JP4686118B2 - Thermoplastic elastomer composition with excellent gas barrier properties - Google Patents

Description

  The present invention relates to a novel thermoplastic elastomer composition which is rich in flexibility, excellent in molding processability and rubber-like properties, and particularly excellent in compression set properties and gas barrier properties.

  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. Moreover, since the crosslinked rubber does not exhibit thermoplasticity, it is generally impossible to perform recycle molding like a thermoplastic resin. For this reason, various thermoplastic elastomers have been developed in recent years that can easily produce molded products using general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding in the same way as ordinary thermoplastic resins. ing. As such thermoplastic elastomers, various types of polymers such as olefin-based, urethane-based, ester-based, styrene-based, and vinyl chloride-based have been developed and are commercially available.

  Among them, as a thermoplastic elastomer composition excellent in gas barrier properties, an isobutylene block copolymer containing a polymer block mainly composed of isobutylene and a polymer block mainly composed of an aromatic vinyl compound is known. (Patent Document 1, Patent Document 2). This composition is excellent in flexibility and gas barrier properties, but has a problem in compression set.

  There is also a thermoplastic elastomer in which an isobutylene polymer having an alkenyl group at the terminal is dynamically cross-linked in a polyolefin (Patent Document 3). This composition is a thermoplastic resin composition excellent in heat resistance, vibration damping properties, compression set, and gas barrier properties among thermoplastic elastomers. This composition can be added with a softening agent to adjust the hardness, but in the case of mineral oils such as general rubber softening agents such as paraffinic oils, naphthenic oils, and aromatic high boiling petroleum components. Although it was possible to reduce the hardness, there was a drawback that the gas barrier properties deteriorated.

  Elastomers used for foods, medical packaging materials and sealing materials are required to have flexibility, compression set and gas barrier properties.

The appearance of a thermoplastic elastomer composition capable of providing a molded article having excellent gas barrier properties while maintaining flexibility and compression set characteristics as compared with conventionally known thermoplastic elastomers is desired.
JP-A-8-301955 JP 11-246733 A WO03 / 002654 Publication

  An object of the present invention is to provide a thermoplastic elastomer composition which is rich in flexibility and excellent in moldability, rubber-like properties, particularly compression set properties and gas barrier properties, in view of the above-mentioned problems of the prior art. .

As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention
(A) A composition obtained by dynamically crosslinking 100 parts by weight of an isobutylene polymer having an alkenyl group at a terminal with a hydrosilyl group-containing polysiloxane,
(B) 5 to 100 parts by weight of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl-based block copolymer;
(C) 70 to 300 parts by weight of polybutene,
Tona is, the polybutene contains as a main component isobutylene skeleton, weight-average molecular weight of the polybutene relates to a thermoplastic elastomer composition characterized and Dearuko 300-20000.

  As a preferred embodiment, the isobutylene polymer having an alkenyl group at the terminal is composed of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer, and polybutene. The present invention relates to a thermoplastic elastomer composition comprising a composition dynamically crosslinked with a hydrosilyl group-containing polysiloxane during melt mixing.

  As a preferred embodiment, the isobutylene polymer having an alkenyl group at the terminal is melt-mixed with at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer. The present invention relates to a thermoplastic elastomer composition comprising a composition dynamically crosslinked with a hydrosilyl group-containing polysiloxane.

  As a preferred embodiment, the present invention relates to a thermoplastic elastomer composition, wherein the polypropylene resin is random polypropylene.

  As a preferred embodiment, the present invention relates to a thermoplastic elastomer composition, wherein the polyethylene-based resin is high-density polyethylene.

  In a preferred embodiment, the aromatic vinyl block copolymer is composed of a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of isobutylene. And a thermoplastic elastomer composition.

  In a preferred embodiment, the aromatic vinyl block copolymer is mainly composed of a polymer block (a) having an aromatic vinyl compound as a main component, and a polymer block (b) having an isobutylene as a main component. The thermoplastic elastomer composition is a triblock copolymer having a weight average molecular weight of 40,000 to 200,000 indicating the structure of the polymer block (a).

  The thermoplastic elastomer composition of the present invention is a novel thermoplastic elastomer composition having excellent gas barrier properties while maintaining good flexibility and compression set properties.

The thermoplastic elastomer composition of the present invention comprises:
(A) A composition obtained by dynamically crosslinking 100 parts by weight of an isobutylene polymer having an alkenyl group at a terminal with a hydrosilyl group-containing polysiloxane,
(B) 5 to 100 parts by weight of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl-based block copolymer;
(C) 70 to 300 parts by weight of polybutene,
Tona is, the polybutene contains as a main component isobutylene skeleton, weight-average molecular weight of the polybutene is a thermoplastic elastomer composition characterized and Dearuko 300-20000.

  The isobutylene polymer having an alkenyl group at the terminal of the present invention refers to a polymer 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 other than isobutylene in the isobutylene polymer having an alkenyl group at the terminal is not particularly limited as long as it is a monomer component capable of cationic polymerization, but aromatic vinyls, aliphatic olefins, isoprene, butadiene And monomers such as dienes such as divinylbenzene, 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 having an alkenyl group at the terminal is 1,000 to 500,000 , and 5,000 to 200,000 is particularly preferable. 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 a crosslinking reaction 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

  Examples of the method for introducing an alkenyl group at the terminal of an isobutylene polymer having an alkenyl group at the terminal of the present invention include hydroxyl groups as disclosed in JP-A-3-152164 and JP-A-7-304909. Examples thereof include a method of introducing a unsaturated group into a polymer by reacting a polymer having a functional 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 end of the isobutylene polymer having an alkenyl group at the end of the present invention can be arbitrarily selected depending on the required properties, but from the viewpoint of the properties after crosslinking, at least 0.2 per molecule. It is a polymer having a terminal alkenyl group . If the number is less than 0.2, the improvement effect due to crosslinking may not be sufficiently obtained. Moreover, the quantity of the terminal alkenyl group is 1-6 pieces from the surface of compression set , and 1.5-2.5 pieces are still more preferable. If the number exceeds 6, a large amount of the crosslinking agent is required, and the cost of the crosslinking agent is increased, and the dispersion of the crosslinking agent during kneading is adversely affected.

  The polypropylene resin used in the present invention is a homopolymer having a propylene content of 50 to 100 mol% or a copolymer with an α-olefin having 3 to 20 carbon atoms, and is a homopolypropylene, a random polypropylene, or a block polypropylene. In particular, random polypropylene is preferable from the viewpoint of the tensile properties of the resulting composition. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1, and the like. These may be used alone or in combination of two or more.

  The polyethylene-based resin used in the present invention is a homopolymer having an ethylene content of 50 to 100 mol% or a copolymer with an α-olefin having 3 to 20 carbon atoms, and includes a high density polyethylene, a low density polyethylene, Linear low-density polyethylene is exemplified, and high-density polyethylene is particularly preferable from the viewpoint of tensile properties and heat resistance of the resulting composition.

  The aromatic vinyl block copolymer used in the present invention is not particularly limited, but a block copolymer comprising a polymer block (a) mainly composed of an aromatic vinyl compound and an isobutylene polymer block (b). It is preferably a coalescence.

  Examples of the aromatic vinyl compound in the polymer block (a) mainly composed of an aromatic vinyl compound include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, Examples include dichlorostyrene, methoxystyrene, indene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinylpyridine. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferable from the balance of cost, physical properties, and productivity, and two or more of them may be selected.

  The isobutylene polymer block (b) 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 other than isobutylene in the isobutylene polymer block (b) 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 structure of the aromatic vinyl block copolymer is not particularly limited, but a combination of a polymer block (a) mainly composed of an aromatic vinyl compound and an isobutylene polymer block (b), (a) A triblock copolymer of-(b)-(a) is preferred in terms of heat resistance and tensile strength of the composition.

  Although there is no restriction | limiting in particular about the ratio of the polymer block (a) which has an aromatic vinyl compound as a main, From the balance of a physical property and workability, isobutylene type polymer block (b) is 95-20 weight%, aromatic The polymer block (a) mainly comprising a vinyl compound is preferably 5 to 80% by weight, the isobutylene polymer block (b) is 90 to 60% by weight, and the polymer block mainly comprising an aromatic vinyl compound. It is particularly preferable that (a) is 10 to 40% by weight.

The number average molecular weight of the aromatic vinyl block copolymer is 15,000 to 400,000 , and 40,000 to 200,000 is particularly preferred. When the number average molecular weight is less than 15,000, mechanical properties and the like are not sufficiently exhibited, and when it exceeds 400,000, the decrease in moldability and the like is large.

  The blending amount of the polypropylene resin, the polyethylene resin, and the aromatic vinyl block copolymer is 100 parts by weight of the isobutylene polymer having an alkenyl group at the terminal, and the polypropylene resin, the polyethylene resin, and the aromatic vinyl. The total amount of the system block copolymers is preferably 5 to 100 parts by weight, and more preferably 10 to 80 parts. When the total amount of the polypropylene resin, polyethylene resin, and aromatic vinyl block copolymer exceeds 100 parts by weight, the compression set characteristics tend to be poor. On the other hand, when the amount is less than 5 parts by weight, there is a tendency that a problem occurs in formability.

  The addition method of the polypropylene resin, the polyethylene resin, and the aromatic vinyl block copolymer is not particularly limited. However, before the dynamic cross-linking step of the isobutylene polymer having an alkenyl group at the terminal, an alkenyl at the terminal is added. At least 5 parts by weight of the total of polypropylene resin, polyethylene resin and aromatic vinyl block copolymer is added to 100 parts by weight of the isobutylene polymer having a group, and the rest should be added after crosslinking. In addition, a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer may all be added before dynamic crosslinking. If the total of the polypropylene resin, the polyethylene resin, and the aromatic vinyl block copolymer is less than 5 parts by weight during the dynamic cross-linking step of the isobutylene polymer having an alkenyl group at the terminal, the share at the time of kneading is not applied. Tends to be biased and the uniformity of the degree of crosslinking tends to be impaired.

The polybutene of the present invention is an oily high molecular weight substance having an isobutylene skeleton as a main component at room temperature. Generally, it is marketed under the trade names of “Idemitsu Polybutene” manufactured by Idemitsu Oil Co., Ltd., “Nissan Polybutene” manufactured by Nippon Oil & Fats Co., Ltd., and “Nisseki Polybutene” manufactured by Nippon Oil Corporation. The weight average molecular weight of polybutene is 300 to 20000 , and 500 to 10,000 is particularly preferable. When the weight average molecular weight is less than 300, the heat resistance of the polybutene is not sufficient, and when it exceeds 20000, the moldability is greatly lowered and the tackiness becomes severe. Polybutene acts as a softening agent, and when blended, the hardness of the thermoplastic composition of the present invention is lowered and flexibility is imparted.

The compounding amount of polybutene is preferably 70 to 300 parts by weight with respect to 100 parts by weight of the isobutylene polymer having an alkenyl group at the terminal. When the blending amount is less than 10 parts by weight, the flexibility is impaired, and when it exceeds 300 parts by weight, there is a problem in mechanical strength reduction and moldability.

  The step of adding polybutene is not particularly limited, and may be added at any step before or after crosslinking of the isobutylene polymer having an alkenyl group at the terminal.

  The means for crosslinking an isobutylene polymer having an alkenyl group at the end is a crosslinking with a hydrosilyl group-containing compound, particularly a hydrosilyl group-containing polysiloxane, because there are no by-products and no unwanted side reactions. Can be used.

Hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 to 500 siloxane units as a hydrosilyl group-containing compound for obtaining a crosslinked product of an isobutylene polymer having an alkenyl group at the terminal of the present invention in it, it is possible to use various ones. More preferably, a polysiloxane having 3 or more hydrosilyl groups and 10 to 200 siloxane units can be used. More preferably, a polysiloxane having 3 or more hydrosilyl groups and 20 to 100 siloxane units can be used. When the number of polysiloxane units is 100 or less, it is preferable because the hydrosilyl group-containing polysiloxane required for hydrosilylation can be reduced. The polysiloxane unit mentioned here refers to the following general formulas (I), (II), and (III). That is, a hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 or more and 500 or less siloxane units, a chain polysiloxane represented by the general formula (IV) or (V);
[Si (R ¹ ) ₂ O] (I)
[Si (H) (R ² ) O] (II)
[Si (R ² ) (R ³ ) O] (III)
_{^{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 (IV)
_{^{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 (V)
(In the formula, 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. B represents 3 ≦ b, a, b. , C represents an integer satisfying 3 ≦ a + b + c ≦ 500.)
A cyclic siloxane represented by the general formula (VI);

（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。ｅは3≦ｂ、ｄ、ｅ、ｆはｄ＋ｅ＋ｆ≦５００を満たす整数を表す。）等の化合物を用いることができる。

(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. E represents 3 ≦ b, d, e , F represents an integer satisfying d + e + f ≦ 500.) And the like can be used.

  In the hydrosilyl group-containing compound of the present invention, when the content of the hydrosilyl group is less than 3, the cross-linking cannot achieve the sufficient growth of the network and the optimal rubber elasticity cannot be obtained, and when there are 501 or more siloxane units, the polysiloxane This is unfavorable because it is not well dispersed in an isobutylene polymer having a high viscosity and having an alkenyl group at the terminal, causing unevenness in the crosslinking reaction.

Although isobutylene polymer and hydrosilyl group-containing polysiloxane having terminal alkenyl groups can be mixed in any proportion, from the viewpoint of curability, the molar ratio of alkenyl groups and hydrosilyl groups (Al Ke alkenyl group / hydrosilyl group ) is Ri range near the 5 to 0.1, further particularly preferably 2.5 to 0.2. When the molar ratio is 5 or more, only a cured product with insufficient strength can be obtained with insufficient crosslinking, and when it is less than 0.1, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

  The cross-linking reaction between the isobutylene polymer having an alkenyl group at the terminal and the hydrosilyl group-containing compound proceeds by mixing and heating the two components, but a hydrosilylation catalyst is added to advance the reaction more rapidly. 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, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 Examples thereof include peroxyketals such as -di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

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. Of these, platinum vinyl siloxane is most preferred in terms of compatibility, crosslinking efficiency, and scorch stability.

Although there is no restriction | limiting in particular as a 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 the isobutylene type polymer component which has an alkenyl group at the terminal, Preferably it is 10 ^<-3> -. It is preferable to use in the range of 10 ⁻⁶ mol. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. Further, since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ⁻¹ mol or more.

  In carrying out dynamic crosslinking simultaneously with melt-kneading, a temperature of 130 to 210 ° C. is preferred. At temperatures lower than 130 ° C, the melting of polypropylene resins, polyethylene resins, aromatic vinyl block copolymers, etc. tends to be insufficient, and kneading tends to be uneven. At temperatures higher than 210 ° C The thermal decomposition of the isobutylene polymer having an alkenyl group at the end tends to proceed.

  The combination for dynamic crosslinking is not particularly limited, but the isobutylene polymer having an alkenyl group at the terminal is selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer. Melting of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl-based block copolymer that dynamically crosslinks when melt mixing with at least one component and polybutene A combination that dynamically crosslinks during mixing is exemplified. At least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer can be blended with these dynamically crosslinked compositions, and polybutene can be blended. You can also

  Further, the composition of the present invention further includes a reinforcing agent and a filler, such as ethylene-propylene copolymer rubber (EPM), ethylene-fluoropropylene, within a range not impairing physical properties according to the required properties according to each application. Flexible olefin polymers such as diene terpolymer rubber (EPDM), ethylene-butene copolymer rubber (EBM), amorphous polyalphaolefin (APAO), ethylene-octene copolymer, styrene-butadiene-styrene block copolymer Copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) obtained by hydrogenating them. ), And other suitable thermoplastic elastomers Rukoto can. In addition, paraffinic oils, naphthenic oils, aromatic oils as softeners, hindered phenol and hindered amine antioxidants, UV absorbers, light stabilizers, pigments, surfactants, flame retardants, etc. Can be appropriately blended. Known coupling agents, organic fillers, inorganic fillers, antiblocking agents, antistatic agents, colorants, inorganic or organic antibacterial agents, lubricants, silicone oils and the like can also be added. Inorganic fillers include 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, lithopone, calcium sulfate, molybdenum disulfide, magnesium hydroxide, and these fillers treated with silane, etc. Any material can be used as long as it can be blended into a product, and two or more types can be used in combination. For example, in applications where transparency is not required, the inclusion of an inorganic filler may improve the blocking property and may be advantageous in terms of cost, and may provide concealment. Moreover, when metal hydroxides, such as magnesium hydroxide, are used as an inorganic filler, the outstanding flame retardance may be provided by using a flame retardant together. 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 a 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. In addition, the thermoplastic elastomer composition of the present invention is excellent in moldability, compression set, and gas barrier properties, and therefore can be particularly preferably used for sealing materials such as packing materials, sealing materials, gaskets, and plugs. In addition, CD dampers, architectural dampers, damping materials such as damping materials for automobiles, vehicles, home appliances, anti-vibration materials, automotive interior materials, cushioning materials, daily necessities, electrical parts, electronic parts, sports parts, grips or It can be effectively used as a cushioning material, wire covering material, packaging material, 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 pressure press sheet was used as a test piece.

(Tensile strength at break)
In accordance with JIS K 6251, a 2 mm thick press sheet was used as a test piece by punching it into a No. 3 type with a dumbbell. The tensile speed was 500 mm / min.

(Tensile breaking elongation)
In accordance with JIS K 6251, a 2 mm thick press sheet was used as a test piece by punching it into a No. 3 type with a dumbbell. The tensile speed was 500 mm / min.

(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 at 100 ° C. for 22 hours under the conditions of 25% deformation.

(Gas barrier properties)
In accordance with JIS K 7126, a 1 mm thick press sheet was used as the test piece, the gas used was air, the measurement method was method A, and room temperature.

  In addition, the abbreviations and specific contents of materials used in Examples and Comparative Examples are as follows.

(Contents of description components such as Examples)
ARPIB: Isobutylene polymer having an allyl group at the terminal (Production Example 1)
PP: Polypropylene, manufactured by Grand Polymer (trade name “Grand Polypro J215W”)
PE: High density polyethylene, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.
SIBS: Styrene-isobutylene-styrene block copolymer (Production Example 2)
Polybutene 1, manufactured by Idemitsu Oil Co., Ltd. (trade name “Idemitsu Polybutene 15H”)
Polybutene 2, manufactured by Idemitsu Oil Co., Ltd. (trade name “Idemitsu Polybutene 100H”)
Polybutene 3, manufactured by Idemitsu Oil Co., Ltd. (trade name “Idemitsu Polybutene 300H”)
Crosslinking agent 1: Hydrosilyl group-containing polysiloxane: Polysiloxane (CH ₃ ) ₃ SiO— [Si (H) (CH ₃ ) O] ₄₈ —Si (CH ₃ ) ₃ represented by the following chemical formula
Softener:
OIL1: Paraffinic process oil, manufactured by JOMO (trade name “P-500”)
OIL2: Paraffinic process oil, manufactured by Idemitsu Kosan Co., Ltd. (trade name “PW380”)
Cross-linking catalyst: 1,1,3,3-tetramethyl-1,3-dialkenyldisiloxane complex of zerovalent platinum, 3% by weight xylene solution.

(Production Example 1) [Production of isobutylene polymer having an allyl group at the terminal (ARPIB)]
A 2 L separable flask was fitted with a three-way cock, a thermocouple, and a stirring seal, and was purged with nitrogen. 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. 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 the inside of the polymerization vessel of the 2 L separable flask was purged 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 the polymerization vessel was cooled in a dry ice / methanol bath at −70 ° C., a Teflon (registered trademark) feeding tube was placed in a pressure-resistant glass liquefied collection tube with a three-way cock containing 232 mL (2871 mmol) of isobutylene monomer. And the 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 the addition of 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.

Example 1
ARPIB, PP, and polybutene 1 were blended in the proportions shown in Table 1 to a total of 40 g, melt-kneaded for 3 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C., and then crosslinking agent 1 Was added at a ratio shown in Table 1, and after adding 12 μl of a crosslinking catalyst, the mixture was further melt-kneaded at 170 ° C. until the torque value reached the maximum value to perform dynamic crosslinking. After showing the maximum value of the torque, it was taken out after kneading for 5 minutes. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. by a pressure press manufactured by Shinfuji Metal Industry Co., Ltd. The obtained sheet was measured for hardness, compression set, tensile properties, and gas barrier properties according to the above methods. Table 1 shows the physical properties of each sheet.

(Example 2)
Except having changed to polybutene 2, the resin composition was shape | molded like Example 1 and the physical property was evaluated. The respective physical properties are shown in Table 1.

(Example 3)
Except having changed to polybutene 3, the resin composition was shape | molded like Example 1 and the physical property was evaluated. The respective physical properties are shown in Table 1.

Example 4
Except having changed the compounding quantity of polybutene 2 into 100 parts, the resin composition was shape | molded like Example 2 and the physical property was evaluated. The respective physical properties are shown in Table 1.

(Example 5)
Except having changed the compounding quantity of polybutene 2 into 125 parts, the resin composition was shape | molded like Example 2 and the physical property was evaluated. The respective physical properties are shown in Table 1.

(Example 6)
Except having changed PP into PE, the resin composition was shape | molded like Example 4 and the physical property was evaluated. The respective physical properties are shown in Table 1.

(Example 7)
A resin composition was molded in the same manner as in Example 6 except that the blending amount of PE was changed to 40 parts and the blending amount of polybutene 2 was changed to 80 parts, and physical properties were evaluated. The respective physical properties are shown in Table 1.

(Example 8)
[Step 1] ARPIB, SIBS, and polybutene 2 were blended in the proportions shown in Table 1 to a total of 40 g, and melt-kneaded for 3 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C. Next, the crosslinking agent 1 was added at the ratio shown in Table 1, and after addition of 12 μl of the crosslinking catalyst, the mixture was further melt-kneaded at 170 ° C. until the torque value reached the maximum value to perform dynamic crosslinking. After showing the maximum value of the torque, it was taken out after kneading for 5 minutes.

  [Step 2] Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) blended to 100 g by weight of the composition obtained in Step 1 so that the total amount is 40 g in the proportions shown in Table 1 and set to 170 ° C. And was taken out after melt-kneading for 10 minutes. The obtained thermoplastic elastomer composition could be easily formed into a sheet shape at 190 ° C. by a pressure press manufactured by Shinfuji Metal Industry Co., Ltd. The obtained sheet was measured for hardness, compression set, tensile properties, and gas barrier properties according to the above methods. Table 1 shows the physical properties of each sheet.

Example 9
[Step 1] A resin composition was obtained in the same manner as in [Step 1] of Example 8 except that SIBS was changed to PP and blended at the ratio shown in Table 1.

  [Step 2] A resin composition was molded and physical properties were obtained in the same manner as in [Step 2] of Example 8 except that PP was changed to SIBS and blended in the proportions shown in Table 1. Table 1 shows the physical properties of the sheet.

(Example 10)
[Step 1] A resin composition was obtained in the same manner as in [Step 1] of Example 9, except that polybutene 2 was changed to softener OIL1 and blended in the proportions shown in Table 1.

  [Step 2] A resin composition was molded and physical properties were obtained in the same manner as in [Step 2] of Example 9 except that SIBS was changed to polybutene 2 and blended in the proportions shown in Table 1. Table 1 shows the physical properties of the sheet.

(Example 11)
[Step 1] A resin composition was obtained in the same manner as in [Step 1] of Example 9 except that the amount of polybutene 2 was changed to 10 parts.

  [Step 2] A resin composition was molded and physical properties were obtained in the same manner as in [Step 2] of Example 9 except that SIBS was not blended, but was changed to polybutene 2 and blended at the ratio shown in Table 1. Table 1 shows the physical properties of the sheet.

(Comparative Example 1)
ARPIB, PP and softening agent OIL1 were blended in the proportions shown in Table 1 to a total of 40 g, melt-kneaded for 3 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C., and then a crosslinking agent 1 was added at a ratio shown in Table 2, and after addition of 12 μl of the crosslinking catalyst, the mixture was further melt-kneaded at 170 ° C. until the torque value reached the maximum value, and dynamic crosslinking was performed. After showing the maximum value of the torque, it was taken out after mixing for 5 minutes. The obtained thermoplastic elastomer composition could be formed into a sheet shape at 190 ° C. by a pressure press manufactured by Shinto Metal Industry. The obtained sheet was measured for hardness, compression set, tensile properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 2)
The resin composition was molded in the same manner as in Comparative Example 1 except that the softening agent was changed to OIL2 and the blending amount was changed to 100 parts, and the physical properties were evaluated. The respective physical properties are shown in Table 2.

(Comparative Example 3)
A resin composition was molded in the same manner as in Comparative Example 2 except that the blending amount of the softening agent OIL2 was changed to 125 parts, and the physical properties were evaluated. The respective physical properties are shown in Table 2.

(Comparative Example 4)
The resin composition was molded in the same manner as in Comparative Example 1 except that PP was changed to PE and the softening agent was changed to OIL2, and the physical properties were evaluated. The respective physical properties are shown in Table 2.

(Comparative Example 5)
[Step 1] ARPIB, SIBS, and softener OIL2 were blended in the proportions shown in Table 1 to a total of 40 g, and melt kneaded for 3 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C. Then, the crosslinking agent 1 was added at the ratio shown in Table 1, and after adding 12 μl of the crosslinking catalyst, the mixture was further melt-kneaded at 170 ° C. until the torque value reached the maximum value, and dynamic crosslinking was performed. After showing the maximum value of the torque, it was taken out after kneading for 5 minutes.

  [Step 2] Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) blended to 100 g by weight of the composition obtained in Step 1 so that PP was blended to a total of 40 g at a ratio shown in Table 2 and set to 170 ° C. And was taken out after melt-kneading for 10 minutes. The obtained thermoplastic elastomer composition could be formed into a sheet shape at 190 ° C. by a pressure press manufactured by Shinto Metal Industry. The obtained sheet was measured for hardness, compression set, tensile properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

(Comparative Example 6)
[Step 1] A resin composition was obtained in the same manner as in [Step 1] of Comparative Example 5 except that SIBS was changed to PP and blended in the proportions shown in Table 2.

  [Step 2] A resin composition was molded and physical properties were obtained in the same manner as in [Step 2] of Comparative Example 5 except that PP was changed to SIBS and blended in the proportions shown in Table 2. Table 2 shows the physical properties of the sheet.

(Comparative Example 7)
[Step 1] A resin composition was obtained in the same manner as in [Step 1] of Comparative Example 6 except that the blending amount of the softening agent OIL2 was changed to 10 parts.

  [Step 2] A resin composition was molded and physical properties were obtained in the same manner as in [Step 2] of Comparative Example 5 except that PP was changed to softener OIL2 and blended in the proportions shown in Table 2. Table 2 shows the physical properties of the sheet.

(Comparative Example 8)
After being melt-kneaded for 10 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) with SIBS 40 g set at 170 ° C., it could be formed into a sheet shape at 170 ° C. with a pressure press manufactured by Shindo Metal Industries . The obtained sheet was measured for hardness, compression set, tensile properties, and gas barrier properties according to the above methods. Table 2 shows the physical properties of each sheet.

本発明の熱可塑性エラストマー組成物、すなわち実施例１〜１１はガスバリア性が５．０〜８．２と良好な値を示した。ポリブテンを使用していない比較例１〜７のガスバリア性は１３．６〜１７．１と実施例１〜１１と比較して悪いことが分かる。比較例８はガスバリア性は良好であるが、圧縮永久歪みは実施例１〜１１に比べかなり悪い。

The thermoplastic elastomer composition of the present invention, that is, Examples 1 to 11, showed good values of gas barrier properties of 5.0 to 8.2. It turns out that the gas-barrier property of Comparative Examples 1-7 which does not use polybutene is 13.6-17.1 and bad compared with Examples 1-11. Although the comparative example 8 has a good gas barrier property, the compression set is considerably worse than those of Examples 1-11.

Claims (6)

(A) A composition obtained by dynamically crosslinking 100 parts by weight of an isobutylene polymer having an alkenyl group at a terminal with a hydrosilyl group-containing polysiloxane,
(B) 5 to 100 parts by weight of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl-based block copolymer;
(C) 70 to 300 parts by weight of polybutene,
Consists of
The polybutene contains an isobutylene skeleton as a main component,
The weight average molecular weight of the polybutene Ri 300-20000 der,
The number average molecular weight of the isobutylene polymer having an alkenyl group at the end is 1,000 to 500,000,
The amount of the terminal alkenyl group in the isobutylene polymer having an alkenyl group at the terminal is 1 to 6 per molecule,
The aromatic vinyl block copolymer has a number average molecular weight of 15,000 to 400,000,
The hydrosilyl group-containing polysiloxane has 3 to 500 hydrosilyl groups,
The molar ratio of the alkenyl group in the isobutylene polymer having an alkenyl group at the terminal to the hydrosilyl group in the hydrosilyl group-containing polysiloxane (alkenyl group / bidrosilyl group) is in the range of 5 to 0.1,
When the isobutylene polymer having an alkenyl group at the terminal is melt-mixed with at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer and polybutene, A thermoplastic elastomer composition comprising a composition dynamically crosslinked with a group-containing polysiloxane . (A) A composition obtained by dynamically crosslinking 100 parts by weight of an isobutylene polymer having an alkenyl group at a terminal with a hydrosilyl group-containing polysiloxane,
(B) 5 to 100 parts by weight of at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl-based block copolymer;
(C) 70 to 300 parts by weight of polybutene,
Consists of
The polybutene contains an isobutylene skeleton as a main component,
The polybutene has a weight average molecular weight of 300-20000,
The number average molecular weight of the isobutylene polymer having an alkenyl group at the end is 1,000 to 500,000,
The amount of the terminal alkenyl group in the isobutylene polymer having an alkenyl group at the terminal is 1 to 6 per molecule,
The aromatic vinyl block copolymer has a number average molecular weight of 15,000 to 400,000,
The hydrosilyl group-containing polysiloxane has 3 to 500 hydrosilyl groups,
The molar ratio of the alkenyl group in the isobutylene polymer having an alkenyl group at the terminal to the hydrosilyl group in the hydrosilyl group-containing polysiloxane (alkenyl group / bidrosilyl group) is in the range of 5 to 0.1,
When the isobutylene-based polymer having an alkenyl group at the terminal is melt-mixed with at least one component selected from the group consisting of a polypropylene resin, a polyethylene resin, and an aromatic vinyl block copolymer, the thermoplastic elastomer composition you comprising a dynamically cross-linked composition by siloxane. The thermoplastic elastomer composition according to claim 1 or 2 , wherein the polypropylene resin is random polypropylene. The thermoplastic elastomer composition according to claim 1 or 2 , wherein the polyethylene resin is high-density polyethylene. Aromatic vinyl block copolymer, the polymer block composed mainly of an aromatic vinyl compound (a), according to claim 1 or characterized in that it comprises from a polymer block mainly comprising isobutylene (b) 2. The thermoplastic elastomer composition according to 2. Polymer block mainly composed of aromatic vinyl compound (a)-Polymer block mainly composed of isobutylene (b)-Polymer block mainly composed of aromatic vinyl compound 6. The thermoplastic elastomer composition according to claim 5 , wherein the thermoplastic elastomer composition is a triblock copolymer having a weight average molecular weight of 40,000 to 200,000 showing the structure of (a).