si (R 2) (R 3) O] c -SiR 1 3 (I)
_{^{HR 1 2 SiO- [Si (R}} 1) 2 O] a - [Si (H) (R 2) O] b - [Si (R 2) (R 3) O] c -SiR 1 2 H (II)
(Wherein R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c satisfying 0 ≦ c ≦ 100.)
A cyclic siloxane represented by the general formula (III);

（式中、Ｒ⁴およびＲ⁵は炭素数１〜６のアルキル基、または、フェニル基、Ｒ⁶は炭素数１〜１０のアルキル基またはアラルキル基を示す。ｄは０≦ｄ≦８、ｅは２≦ｅ≦１０、ｆは０≦ｆ≦８の整数を表し、かつ３≦ｄ＋ｅ＋ｆ≦１０を満たす。）等の化合物を用いることができる。さらに上記のヒドロシリル基（Ｓｉ−Ｈ基）を有する化合物のうち、相溶性が良いという点から、特に下記の一般式（ＩＶ）で表されるものが好ましい。

(In the formula, R ⁴ and R ⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. D represents 0 ≦ d ≦ 8, e 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and 3 ≦ d + e + f ≦ 10 is satisfied). Furthermore, among the compounds having the above hydrosilyl group (Si—H group), those represented by the following general formula (IV) are particularly preferable from the viewpoint of good compatibility.

（式中、ｇ、ｈは整数であり２≦ｇ+ｈ≦５０、２≦ｇ、０≦ｈである。Ｒ⁷は水素原子またはメチル基を表し、Ｒ⁸は炭素数２〜２０の炭化水素基で１つ以上の芳香環を有していても良い。ｉは０≦ｉ≦５の整数である。

(In the formula, g and h are integers, and 2 ≦ g + h ≦ 50, 2 ≦ g, and 0 ≦ h. R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents carbonization having 2 to 20 carbon atoms. The hydrogen group may have one or more aromatic rings, i is an integer of 0 ≦ i ≦ 5.

  The isobutylene polymer (a) having an alkenyl group at the terminal and the hydrosilyl group-containing compound (c) can be mixed at an arbitrary ratio. However, in terms of reactivity, the molar ratio of the alkenyl group to the hydrosilyl group is 5 to 5. It is preferably in the range of 0.2, and more preferably 2.5 to 0.4. When the molar ratio is 5 or more, the crosslinking is insufficient and sticky, and the compression set tends to deteriorate. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain after crosslinking. Hydrogen gas is generated by hydrolysis and tends to cause cracks and voids.

  The cross-linking reaction between the isobutylene polymer (a) and the hydrosilyl group-containing compound (c) proceeds by mixing and heating the two components, but a hydrosilylation catalyst is added to accelerate the reaction. be able to. Such hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

  The radical initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, of m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1- Peroxyketals such as di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2′-azobisisobutyronitrile, 2,2 '-Azobis-2-methylbutyronitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azoisobutyrovalero Examples include azo compounds such as nitriles.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex and a platinum (0) -dialkenyltetramethyldisiloxane complex. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of (a) component, Preferably it is the range of 10 ^{< -3} > ^-10 <^-6> mol. It is good to use. When the amount is less than 10 ⁻⁸ mol, crosslinking tends not to proceed sufficiently. Moreover, since a clear effect is not seen even if it uses 10 ^<-1 > mol or more, it is preferable that it is less than 10 ^{< -1} > mol from the surface of economical efficiency. Of these, platinum vinyl siloxane is most preferred in terms of compatibility, crosslinking efficiency, and scorch stability.

  In the resin compositions (A) to (C), the dynamic cross-linking of the isobutylene polymer (a) with the hydrosilyl group-containing compound (c) is performed by (b) a polypropylene resin or (d) a polyethylene resin or (e) It is carried out by melt-kneading in the presence of an isobutylene block copolymer comprising a polymer block (I) mainly composed of an aromatic vinyl compound and an isobutylene polymer block (II).

  The polypropylene resin (b) of the present invention is a homopolymer or copolymer having propylene as a main component. The monomer to be copolymerized is a monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms.

  The addition amount of the polypropylene resin (b) of the present invention is preferably 5 to 300 parts by weight, more preferably 10 to 100 parts by weight, based on the isobutylene polymer (a). (B) When the blending amount of the polypropylene resin exceeds 300 parts by weight, the compression set characteristic tends to deteriorate significantly, and when it is less than 10 parts by weight, the moldability tends to deteriorate significantly.

  The polyethylene resin (d) of the present invention is a homopolymer or copolymer having ethylene as a main component. The monomer to be copolymerized is a monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms.

  The addition amount of the polyethylene resin (d) of the present invention is preferably 5 to 300 parts by weight, more preferably 10 to 100 parts by weight, based on the isobutylene polymer (A) (a). (D) When the blending amount of the polyethylene resin exceeds 300 parts by weight, the compression set characteristic tends to deteriorate significantly, and when it is less than 10 parts by weight, the moldability tends to deteriorate significantly.

  The (e) isobutylene block copolymer of the present invention comprises a polymer block (I) mainly composed of an aromatic vinyl compound and an isobutylene polymer block (II).

  The polymer block (I) mainly composed of an aromatic vinyl compound is a polymer block composed of 60 wt% or more, preferably 80 wt% or more of units derived from an aromatic vinyl compound.

  Aromatic vinyl compounds include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o. -Methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2 , 4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethyl Styrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m- Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or p- t-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene And vinyl naphthalene. Among these, styrene, α-methylstyrene, and a mixture thereof are preferable from the viewpoint of industrial availability and glass transition temperature.

  The polymer block (II) mainly composed of isobutylene is a polymer block composed of 60% by weight or more, preferably 80% by weight or more of units derived from isobutylene.

  In any of the polymer blocks (I) and (II), a mutual monomer can be used as a copolymerization component, and other cationically polymerizable monomer components can be used. Examples of such a monomer component include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene, and acenaphthylene. These can be used alone or in combination of two or more.

  Aliphatic olefin monomers include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane Octene, norbornene and the like.

  Examples of the diene monomer include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene.

  Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, tert-, iso) butyl vinyl ether, methyl propenyl ether, ethyl propenyl ether and the like.

  Examples of the silane compound include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3. , 3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.

  The component (e) of the present invention is not particularly limited as long as it is composed of the block (I) and the block (II), and has, for example, a linear, branched, star-like structure. Any of a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock copolymer, and the like can be selected. A preferable structure includes a triblock copolymer composed of (I)-(II)-(I) from the viewpoint of physical property balance and molding processability. These may be used alone or in combination of two or more in order to obtain desired physical properties and moldability.

  The ratio of the block (I) to the block (II) is not particularly limited, but from the viewpoint of flexibility and rubber elasticity, the content of the block (I) in the component (e) is 5 to 50% by weight. Is preferable, and it is further more preferable that it is 10 to 40 weight%.

  The molecular weight of component (e) is not particularly limited, but is preferably 30,000 to 500,000 in terms of weight average molecular weight by GPC measurement from the viewpoint of fluidity, molding processability, rubber elasticity, and the like. 000 to 300,000 is particularly preferable. When the weight average molecular weight is lower than 30,000, mechanical properties tend not to be sufficiently exhibited, whereas when it exceeds 500,000, fluidity and workability tend to deteriorate.

Although there is no restriction | limiting in particular about the manufacturing method of (e) component, For example, it can obtain by polymerizing a monomer component in presence of the compound represented by following General formula (1).
(CR ¹ R ² X) _n R ³ (1)
[Wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R ¹ and R ² are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ¹ , R ² may be the same or different, R ³ is a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6. . ]

  The compound represented by the general formula (1) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. Examples of the compound of the general formula (1) used in the present invention include the following compounds.

(1-Chloro-1-methylethyl) benzene [C ₆ H ₅ C (CH ₃ ) ₂ Cl], 1,4-bis (1-chloro-1-methylethyl) benzene [1,4-Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1,3-bis (1-chloro-1-methylethyl) benzene [1,3-Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1,3,5-tris (1-chloro-1-methylethyl) benzene [1,3,5- (ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ], 1,3-bis (1-Chloro-1-methylethyl) -5- (tert-butyl) benzene [1,3- (C (CH ₃ ) ₂ Cl) ₂ -5- (C (CH ₃ ) ₃ ) C ₆ H ₃ ]

Of these, bis (1-chloro-1-methylethyl) benzene [C ₆ H ₄ (C (CH ₃ ) ₂ Cl) ₂ ], tris (1-chloro-1-methylethyl) benzene [( ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ]. [Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, and tris (1-chloro- 1-methylethyl) benzene is also referred to as tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene, or tricumyl chloride.

When the component (e) is produced, a Lewis acid catalyst can coexist. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ , ZnBr ₂ , AlCl ₃ , AlBr _3, etc .; metal halides such as Et ₂ AlCl, EtAlCl _2, etc. can be preferably used. Of these, TiCl ₄ , BCl ₃ , and SnCl ₄ are preferable in view of the ability as a catalyst and industrial availability. The amount of Lewis acid used is not particularly limited, but can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it is 0.1-100 mol equivalent with respect to the compound represented by General formula (1), Preferably it is the range of 1-50 mol equivalent.

  In the production of the component (e), an electron donor component can be allowed to coexist if necessary. This electron donor component is believed to have the effect of stabilizing the growth carbon cation during cationic polymerization, and the addition of an electron donor produces a polymer with a narrow molecular weight distribution and a controlled structure. be able to. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.

  The polymerization of the component (e) can be carried out in an organic solvent as necessary, and the organic solvent can be used without particular limitation as long as it does not substantially inhibit cationic polymerization. Specifically, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene; benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, etc. Alkylbenzenes; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2 Branched aliphatic hydrocarbons such as 1,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; paraffin oil obtained by hydrorefining petroleum fractions, etc. .

  These solvents can be used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomer constituting the component (e) and the solubility of the polymer to be formed.

  The amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the resulting polymer solution and the ease of heat removal.

  In carrying out the actual polymerization, each component is mixed at a temperature of, for example, −100 ° C. or more and less than 0 ° C. under cooling. In order to balance the energy cost and the stability of polymerization, a particularly preferred temperature range is −30 ° C. to −80 ° C.

  The addition amount of the polyethylene resin (d) of the present invention is preferably 5 to 300 parts by weight, more preferably 10 to 100 parts by weight with respect to the isobutylene polymer (a). (D) When the blending amount of the polyethylene resin exceeds 300 parts by weight, the compression set characteristic tends to deteriorate significantly, and when it is less than 10 parts by weight, the moldability tends to deteriorate significantly.

  The addition amount of the isobutylene block copolymer (e) of the present invention is preferably 5 to 300 parts by weight, more preferably 10 to 100 parts by weight, based on the isobutylene polymer (A). When the blending amount of the isobutylene block copolymer (e) exceeds 300 parts by weight, the compression set characteristic tends to deteriorate significantly, and when it is less than 10 parts by weight, the physical strength and moldability tend to decrease remarkably. is there.

  The total amount of the polypropylene resin (b), polyethylene resin (d) and isobutylene block copolymer (e) of the present invention is 10 to 300 parts by weight based on the isobutylene polymer (a). It is more preferable that it is 10-100 weight part. When the blending amount of the components (b), (d) and (e) exceeds 300 parts by weight, the compression set characteristic tends to be remarkably deteriorated, and when it is less than 10 parts by weight, the physical strength and the moldability are deteriorated. There is a remarkable tendency.

  In the present invention, as the component (D), a softener can be used as necessary for the purpose of imparting flexibility and molding fluidity. Although it does not specifically limit as a softening agent, Generally, a liquid or liquid material is used suitably at room temperature. Examples of such softeners include various rubber or resin softeners such as mineral oils, vegetable oils, and synthetics. Mineral oils include naphthenic and paraffinic process oils, and vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine Examples of synthetic systems include oil and olive oil, and polybutene and low molecular weight polybutadiene. Among these, polybutene is preferably used from the viewpoint of compatibility with the component (a) and gas barrier properties. These softeners can be used in an appropriate combination of two or more in order to obtain the desired hardness and melt viscosity.

  The amount of component (D) is preferably 1 to 500 parts by weight, more preferably 1 to 50 parts by weight, and more preferably 1 to 30 parts by weight per 100 parts by weight of component (a). Is more preferable. When the amount exceeds 100 parts by weight, the softening agent tends to bleed out from the surface of the molded body, which is not preferable.

  The timing of adding the component (D) is not particularly limited, and may be added during the production of the components (A), (B), and (C), or the components (A), (B), and (C). (D) component may be added together when mixing.

  In order to perform dynamic crosslinking in order to obtain the components (A), (B), and (C), a known method may be employed. For example, a batch kneader or a continuous kneader can be used. For example, when manufacturing using a closed or open batch type kneader such as a lab plast mill, brabender, banbury mixer, kneader, roll, etc., all components other than the premixed crosslinking agent are kneaded. And then kneading and kneading until uniform, then adding a cross-linking agent to the cross-linking reaction and then stopping the melt-kneading.

  In addition, when producing using a continuous melt-kneading apparatus such as a single-screw extruder or a twin-screw extruder, all components other than the crosslinking agent are made uniform in advance by a melt-kneading apparatus such as an extruder. After melt-kneading and pelletizing, the pellet is dry-blended with a crosslinking agent, and then melt-kneaded with a melt-kneading apparatus such as an extruder or a Banbury mixer to move the isobutylene polymer (a) having an alkenyl group at the terminal. All components other than the cross-linking method and a cross-linking agent are melt-kneaded by a melt-kneading apparatus such as an extruder, a cross-linking agent is added to the middle of the cylinder of the extruder, and further melt-kneaded. Examples thereof include a method of dynamically crosslinking the isobutylene polymer (a) having a group.

  In performing melt kneading, a temperature range of 140 to 210 ° C is preferable, and a temperature range of 150 to 200 ° C is more preferable. When the melt kneading temperature is lower than 140 ° C., the components (b), (d), and (e) tend not to melt and cannot be sufficiently mixed. When the melt kneading temperature is higher than 210 ° C., the isobutylene polymer (a ) Tend to begin to decompose.

  In the present invention, by melt-kneading at least two types selected from the components (A), (B), and (C) that are dynamically crosslinked compositions of the isobutylene polymer (a) obtained by the above-described method, A desired thermoplastic elastomer composition is obtained.

  For melt kneading, a known method may be employed, and the above-described batch kneader or continuous kneader can be used. For example, after the components (A), (B), and (C) are weighed, mixed with a tumbler, Henschel mixer, riboblender, etc., and then melt-kneaded with an extruder, Banbury mixer, roll, or the like. . Although the kneading | mixing temperature at this time does not have limitation in particular, the range of 100-250 degreeC is preferable, and the range of 150-220 degreeC is more preferable. When the kneading temperature is lower than 100 ° C., melting tends to be insufficient, and when it is higher than 250 ° C., deterioration due to heating tends to start.

  In addition, the composition of the present invention can be further subjected to, for example, ethylene-propylene copolymer rubber (EPM) or ethylene-propylene-diene terpolymer in a range that does not impair the physical properties according to the required properties according to each application. Flexible olefin-based polymers such as rubber (EPDM), ethylene-butene copolymer rubber (EBM), amorphous poly α-olefin (APAO), ethylene-octene copolymer, in addition to hindered phenols and phosphorus, Sulfur antioxidants, hindered amine UV absorbers, light stabilizers, pigments, surfactants, flame retardants, antiblocking agents, antistatic agents, lubricants, silicone oils, fillers, reinforcing agents, etc. can do. As inorganic fillers, light calcium carbonate, heavy or calcium carbonate, other calcium fillers, hard clay, soft clay, kaolin clay, talc, wet silica, dry silica, amorphous silica, wollastonite, synthetic or natural zeolite Diatomaceous earth, silica sand, pumice powder, slate powder, alumina, aluminum sulfate, barium sulfate, calcium sulfate, molybdenum disulfide, magnesium hydroxide, aluminum hydroxide, and those obtained by silane treatment. These additives can be used in combination of two or more. For example, it is possible to improve hardness and tensile strength by including an inorganic filler. In addition, when a metal hydroxide such as magnesium hydroxide or aluminum hydroxide is used as the inorganic filler, it may be possible to impart excellent flame retardancy. Further, as the anti-blocking agent, for example, silica, zeolite and the like are suitable, and these may be either natural or synthetic, and true spherical crosslinked particles such as crosslinked acrylic true spherical particles are also suitable. As the antistatic agent, N, N-bis- (2-hydroxyethyl) -alkylamines and glycerin fatty acid esters having an alkyl group having 12 to 18 carbon atoms are preferable. Further, the lubricant is preferably a fatty acid amide, and specific examples include erucic acid amide, behenic acid amide, stearic acid amide, oleic acid amide and the like.

  The thermoplastic elastomer composition of the present invention can be molded using a molding method and molding apparatus generally employed for a thermoplastic resin composition, for example, melt molding by extrusion molding, injection molding, press molding, blow molding or the like. it can. Further, the thermoplastic elastomer composition of the present invention is excellent in moldability, hygiene, vibration damping, gas barrier properties, compression set properties, sealing materials such as packing materials, sealing materials, gaskets, plugs, Specifically, medical medicine plugs and beverage cap liners, CD dampers, architectural dampers, vibration control materials such as vibration control materials for automobiles, vehicles and home appliances, vibration damping materials, automotive interior materials, cushion materials, daily necessities It can be used effectively as electrical parts, electronic parts, sports members, grips or cushioning materials, wire covering materials, packaging materials, various containers, and stationery parts.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these.
Prior to the examples, various measurement methods, evaluation methods, and examples will be described.

(hardness)
In accordance with JIS K 6352, a 12.0 mm thick press sheet was used as a test piece.

(Compression set)
In accordance with JIS K 6262, a 12.0 mm thick press sheet was used as the test piece. The measurement was performed under the conditions of 70 ° C. × 22 hours or 100 ° C. × 22 hours and 25% deformation.

(Tensile properties)
The tensile properties are in accordance with JIS K-6251 (vulcanized rubber tensile test method), and a press sheet having a thickness of 2.0 mm is punched into a dumbbell-shaped No. 3 test piece, and the conditions are 23 ° C. and 500 mm / min. Measured with The apparatus used is Autograph AG-10TB (manufactured by Shimadzu Corporation).

(Vibration control)
For damping properties, dynamic viscoelastic properties were evaluated. The dynamic viscoelastic properties were obtained by cutting out two 5 mm × 6 mm test pieces from a 2.0 mm thick sheet obtained by hot press molding, and JIS K 6394 (Testing method for dynamic properties of vulcanized rubber and thermoplastic rubber). In accordance with the above, measurement was performed in a shear mode under conditions of a frequency of 10 Hz and a strain of 0.05%. The apparatus used is a dynamic viscoelasticity measuring apparatus DVA-200 (made by IT Measurement Control Co., Ltd.).

(Gas permeability)
The gas permeability was evaluated by the oxygen permeability coefficient. The oxygen permeability coefficient was measured by a differential pressure method at 23 ° C. and 1 atm in accordance with JIS K7126 by cutting out a test piece of 100 mm × 100 mm from a 2.0 mm thick sheet obtained by hot press molding.

(Contents of description components such as Examples)
Component (a):
APIB: Polyisobutylene having an allyl group introduced at the end (Production Example 1)
Component (b):
RPP: Polypropylene, manufactured by Prime Polymer Co., Ltd. (trade name “Prime Polypro J215W”)
Component (c):
Polysiloxane: Methyl hydrogen polysiloxane, manufactured by Toshiba Silicone (trade name “TSF484”)
Component (d):
HDPE: High-density polyethylene, manufactured by Prime Polymer (trade name “Hi-Zex 2200J”)
Ingredient (e):
SIBS: Styrene-isobutylene-styrene block copolymer (Production Example 2)
Cross-linking catalyst:
1, valent 3,3-tetramethyl-1,3-dialkenyldisiloxane complex of zero-valent platinum, 3% by weight xylene solution components (A1) to (A3)
Resin composition obtained by dynamically crosslinking isobutylene polymer (a) with hydrosilyl group-containing compound (c) during melt kneading with polypropylene resin (b) (Production Examples 3 to 5)
Ingredients (B1) to (B2)
Resin compositions obtained by dynamically cross-linking isobutylene polymer (a) with hydrosilyl group-containing compound (c) during melt-kneading with polyethylene resin (d) (Production Examples 6 to 7)
Ingredients (C1) to (C2)
Resin compositions obtained by dynamically crosslinking (a) isobutylene polymer with hydrosilyl group-containing compound (c) during melt kneading with (e) isobutylene block copolymer (Production Examples 8 to 9)
Component (D):
Polybutene: Made by Idemitsu Kosan Co., Ltd. (trade name “Idemitsu Polybutene 100R”)

(Production Example 1) [Production of Isobutylene Copolymer (APIB2) Introduced with Alkenyl Group at Terminal]
A 3 L faucet, a thermocouple, and a stirring seal were attached to a 2 L separable flask, and nitrogen substitution was performed. After nitrogen substitution, nitrogen was flowed using a three-way cock. To this, 785 ml of toluene and 265 ml of ethylcyclohexane were added using a syringe. After adding the solvent, the water content was measured with a Karl Fischer moisture system. After the measurement, it was cooled to about -70 ° C. 277 ml (2933 mmol) of isobutylene monomer was added. After cooling to about −70 ° C. again, 0.85 g (3.7 mmol) of p-dicumyl chloride and 0.68 g (7.4 mmol) of picoline were dissolved in 10 ml of toluene and added. When the internal temperature of the reaction system became -74 ° C and stabilized, 19.3 ml (175.6 mmol) of titanium tetrachloride was added to initiate polymerization. When the polymerization reaction was completed (90 minutes), 1.68 g (11.0 mmol) of a 75% allylsilane / toluene solution was added, and the reaction was further continued for 2 hours. Then, it deactivated with the pure water heated at about 50 degreeC, Furthermore, the organic layer was wash | cleaned 3 times with pure water (70 to 80 degreeC), the organic solvent was removed at 80 degreeC under pressure reduction, and APIB was obtained. A polymer having Mn of 45500, Mw / Mn of 1.10, and an allyl group content of 2.0 / mol was obtained.

(Production Example 2) [Production of styrene-isobutylene-styrene block copolymer (SIBS)]
After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, 456.1 mL of n-hexane (dried with molecular sieves) and 656.5 mL of butyl chloride (dried with molecular sieves) were added using a syringe. After cooling the polymerization vessel in a dry ice / methanol bath at −70 ° C., a polytetrafluoroethylene liquid feeding tube was placed on a pressure-resistant glass liquefied collection tube with a three-way cock containing 232 mL (2871 mmol) of isobutylene monomer. Then, isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.647 g (2.8 mmol) of p-dicumyl chloride and 1.22 g (14 mmol) of N, N-dimethylacetamide were added. Next, 8.67 mL (79.1 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, a mixed solution of 77.9 g (748 mmol) of styrene monomer, 23.9 mL of n-hexane and 34.3 mL of butyl chloride, which had been cooled to −70 ° C. in advance, was added to the polymerization vessel. 45 minutes after adding the mixed solution, about 40 mL of methanol was added to terminate the reaction.

  After distilling off the solvent from the reaction solution, it was dissolved in toluene and washed twice with water. Further, the toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. The block copolymer in which the Mn of the isobutylene polymer before styrene addition is 50,000 and Mw / Mn is 1.40, the Mn of the block copolymer after styrene polymerization is 67,000 and Mw / Mn is 1.50. A polymer was obtained.

(Production Example 3) [Production of component (A1)]
Lab plastoyl ((stock), which was weighed to a total of 40 g of the components (a) APIB, (b) RPP, and (D) polybutene obtained in Production Example 1 and set to 170 ° C. ) Manufactured by Toyo Seiki Seisakusho Co., Ltd. for 3 minutes, and then (c) polysiloxane was added at the rate shown in Table 1, and the crosslinking catalyst was added at the rate shown in Table 1, and the torque value was the highest. Dynamic crosslinking was carried out by further melt-kneading at 170 ° C. until a value was shown. After kneading for 3 minutes after showing the maximum value of the torque, the dynamic crosslinking composition (A1) was taken out.

(Production Example 4) [Production of component (A2)]
Kneading was carried out in the same manner as in Production Example 3 except that the blending amounts of the component (a), the component (c), the component (D) and the crosslinking catalyst were changed (see Table 1), and the dynamic crosslinked composition (A2) was obtained. I took it out.

(Production Example 5) [Production of component (A3)]
Kneading is carried out in the same manner as in Production Example 3 except that the blending amounts of the component (a), the component (b), the component (c), the component (D), and the crosslinking catalyst are changed (see Table 1). A thing (A3) was taken out.

(Production Example 6) [Production of component (B1)]
Kneading was carried out in the same manner as in Production Example 3 except that the component (a) was changed to the component (d) (see Table 1), and the dynamically crosslinked composition (B1) was taken out.

(Production Example 7) [Production of component (B2)]
Kneading was carried out in the same manner as in Production Example 6 except that the blending amounts of the component (a), the component (c), the component (D), and the crosslinking catalyst were changed (see Table 1), and the dynamically crosslinked composition (B2) was taken out. .

(Production Example 8) [Production of component (C1)]
Kneading was carried out in the same manner as in Production Example 3 except that the component (a) was changed to the component (d) and the component (D) was removed (see Table 1), and the dynamic crosslinking composition (C1) was taken out.

(Production Example 9) [Production of component (C2)]
Kneading was carried out in the same manner as in Production Example 8 except that the blending amounts of the component (a), the component (c) and the crosslinking catalyst were changed (see Table 1), and the dynamic crosslinking composition (C2) was taken out.

Example 1
The component (A1) obtained in Production Example 3 and the component (B1) obtained in Production Example 6 were weighed to a total of 40 g in the proportions shown in Table 2, and a lab plast mill set at 180 ° C. was used. For 5 minutes, and the thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Example 2)
The component (B1) obtained in Production Example 6 and the component (C1) obtained in Production Example 8 were weighed to a total of 40 g in the proportions shown in Table 2, and a lab plast mill set at 180 ° C. was used. For 5 minutes, and the thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Example 3)
A thermoplastic elastomer composition was obtained in the same manner as in Example 2 except that the component (A1) was used instead of the component (B1), and the physical properties were evaluated. The respective physical properties are shown in Table 2.

Example 4
Ingredient (A1) obtained in Production Example 3, Component (B1) obtained in Production Example 6, Component (C1) obtained in Production Example 8, and RPP so that the total amount is 40 g in the proportions shown in Table 2. And melt-kneaded for 5 minutes using a lab plast mill set at 180 ° C. to take out the thermoplastic elastomer composition. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Example 5)
The component (A1) obtained in Production Example 3, the component (B1) obtained in Production Example 6, and the component (e) obtained in Production Example 2 were weighed so as to have a total of 40 g in the proportions shown in Table 2. The mixture was melt kneaded for 5 minutes using a Laboplast mill set at 180 ° C., and the thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Example 6)
The component (A1) obtained in Production Example 3, the component (C1) obtained in Production Example 8, RPP, and the component (D) polybutene were weighed to a total of 40 g in the proportions shown in Table 2, and 180 ° C. The mixture was melt-kneaded for 5 minutes using a lab plast mill set to 1, and the thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 1)
The component (A2) and component (d) HDPE obtained in Production Example 4 were weighed to a total of 40 g in the proportions shown in Table 2, and melt kneaded for 5 minutes using a lab plast mill set at 180 ° C. The thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition was able to be formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 2)
Component (B2) and component (b) RPP obtained in Production Example 7 were weighed to a total of 40 g in the proportions shown in Table 2, and melt-kneaded for 5 minutes using a lab plast mill set at 180 ° C. The thermoplastic elastomer composition was taken out. The obtained thermoplastic elastomer composition was able to be formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 3)
Component (C2), component (d) HDPE, and (D) polybutene obtained in Production Example 9 were weighed to a total of 40 g in the proportions shown in Table 2, and using a lab plast mill set at 180 ° C. The thermoplastic elastomer composition was taken out by melt-kneading for 5 minutes. The obtained thermoplastic elastomer composition was able to be formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 4)
A thermoplastic elastomer composition was obtained in the same manner as in Comparative Example 3 except that (d) component HDPE was replaced with (b) RPP, and physical properties were evaluated. The respective physical properties are shown in Table 2.

(Comparative Example 5)
Component (A3) obtained in Production Example 5, component (d) HDPE, (e) SIBS obtained in Production Example 2 were weighed to a total of 40 g in the proportions shown in Table 2, and set to 180 ° C. The resulting thermoplastic elastomer composition was taken out by melting and kneading for 5 minutes using the Laboplast mill. The obtained thermoplastic elastomer composition was able to be formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 6)
Component (A3) obtained in Production Example 5, component (b) RPP, (e) SIBS obtained in Production Example 2 and polybutene Weighed to a total of 40 g in the proportions shown in Table 2, and brought to 180 ° C. It melt-kneaded for 5 minutes using the set lab plast mill, and took out the thermoplastic elastomer composition. The obtained thermoplastic elastomer composition was able to be formed into a sheet shape at 190 ° C. with a heating press (manufactured by Shindo Metal Industry Co., Ltd.). The obtained sheet was measured for hardness, compression set, tensile properties, vibration damping properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

  Example 1 is a composition composed of the component (A) and the component (B), and Comparative Example 1 is a composition composed of the component (A) and HDPE, but the constituent components are finally the same. However, Table 2 shows that Example 1 is superior to Comparative Example 1 in compression set characteristics and tensile characteristics. Example 2 and Comparative Example 2, Example 3 and Comparative Examples 3 and 4, Example 4 and Comparative Example 5, Example 5 and Comparative Example 6 were also conducted in compression set characteristics and tensile characteristics as in the above comparison. You can see that the example is better.

Claims (6)

It contains at least two or more selected from the following three resin compositions (A), (B) and (C), and the total amount of components (b), (d) and (e) is (a ) A thermoplastic elastomer composition that is 10 to 300 parts by weight per 100 parts by weight of the component.
(A): (a) Resin composition obtained by dynamically crosslinking an isobutylene polymer having an alkenyl group at the terminal with (c) a hydrosilyl group-containing compound during melt kneading with (b) polypropylene resin (B): ( a) Resin composition obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at a terminal with (c) a hydrosilyl group-containing compound during melt kneading with a polyethylene resin (C): (a) an alkenyl at the terminal When the isobutylene polymer having a group is melt-kneaded with (e) an isobutylene block copolymer consisting of a polymer block (I) mainly composed of an aromatic vinyl compound and an isobutylene polymer block (II) ( c) Resin composition dynamically crosslinked with a hydrosilyl group-containing compound   The thermoplastic elastomer composition according to claim 1, further comprising (D) a softening agent in an amount of 1 to 500 parts by weight per 100 parts by weight of the isobutylene polymer (a) having an alkenyl group at the terminal. 3. The thermoplastic elastomer composition according to claim 1, wherein an oxygen permeability coefficient (JIS K 7126A method) is 15 × 10 ⁻¹⁶ mol · m / m ² · s · Pa or less. A medical drug stopper comprising the thermoplastic elastomer composition according to any one of claims 1 to 3. A cap liner for beverages comprising the thermoplastic elastomer composition according to claim 1. A vibration damping material comprising the thermoplastic elastomer composition according to any one of claims 1 to 3.