JP2006152030A - Method for producing thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition excellent in not only rubber-like characteristics, a gas barrier property and a vibration-damping property, but also excellent in a permanent compression set characteristic, moldability and processability and the balance of hardness, tensile strength and elongation properties. <P>SOLUTION: The method for producing the thermoplastic elastomer comprises melting and kneading a resin component composed of an isobutylene-based polymer having an alkenyl group at the end and a polyethylene-based resin and/or a polypropylene-based resin with in inorganic filler, then adding a hydrosilyl group-containing polysiloxane thereto, further melting and kneading these components and dynamically crosslinking the isobutylene-based polymer with the hydrosilyl group-containing polysiloxane or melting and kneading the isobutylene-based polymer having an alkenyl group at the end with the inorganic filler and the hydrosilyl group-containing polysiloxane, dynamically crosslinking the isobutylene-based polymer with the hydrosilyl group-containing polysiloxane, adding a resin component composed of the polyethylene-based resin and/or the polypropylene-based resin thereto and further melting and kneading these components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for producing a novel thermoplastic elastomer composition which is rich in flexibility, excellent in moldability and rubber-like properties, and particularly excellent in compression set 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. 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, Patent Documents 1-9, etc.). .

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. In addition, the cross-linked thermoplastic elastomer improves the compression set by increasing the degree of cross-linking, thereby reducing flexibility, heat resistance, breaking strength and breaking elongation in a tensile test, or softening agent on the composition surface. Bleed and the like occur. As described above, it is difficult to obtain a thermoplastic composition having an excellent balance of physical properties, and as with conventional thermoplastic resins, it can be easily molded by a hot press or the like, and a heat property having an excellent balance of physical properties. Development of a plastic elastomer composition 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 properties, gas barrier properties, and vibration damping properties, but also exhibits particularly good compression set properties and molding processability. Another object of the present invention is to provide a production method for obtaining a thermoplastic elastomer composition having an excellent balance of hardness-tensile strength and elongation property, and a thermoplastic elastomer composition.

As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention melts an isobutylene polymer (A) having an alkenyl group at the terminal, a resin component (B) composed of a polyethylene resin (B1) and / or a polypropylene resin (B2), and an inorganic filler (C). Kneading, then adding hydrosilyl group-containing polysiloxane (D) and further melt-kneading to dynamically crosslink the isobutylene polymer (A) with hydrosilyl group-containing polysiloxane (D) The present invention relates to a method for producing a plastic elastomer composition.

In the present invention, the isobutylene polymer (A) having an alkenyl group at the terminal, the inorganic filler (C), and the hydrosilyl group-containing polysiloxane (D) are melt kneaded to convert the isobutylene polymer (A) into a hydrosilyl group. A heat characterized by dynamically crosslinking with the polysiloxane (D), adding a resin component (B) comprising a polyethylene resin (B1) and / or a polypropylene resin (B2), and further melt-kneading. The present invention also relates to a method for producing a plastic elastomer composition.

As a preferred embodiment, the present invention relates to a method for producing the thermoplastic elastomer composition, wherein the melt kneading temperature is 130 to 260 ° C.

The present invention also relates to a thermoplastic elastomer composition obtained by the above method.

As a preferable embodiment, 5 to 100 parts by weight of the resin component (B) composed of the polyethylene resin (B1) and / or the polypropylene resin (B2) is contained with respect to 100 parts by weight of the isobutylene polymer (A). The above-mentioned thermoplastic elastomer composition.

As a preferred embodiment, the present invention relates to the thermoplastic elastomer composition, wherein 1 to 300 parts by weight of the inorganic filler (C) is contained with respect to 100 parts by weight of the isobutylene polymer (A).

The hydrosilyl group-containing polysiloxane (D) was mixed so that the ratio of the hydrylsilyl group in the polysiloxane (D) was 0.2 to 10 mol with respect to 1 mol of the alkenyl group in the isobutylene polymer (A). It is related with the said thermoplastic elastomer composition characterized by the above-mentioned.

In a preferred embodiment, the thermoplastic elastomer composition further comprises 1 to 300 parts by weight of a softening agent (E) with respect to 100 parts by weight of the isobutylene polymer (A).

In a preferred embodiment, the thermoplastic elastomer composition is characterized in that the polyethylene resin (B1) is high-density polyethylene.

In a preferred embodiment, the thermoplastic elastomer composition is characterized in that the polypropylene resin (B2) is random polypropylene.

A preferred embodiment relates to the thermoplastic elastomer composition, wherein the inorganic filler (C) is at least one selected from the group consisting of talc, calcium carbonate and silica.

In a preferred embodiment, the thermoplastic elastomer composition is characterized in that the softening agent (E) is paraffinic oil or polybutene.

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 compression set characteristics, and is excellent in hardness-tensile strength and elongation characteristic balance. For this reason, it can be used suitably for various uses, such as sealing materials, such as a packing material, a damping material, a vibration proof material, a vehicle interior material, a cushion material.

The method for producing a thermoplastic elastomer of the present invention comprises an isobutylene polymer (A) having an alkenyl group at the terminal, a resin component (B) comprising a polyethylene resin (B1) and / or a polypropylene resin (B2), and an inorganic material. The isobutylene polymer (A) is dynamically cross-linked with the hydrosilyl group-containing polysiloxane (D) by melt-kneading the filler (C), then adding the hydrosilyl group-containing polysiloxane (D) and further melt-kneading. This is a method for producing a thermoplastic elastomer composition.

The method for producing the thermoplastic elastomer of the present invention comprises isobutylene-based heavy polymer by melt-kneading an isobutylene polymer (A) having an alkenyl group at the terminal, an inorganic filler (C) and a hydrosilyl group-containing polysiloxane (D). After the coalescence (A) is dynamically cross-linked with the hydrosilyl group-containing polysiloxane (D), the resin component (B) composed of the polyethylene resin (B1) and / or the polypropylene resin (B2) is added and further melt kneaded. This is also a method for producing a thermoplastic elastomer composition.

The isobutylene polymer (A) used in the present invention is 50% by weight or more, preferably 70% by weight of monomer components derived from isobutylene among the monomer components constituting the main chain of the polymer (A). %, More preferably 90% by weight or more. The monomer other than isobutylene in the isobutylene-based polymer (A) having an alkenyl group at the terminal or a polymer block mainly composed of isobutylene is not particularly limited as long as it is a monomer component capable of cationic polymerization. Examples include aromatic vinyls, aliphatic olefins, dienes such as isoprene, butadiene and divinylbenzene, monomers such as vinyl ethers and β-pinene. These may be used alone or in combination of two or more.

The molecular weight of the isobutylene polymer (A) having an alkenyl group at the terminal is not particularly limited, but the number average molecular weight 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 at the end of the isobutylene polymer (A) is a group containing a carbon-carbon double bond that is active for the crosslinking reaction of the component (A) for achieving the object of the present invention. There is no particular limitation. 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 into the terminal of the isobutylene polymer (A) having an alkenyl group at the terminal 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 (A) 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 are terminated. It is preferable that the polymer has If the number is less than 0.2, the improvement effect due to crosslinking may not be sufficiently obtained.

The resin component (B) is composed of a polyethylene resin (B1) and / or a polypropylene resin (B2). The resin component (B) may be added when the isobutylene polymer (A) having an alkenyl group at the terminal is dynamically cross-linked (during melt-kneading), or for the dynamically cross-linked composition Can also be added. The resin component (B) is blended in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the isobutylene polymer (A). If the blending amount exceeds 100 parts by weight, the effect of improving compression set characteristics tends to be poor. On the other hand, if it is less than 5 parts by weight, sufficient fluidity cannot be obtained during molding, and the moldability is impaired. The blending amount of the resin component (B) is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the isobutylene polymer (A) from the viewpoint of moldability and rubber elasticity.

The polyethylene-based resin (B1) is an ethylene homopolymer obtained by polymerizing a monomer component containing 50 to 100 mol% of ethylene among all monomer components, or ethylene and 3 to 20 carbon atoms. It is a copolymer with an α-olefin. Examples of such a material include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, and high-density polyethylene is particularly preferable from the viewpoint of tensile properties and heat resistance of the resulting composition.

The polypropylene resin (B2) is a homopolymer of propylene obtained by polymerizing a monomer component containing 50 to 100 mol% of propylene among all the monomer components, or propylene and α having 3 to 20 carbon atoms. -Copolymers with olefins. Examples of such a material include homopolypropylene, random polypropylene, and block polypropylene, and a random copolymer is particularly preferable from the viewpoint of tensile properties of the resulting composition. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and the like may be used alone or in combination of two or more. .

The inorganic filler (C) used in the present invention is not particularly limited, and is clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, mica, graphite, aluminum hydroxide, magnesium hydroxide, natural silicic acid. And inorganic fillers such as synthetic silicic acid (white carbon) and metal oxides (titanium oxide, magnesium oxide, zinc oxide). Of these, calcium carbonate, talc, and silica are particularly preferable from the viewpoint of cost and mechanical strength.

The inorganic filler (C) used in the present invention can be used in combination of two or more kinds from the above filler group, and the inorganic filler (C) is 1 part per 100 parts by weight of the isobutylene polymer (A). ˜300 parts by weight, preferably 10 to 200 parts by weight are used. When the amount is less than 1 part by weight, the reinforcing effect by the inorganic filler cannot be sufficiently obtained, and when it exceeds 300 parts by weight, a problem tends to occur in terms of moldability.

Although there is no limitation in particular about hydrosilyl group containing polysiloxane (D), various things can be used. Among them, a hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 or more and 500 or less siloxane units is preferable, and a polysiloxane having 3 or more hydrosilyl groups and 10 or more and 200 or less siloxane units is further included. Polysiloxane having 3 or more hydrosilyl groups and 20 to 100 siloxane units is particularly preferable. When the content of hydrosilyl groups is less than 3, sufficient network growth due to crosslinking cannot be achieved, and optimal rubber elasticity cannot be obtained. On the other hand, when the number of siloxane units is more than 500, the polysiloxane has a high viscosity and is not favorably dispersed in the isobutylene polymer (A) having an alkenyl group at the terminal, and unevenness occurs in the crosslinking reaction, which is not preferable. Further, it is preferable that the number of polysiloxane units is 100 or less because the hydrosilyl group-containing polysiloxane (D) necessary for hydrosilylation can be reduced. The polysiloxane unit mentioned here refers to the following general formulas (I), (II), and (III).
[Si (R ¹ ) ₂ O] (I)
[Si (H) (R ² ) O] (II)
[Si (R ² ) (R ³ ) O] (III)
As the hydrosilyl group-containing polysiloxane (D), a linear polysiloxane represented by the general formula (IV) or (V);
_{^{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, and 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);

(In the formula, R ⁴ and R ⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. E represents 3 ≦ e, d, e , F represents an integer satisfying d + e + f ≦ 500.) And the like can be used.

The isobutylene polymer (A) and the hydrosilyl group-containing polysiloxane (D) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the hydrosilyl group is 0.2 to 10 per 1 mol of the alkenyl group. It is preferably in a molar range, and more preferably 0.4 to 5. When the amount of hydrosilyl groups is less than 0.2 mol, only a cured product with insufficient cross-linking and stickiness and low strength can be obtained, and when it exceeds 10 mol, a large amount of active hydrosilyl groups are present in the cured product even after curing. Therefore, cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The cross-linking reaction between the isobutylene polymer (A) having an alkenyl group at the terminal and the hydrosilyl group-containing polysiloxane (D) proceeds by mixing and heating the two components, but in order to proceed the reaction more quickly. A hydrosilylation catalyst can be added. 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 peroxide 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 (0) -dialkenyltetramethyldisiloxane complex is preferable and platinumdivinyltetramethyldisiloxane is most preferable in view of compatibility, crosslinking efficiency, and scorch stability.

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. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. Moreover, since a hydrosilylation catalyst is expensive, it is preferable not to use more than 10 ^<-1 > mol.

In the first aspect of the present invention, the hydrosilyl group-containing polysiloxane (D) is derived from an isobutylene polymer (A) having a terminal alkenyl group, a polyethylene resin (B1) and / or a polypropylene resin (B2). The resin component (B) to be obtained and the inorganic filler (C) are added after melt-kneading. By this operation, dynamic crosslinking is performed between the isobutylene polymer (A) having an alkenyl group at the terminal and the hydrosilyl group-containing polysiloxane (D). When the catalyst is used in this embodiment, the catalyst is not particularly limited at the time of addition, but it is added before the hydrosilyl group-containing polysiloxane (D) or added simultaneously with the hydrosilyl group-containing polysiloxane (D). It is preferable.

In the second embodiment of the present invention, the polyethylene resin (B1) and / or the polypropylene resin (B2) are an isobutylene polymer (A), an inorganic filler (C), and a hydrosilyl group-containing polysiloxane (D). Is melt-kneaded to dynamically add the isobutylene polymer (A) after dynamically crosslinking with the hydrosilyl group-containing polysiloxane (D). When the above catalyst is used in this embodiment, when the components (A), (C) and (D) are melt-kneaded, (A), (C) and (D) so that the catalyst is present in the system. It is preferable to add a catalyst before or during melt kneading of the components.

In order to further improve the moldability and flexibility, the softener (E) can be further added to the composition produced by the production method of the present invention. As the softening agent, mineral oil used in rubber processing, or a liquid or low molecular weight synthetic softening agent can be used. Mineral oils include paraffinic oils, naphthenic oils, and aromatic high boiling petroleum components. Of these, paraffinic oil that does not inhibit the crosslinking reaction is preferred. The liquid or low molecular weight synthetic softening agent is not particularly limited, and examples thereof include polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, and poly α-olefins. Of these, polybutene is preferred from the viewpoint of gas barrier properties.

One or more of these softeners can be used. The amount of the softening agent (E) used is 1 to 300 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the isobutylene polymer (A) having an alkenyl group at the terminal. When the blending amount exceeds 300 parts by weight, there may be a problem in mechanical strength reduction and moldability. On the other hand, when the amount is less than 1 part by weight, the softening effect tends not to be sufficiently exhibited.

The step of adding the softening agent (E) is not particularly limited, and it may be added before or after the isobutylene block copolymer (A) having an alkenyl group at the terminal is crosslinked. Also good. The softener added before, during and after the isobutylene block copolymer (A) having an alkenyl group at the terminal may be the same softener or a different softener.

Further, in the method for producing the thermoplastic elastomer composition of the present invention, a reinforcing agent, a filler such as ethylene-propylene copolymer rubber (EPM), ethylene is used in accordance with the required characteristics according to each application within a range not to impair physical properties. -Flexible olefin polymers such as propylene-diene terpolymer rubber (EPDM), ethylene-butene copolymer rubber (EBM), amorphous polyalphaolefin (APAO), ethylene-octene copolymer, styrene-butadiene-styrene Block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer Combined (SEPS), styrene-isobutylace Suitable blends of thermoplastic elastomers such as renblock copolymer (SIBS), hindered phenol and hindered amine antioxidants, UV absorbers, light stabilizers, pigments, surfactants and flame retardants can do. Known coupling agents, organic fillers, antiblocking agents, antistatic agents, flame retardants, antioxidants, UV absorbers, softeners, colorants, inorganic or organic antibacterial agents, lubricants, silicone oils, etc. can also be added. . 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 method for producing the thermoplastic elastomer composition of the present invention comprises a resin component (B) comprising an isobutylene polymer (A) having an alkenyl group at the terminal, a polyethylene resin (B1) and / or a polypropylene resin (B2), In addition, the inorganic filler (C) is melt-kneaded, and then the hydrosilyl group-containing polysiloxane (D) is added and further melt-kneaded, whereby the isobutylene polymer (A) is dynamically added to the hydrosilyl group-containing polysiloxane (D). It crosslinks. Alternatively, the isobutylene polymer (A) having an alkenyl group at the terminal, the inorganic filler (C), and the hydrosilyl group-containing polysiloxane (D) are melt-kneaded to convert the isobutylene polymer (A) into the hydrosilyl group-containing polysiloxane. After dynamically crosslinking by (D), the resin component (B) composed of the polyethylene resin (B1) and / or the polypropylene resin (B2) is added and further melt-kneaded.

The above-described method of dynamically crosslinking simultaneously with melt kneading is preferably performed at a temperature of 130 to 260 ° C. When the temperature is lower than 130 ° C, the polyethylene resin (B) is insufficiently melted and tends to be non-uniformly kneaded. When the temperature is higher than 260 ° C, the isobutylene block copolymer having an alkenyl group at the end is used. There exists a tendency for thermal decomposition of a coalescence (A) to advance.

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 6253, a 12.0 mm thick press sheet was used as a test piece, and measurement was performed with a type A durometer.

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

(Tensile breaking elongation)
In accordance with JIS K 6251, a 2 mm-thick press sheet punched into a No. 3 type with a dumbbell was prepared as a test piece, and this was used for measurement. 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 a test piece. The measurement was performed under the conditions of 100 ° C. × 22 hours and 25% deformation.

(Melt viscosity)
The resin composition containing the component (A) and the component (B) has a melt viscosity of a test temperature of 200 ° C., shear rates of 121.6 and 1216 sec ⁻¹ , a die radius of 1 mm, and a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) Was used to measure the melt viscosity (unit: poison (= 0.1 Pa · s)).

(Molecular weight measurement)
The molecular weight shown in this production example was measured by the GPC analyzer shown below, and GPC measurement using a polystyrene gel column was performed using chloroform as a mobile phase to obtain the molecular weight in terms of polystyrene. GPC measurement was performed with a GPC analyzer (system: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK). The molecular weight in terms of polystyrene was determined using chloroform as the mobile phase.

(Measurement of the content of allyl group)
An isobutylene polymer was dissolved in deuterated chloroform, NMR was measured, and the ratio of allyl groups to the initiator was determined to determine the amount of allyl groups per molecule.

(TEM)
The thermoplastic elastomer composition obtained in Example 1 and Comparative Example 1 was molded into a sheet shape with a pressure press manufactured by Shindo Metal Industry Co., Ltd. at 190 ° C., and the surface of the obtained sheet was dyed with RuO _4. After that, a TEM image was obtained by observing under the condition of an acceleration voltage of 80 kw using JEOL JEM-1200FX.

Moreover, the symbol of the material used by the Example and the comparative example and the specific content are as follows.
Component (A) Polyisobutylene having an allyl group at the terminal (Production Example 1)
Component (B1): High-density polyethylene, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd. (trade name “Hi-X” 2200J)
Component (B2): Polypropylene, manufactured by Grand Polymer Co., Ltd. (trade name “Grand Polypro J215W” random polypropylene)
Ingredient (C): Inorganic filler (C-1): Silica Nippon Silica Kogyo Co., Ltd. (trade name “Nip seal VN3”)
(C-2): Talc Fuji Talc Kogyo Co., Ltd. (trade name “LMS-300”)
(C-3): Calcium carbonate Shiraishi Kogyo Co., Ltd. (trade name “SILVER-W”)
(C-4): Calcium carbonate Shiraishi Kogyo Co., Ltd. (trade name “Vigot-15”)
Component (D): 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
catalyst:
1,1,3,3-tetramethyl-1,3-dialkenyldisiloxane complex of zero-valent platinum, 3 wt% xylene solution component (E): softener paraffin process oil, manufactured by JOMO (trade name “P -500 ")

(Production Example 1) [Production of isobutylene-based copolymer (ARPIB2) having an alkenyl group at the terminal]
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. 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 again to about −70 ° C., 0.85 g (3.7 mmol) of 1,4-bis (2-chloro-2-propyl) benzene and 0.68 g (7.4 mmol) of picoline were dissolved in 10 ml of toluene and added. It was. 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 degreeC-80 degreeC), the organic solvent was removed at 80 degreeC under pressure reduction, and ARPIB2 was obtained. A polymer having a number average molecular weight (Mn) of 45500, a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.10, and a contained allyl group of 2.0 / mol was obtained.

Ingredient (A), ingredient (B2), ingredient (C-1) were blended in the proportions shown in Table 1, and melt kneaded for 3 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C. Next, component (E) is added in the proportion shown in Table 1 and kneaded for 3 minutes, then component (D) is added in the proportion shown in Table 1 and kneaded for 1 minute, and then the crosslinking catalyst is shown in Table 1. Then, 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. The obtained thermoplastic elastomer composition could be easily formed into a sheet by performing a pressure press at 190 ° C. (manufactured by Shinfuji Metal Industry Co., Ltd.). The hardness, compression set, and tensile properties of the obtained sheet were measured according to the above methods. Table 1 shows the physical properties of each sheet.

Except having changed component (C-1) to (C-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.

The addition of 25 parts by weight of component (B2) is changed to 40 parts by weight of component (B1), the addition of 40 parts by weight of component (C-1) is changed to 60 parts by weight of (C-3), and Except having changed the addition amount into 110 weight part, 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 except that the addition amount of the component (B) was changed to 30 parts by weight, the addition amount of the component (C-3) was changed to 40 parts by weight, and the addition amount of the component (E) was changed to 150 parts by weight. The resin composition was molded in the same manner as in Example 3, and the physical properties were evaluated. The respective physical properties are shown in Table 1.

A resin composition was molded in the same manner as in Example 3 except that the component (C-3) was changed to the component (C-4), and the physical properties were evaluated. The respective physical properties are shown in Table 1.

(Comparative Example 1)
Ingredients (A) and (B2) were blended in the proportions shown in Table 1, and melt kneaded for 3 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C., and then component (E) Was added at the rate shown in Table 1 and kneaded for 3 minutes, then component (D) was added at the rate shown in Table 1 and kneaded for 1 minute, and then the crosslinking catalyst was added at the rate shown in Table 1, Dynamic crosslinking was performed by further melt-kneading at 170 ° C. until the torque value reached the maximum value. The component (C-1) was added after showing the maximum value of torque, and it was taken out after kneading for 5 minutes. The obtained thermoplastic elastomer composition could be formed into a sheet by pressurizing at 190 ° C. (manufactured by Shinfuji Metal Industry Co., Ltd.). The hardness, compression set, and tensile properties of the obtained sheet were measured according to the above methods. Table 1 shows the physical properties of the sheet.

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

(Comparative Example 3)
The addition of 25 parts by weight of component (B2) is changed to 40 parts by weight of component (B1), the addition of 40 parts by weight of component (C-1) is changed to 60 parts by weight of (C-3), and A resin composition was molded in the same manner as in Comparative Example 1 except that the addition amount was changed to 110 parts by weight, and the physical properties were evaluated. The respective physical properties are shown in Table 1.

(Comparative Example 4)
Comparative example except that the addition amount of component (B) was changed to 30 parts by weight, the addition amount of component (C-3) was changed to 40 parts by weight, and the addition amount of component (E) was changed to 150 parts by weight The resin composition was molded in the same manner as in Example 3, and the physical properties were evaluated. The respective physical properties are shown in Table 1.

(Comparative Example 5)
A resin composition was molded in the same manner as in Comparative Example 1 except that the amount of component (C-1) added was changed to 0 part by weight, and the physical properties were evaluated. The respective physical properties are shown in Table 1.

From Table 1, Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, 3, and 4 are compared, and in Examples 1, 2, 3, and 4 in which component (C) is added together with component (A), The compression set is smaller than 30%, the tensile breaking strength is 3 MPa or more, the tensile breaking elongation is 350% or more, and Examples 1, 2, 3, and 4 are superior to Comparative Examples 1, 2, 3, and 4. I understand that Moreover, when Examples 1-4 and Comparative Examples 1-4 are compared by the same mixing | blending, it turns out that the melt viscosity is smaller in Examples 1-4 and is excellent in fluidity | liquidity, respectively.

From the above, it can be seen that a thermoplastic resin composition excellent in compression set, tensile properties and fluidity can be obtained by adding the filler as the component (C) before dynamically crosslinking.

1 and 2 are TEM images of the sheet surface on which the thermoplastic resin composition obtained in Example 1 was molded. 3 and 4 are TEM images of the sheet surface on which the thermoplastic resin composition obtained in Comparative Example 1 was molded. The thermoplastic resin compositions obtained in Example 1 and Comparative Example 1 have the same blending, but the addition order of component (C-1) is different. 1-4, the gray part with the widest area is the component (A), the gray part dispersed in the component (A) is the component (B1), and the black part with the highest staining is the component (B). C-1). It can be seen that FIG. 1 or 2 and FIG. 3 or 4 differ in the location of the component (C-1). That is, the component (C-1) is present in the component (A) in FIGS. 1 and 2 and in the components (B) and the interface between the component (A) and the component (B1) in FIGS. From this, it is considered that the location of the component (C-1) affects the physical properties of the thermoplastic resin composition of the present invention. It is considered that improvement in rubber elasticity and tensile properties can be achieved by incorporating the component (C-1) into the component (A) and increasing the apparent volume of the component (A).

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. Further, since the thermoplastic elastomer composition of the present invention is excellent in moldability, compression set, and gas barrier properties, it is a sealing material such as a packing material, a sealing material, a gasket and a plug, a CD damper, an architectural damper, an automobile. , Vibration control materials such as vibration control materials for vehicles and home appliances, anti-vibration materials, automotive interior materials, cushion materials, daily necessities, electrical parts, electronic parts, sports materials, grips or cushioning materials, wire coating materials, packaging materials, various types It can be used effectively as a container and stationery component.

TEM image (magnification: × 10000) of the sheet surface on which the thermoplastic resin composition obtained in Example 1 was molded TEM image (magnification: × 4800) of the sheet surface on which the thermoplastic resin composition obtained in Example 1 was molded TEM image (magnification: × 10000) of the sheet surface on which the thermoplastic resin composition obtained in Comparative Example 1 was molded TEM image (magnification: x4800) of the sheet surface on which the thermoplastic resin composition obtained in Comparative Example 1 was molded

Claims (12)

An isobutylene polymer (A) having an alkenyl group at the terminal, a resin component (B) comprising a polyethylene resin (B1) and / or a polypropylene resin (B2), and an inorganic filler (C) are melt-kneaded, and then hydrosilylated A thermoplastic elastomer composition characterized in that an isobutylene polymer (A) is dynamically crosslinked with a hydrosilyl group-containing polysiloxane (D) by adding a group-containing polysiloxane (D) and further melt-kneading. Manufacturing method. An isobutylene polymer (A) having an alkenyl group at the terminal, an inorganic filler (C), and a hydrosilyl group-containing polysiloxane (D) are melt-kneaded to convert the isobutylene polymer (A) into a hydrosilyl group-containing polysiloxane (D Of the thermoplastic elastomer composition, wherein the resin component (B) composed of the polyethylene resin (B1) and / or the polypropylene resin (B2) is added and further melt-kneaded. Manufacturing method. The method for producing a thermoplastic elastomer composition according to claim 1 or 2, wherein the melt kneading temperature is 130 to 260 ° C. A thermoplastic elastomer composition obtained by the method according to claim 1. The resin component (B) comprising the polyethylene resin (B1) and / or the polypropylene resin (B2) is contained in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the isobutylene polymer (A). Item 5. The thermoplastic elastomer composition according to Item 4. 6. The thermoplastic elastomer composition according to claim 4, comprising 1 to 300 parts by weight of the inorganic filler (C) with respect to 100 parts by weight of the isobutylene polymer (A). The hydrosilyl group-containing polysiloxane (D) was mixed so that the ratio of the hydrylsilyl group in the polysiloxane (D) was 0.2 to 10 mol with respect to 1 mol of the alkenyl group in the isobutylene polymer (A). The thermoplastic elastomer composition according to any one of claims 4 to 6, wherein: The thermoplastic elastomer composition according to any one of claims 4 to 7, further comprising 1 to 300 parts by weight of the softening agent (E) with respect to 100 parts by weight of the isobutylene polymer (A). The thermoplastic elastomer composition according to any one of claims 4 to 8, wherein the polyethylene resin (B1) is high-density polyethylene. The thermoplastic elastomer composition according to any one of claims 4 to 9, wherein the polypropylene resin (B2) is random polypropylene. The thermoplastic elastomer composition according to any one of claims 4 to 10, wherein the inorganic filler (C) is at least one selected from the group consisting of talc, calcium carbonate, and silica. The thermoplastic elastomer composition according to any one of claims 8 to 11, wherein the softening agent (E) is paraffinic oil or polybutene.