JP2007262424A - Thermoplastic elastomer resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an isobutylene-based thermoplastic elastomer resin composition which maintains the basic characteristics of the thermoplastic elastomer resin composition, such as mechanical strengths, moldability and appearance, has improved flexibility such as low hardness and low impact resilience, and does not bleed out a plasticizer, and to provide various packings. <P>SOLUTION: This thermoplastic elastomer resin composition comprises: (a) 100 pts.wt. of an isoprene-based triblock copolymer comprising a polymer block containing an aromatic vinylic compound as a main monomer component, a polymer block containing isoprene as a main monomer component, and a polymer block containing an aromatic vinylic compound as a main component; (b) 10 to 25 pts.wt. of a polyolefin-based polymer; and 0.1 to 50 pts.wt. of a filler. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic elastomer resin composition comprising an isobutylene block copolymer and a polyolefin polymer, and more specifically, a thermoplastic elastomer characterized by low hardness and low resilience and useful as various packings. The present invention relates to a resin composition.

  Molded articles made of thermoplastic resins are widely used for automobile parts, household electrical appliance parts, daily necessities, sports equipment, toys, industrial parts, and the like. Among these, polyolefin resins are used as a wide range of molded articles because of their excellent balance between cost, moldability, and physical properties.

  On the other hand, in recent years, it is a rubber-like soft material that does not require a vulcanization process, and a thermoplastic elastomer having molding processability similar to that of a thermoplastic resin is used for automobile parts, home appliance parts, miscellaneous goods, footwear, wire coating, etc. Furthermore, it is attracting attention in the packing field. As such thermoplastic elastomers, various polymers such as polyolefin-based, polyurethane-based, polyester-based, polystyrene-based, and polyvinyl chloride-based polymers have been developed and are commercially available. These thermoplastic elastomers may be used by themselves, but thermoplastic elastomer resin compositions in which various combinations of thermoplastic resins and thermoplastic elastomers are being studied in order to meet various needs of users.

  In particular, a thermoplastic elastomer resin composition comprising a polyolefin-based resin and a polystyrene-based elastomer such as styrene-butadiene-block copolymer (SBS) or styrene-isoprene-block polymer (SIS) and a softening agent has hardness, flexibility, cushioning resistance, It has been widely used as a material having a good balance of impact properties, rubber elasticity, moldability, and the like.

  However, the conventional thermoplastic elastomer resin composition of polyolefin-based resin and polystyrene-based elastomer has a problem that heat resistance (heat aging resistance) and weather resistance are not sufficient, and further, a softener, a lubricant, There was a problem that low molecular weight components such as paraffin oil were contained.

  In order to solve this problem, an attempt has been made to obtain a thermoplastic elastomer resin composition having improved thermal stability by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene. .

  For example, Japanese Patent Publication No. 6-88608 discloses a container lid with a liner made of a composition containing liquid paraffin and a propylene resin in a hydrogenated styrene / butadiene block copolymer having a specific MI. No. 239481 discloses a resin containing a hydrogenated vinyl aromatic / conjugated diene block copolymer having a specific Mn, a propylene-based polymer having a specific MI, a propylene-based copolymer having a specific melting point, and the like. Compositions and liner materials have been proposed. However, although these compositions have hydrogenated conjugated diene blocks, they may have residual double bonds in the molecule, so that there are problems with heat stability (heat aging resistance), weather resistance, and the like. Furthermore, they have high hardness, high resilience, and insufficient flexibility. On the other hand, in order to impart flexibility, the addition of a plasticizer or softener has been essential. In order to solve this, there can be no residual double bond in the molecule, specifically, thermal stability, weather resistance, vibration damping, gas barrier properties, and flexibility are improved, and An isobutylene / styrene-based thermoplastic elastomer resin composition without a plasticizer bleed-out is desired. Regarding these, JP-A-9-87438 discloses a resin composition and a closure mainly composed of a polyolefin resin, an aromatic vinyl / isobutylene block copolymer, and JP-A-11-293083 discloses an isobutylene. A thermoplastic resin composition comprising a system block copolymer, a polyolefin resin, and a softening agent has been proposed. However, these compositions also have high hardness and high impact resilience, insufficient flexibility, and the addition of a plasticizer or softener was essential.

  The object of the present invention is to improve the flexibility such as low hardness and low rebound resilience while maintaining the basic properties of the thermoplastic elastomer resin composition such as mechanical strength, moldability and appearance, and An object of the present invention is to provide an isobutylene-based thermoplastic elastomer resin composition, various packings, and the like, characterized by having no bleed-out.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic elastomer resin composition containing an isobutylene block copolymer and a polyolefin polymer solves the above problems. This is the headline and the present invention.

  That is, the present invention includes (a) a polymer block having an aromatic vinyl compound as a monomer main component-a polymer block having an isobutylene as a monomer main component-an aromatic vinyl compound as a monomer main component. A thermoplastic elastomer comprising 100 parts by weight of an isobutylene-based triblock copolymer comprising a polymer block, (b) 10 to 25 parts by weight of a polyolefin polymer, and 0.1 to 50 parts by weight of a filler. It is a resin composition. In the present invention, the rebound resilience of the thermoplastic elastomer resin composition obtained in accordance with JIS K 6255 using a 12.0 mm thick press sheet is preferably 40% or less, and 30% or less. Is more preferable. The component (b) is preferably a polypropylene polymer.

The elastomer resin composition obtained by the method of the present invention is rich in flexibility and cushioning properties, that is, has characteristics such as low hardness and low rebound resilience, rubber characteristics, heat resistance, oil resistance, retort resistance, mechanical Of thermoplastic elastomer resin compositions with balanced properties such as mechanical strength, moldability, heat stability, weather resistance, vibration damping, gas barrier properties and appearance, and lack of bleed-out of plasticizer. Is useful.

  The isobutylene block copolymer which is the component (a) of the present invention has a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component. There is no particular limitation as long as it is, for example, a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock copolymer, etc. having a linear, branched, or star structure. Any of them can be selected, and one or two or more selected from viscoelastic properties, physical properties and molding processability may be selected and used.

  As a preferred structure of the isobutylene block copolymer of the present invention, a polymer block-isobutylene having an aromatic vinyl compound as a main monomer component is used as a monomer from the viewpoint of physical properties and processability of the resulting composition. Polymer block having main component-triblock copolymer formed from polymer block having main component of aromatic vinyl compound as monomer main component, Polymer block-aromatic vinyl having main component of isobutylene as main component of monomer Polymer block mainly composed of monomeric compound-Triblock copolymer formed from polymer block composed mainly of monomer based on isobutylene, polymer block composed mainly of aromatic vinyl compound Diblock copolymer formed from polymer block having monomer block-isobutylene as monomer main component, and aromatic vinyl compound as monomer main component Polymer block - is at least one diblock copolymer formed isobutylene from the polymer block whose monomer major component is selected from the group consisting of star-shaped polymer to be the arm.

  Examples of the aromatic vinyl compound of the present invention include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α- Methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methyl Styrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2, 4-dimethylstyrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro Ro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichloro Styrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m -Or p-t-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, substituted with a silyl group Examples thereof include styrene derivatives, indene, vinyl naphthalene and the like. These may be used alone or in combination of two or more.

  In the polymer block containing the aromatic vinyl compound of the present invention as the main component of the monomer, components other than the main component are 40% by weight or less in the block, preferably 20% by weight or less, preferably 5% by weight. More preferably, it is as follows. Specifically, it is not particularly limited as long as it is a monomer component capable of cationic polymerization, and examples include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene, and acenaphthylene. it can. These may be used alone or in combination of two or more.

  Aliphatic olefin monomers include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane Octene, norbornene and the like. These may be used alone or in combination of two or more.

  Examples of the diene monomer include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene. These may be used alone or in combination of two or more.

  Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, tert-, iso) butyl vinyl ether, methyl propenyl ether, ethyl propenyl ether and the like. These may be used alone or in combination of two or more.

  Examples of the silane compound include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3. , 3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like. These may be used alone or in combination of two or more.

  In addition, the block comprising the aromatic vinyl compound of the present invention as the main component of the monomer has a content of aromatic vinyl compound of 60% by weight or more, preferably 80% by weight, from the balance between physical properties and polymerization characteristics. Above, more preferably 95% or more. As the aromatic vinyl compound, it is preferable to use at least one monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and indene. From the viewpoint of cost, styrene, α-methyl It is particularly preferable to use styrene or a mixture thereof.

  The block mainly composed of isobutylene of the present invention may or may not contain a monomer other than isobutylene. Usually, isobutylene is 60% by weight or more, preferably 80% by weight or more. More preferably, it is a monomer component containing 95% or more. The monomer other than isobutylene is not particularly limited as long as it is a monomer capable of cationic polymerization, and examples thereof include the above monomers.

  The ratio of the polymer block containing isobutylene as the main monomer component and the polymer block containing the aromatic vinyl compound as the main monomer component is not particularly limited, but from the balance of processability and physical properties, isobutylene can be used. It is preferable that the polymer block containing a monomer as a main component is 98 to 40% by weight, and the polymer block containing an aromatic vinyl compound as a monomer as a main component is 2 to 60% by weight. It is particularly preferable that the polymer block containing 95 to 60% by weight of the main component and the polymer block containing aromatic vinyl compound as the main component of the monomer is 5 to 40% by weight, and isobutylene is the main component of the monomer. It is particularly preferred that 90 to 70% by weight of the polymer block and 10 to 30% by weight of the polymer block containing an aromatic vinyl compound as the main monomer component.

  Moreover, although there is no restriction | limiting in particular also in the weight average molecular weight of an isobutylene type block copolymer, From surfaces, such as a moldability, workability, and a physical property, it is 5000-150,000, It is preferable that it is 10000-500000, 20000-250,000 Particularly preferred is 40,000 to 125,000. When the weight average molecular weight of the isobutylene block copolymer is less than 5,000, the physical properties are not sufficiently exhibited, and when it exceeds 1500,000, it is disadvantageous in terms of the balance among moldability, workability, and physical properties.

  The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 3 or less.

  The block copolymer of the present invention includes an aromatic vinyl-conjugated diene thermoplastic elastomer, such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS). Moreover, at least 1 sort (s), such as a styrene-ethylene butylene-styrene block copolymer (SEBS) and styrene-ethylene propylene-styrene block copolymer (SEPS) which hydrogenated them, may be contained.

Although there is no restriction | limiting in particular about the manufacturing method of an isobutylene type block copolymer, For example, in presence of the compound represented by following General formula (1), the monomer which has isobutylene as a main component, and isobutylene as a main component It is obtained by polymerizing monomer components that do not.
(CR ¹ R ² X) _n R ³ (1)
[Wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R ¹ and R ² are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ¹ , R ² may be the same or different, R ³ is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6.

  Examples of the halogen atom include chlorine, fluorine, bromine and iodine. It does not specifically limit as said C1-C6 alkoxyl group, For example, a methoxy group, an ethoxy group, n-, or an isopropoxy group etc. are mentioned. It does not specifically limit as said C1-C6 acyloxyl group, For example, an acetyloxy group, a propionyloxy group, etc. are mentioned. It does not specifically limit as said C1-C6 hydrocarbon group, For example, a methyl group, an ethyl group, n-, or an isopropyl group etc. are mentioned.

The compound represented by the general formula (1) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. Examples of the compound of the general formula (1) used in the present invention include the following compounds.
(1-Chloro-1-methylethyl) benzene [C ₆ H ₅ C (CH ₃ ) ₂ Cl], 1,4-bis (1-chloro-1-methylethyl) benzene [1,4-Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1,3-bis (1-chloro-1-methylethyl) benzene [1,3-Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1,3,5-tris (1-chloro-1-methylethyl) benzene [1,3,5- (ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ], 1,3-bis (1-chloro-1-methylethyl)-5-(tert-butyl) benzene _{[1,3- (C (CH 3) 2} Cl) 2 -5- (C (CH 3) 3) C 6 H 3 ] .

Among these, bis (1-chloro-1-methylethyl) benzene [C ₆ H ₄ (C (CH ₃ ) ₂ Cl) ₂ ], tris (1-chloro-1-methylethyl) benzene [( ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ].

  Note that bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, and tris (1-chloro-1 -Methylethyl) benzene is also called tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene or tricumyl chloride.

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

  In the polymerization of the isobutylene block copolymer, an electron donor component can be further present if necessary. This electron donor component is considered to have an effect of stabilizing the growth carbon cation during cationic polymerization, and a polymer having a controlled structure with a narrow molecular weight distribution is formed by addition of the electron donor. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.

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

  These solvents are used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer. The amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the resulting polymer solution and the ease of heat removal.

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

  Polymer block comprising aromatic vinyl compound as monomer main component-Method for producing star polymer having diblock copolymer as arm formed from polymer block comprising isobutylene as monomer main component Although there is no particular limitation, for example, in the presence of a compound having three or more cationic polymerization initiation points, a monomer having an aromatic vinyl compound as a main component and a monomer component having isobutylene as a main component. A polymerization method, a monomer containing an aromatic vinyl compound as a main component and a monomer component containing isobutylene as a main component are produced to produce a diblock copolymer, and then a polyfunctional compound is cupped. Examples thereof include a method of coupling (bonding) the diblock copolymer using as a ring agent (binder).

  As said polyfunctional compound, the compound etc. which have the reaction point (functional group) which can be coupled 3 or more per molecule can be used. When a compound having two reaction points per molecule is polymerized or reacted to form a polymer to have three or more reaction points (functional groups), the use is not hindered.

  Examples of such polyfunctional compounds include 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diiso Propenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributyl Divinyl aromatic compounds such as naphthalene and 2,2′-divinyl-4-ethyl-4′-propylbiphenyl; 1,2,4-trivinylbenzene, 1,3,5-trivinylnaphthalene, 3,5 Trivinyl aromatic compounds such as 4′-trivinylbiphenyl and 1,5,6-trivinyl-3,7-diethylnaphthalene; cyclohexane diepoxy 1, epoxides such as 1,4-pentane diepoxide, 1,5-hexane diepoxide; diketones such as 2,4-hexane-dione, 2,5-hexane-dione, 2,6-heptane-dione; Examples include dialdehydes such as 4-butane dial, 1,5-pentane dial, and 1,6-hexane dial; siloxane compounds and calixarene. These may be used alone or in combination of two or more.

  Among these, divinyl aromatic compounds are preferably used from the viewpoint of reactivity, physical properties of the obtained star polymer, and the like, and particularly preferable are 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-di It is at least one selected from the group consisting of isopropenylbenzene and 1,4-diproisophenylbenzene. The above compound is usually commercially available as a mixture with, for example, ethyl vinyl benzene, and can be used as it is if the above divinyl aromatic compound is the main component. It may be used.

  Maintains excellent heat resistance, oil resistance, heat stability, etc. of isobutylene block copolymer, and improves moldability, flexibility during heat and oil resistance, cushioning, sealing, and impact resistance The (b) polyolefin polymer of the present invention used for the purpose is a homopolymer of ethylene or α-olefin, or a random copolymer, a block copolymer and a mixture thereof, or ethylene or α-olefin. Random copolymers, block copolymers, graft copolymers, modified products of these polymers, and the like can be used singly or in combination. Specifically, polyethylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate Copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl (meth) acrylate copolymer, polyethylene polymer such as chlorinated polyethylene, polypropylene, propylene-ethylene random copolymer, propylene-butene-1 random copolymer Polymers, propylene-hexene-1 random copolymers, propylene-4-methyl-1-pentene random copolymers, propylene-ethylene block copolymers, polypropylene polymers such as chlorinated polypropylene, polybutene, polyisobutylene, Polymethylpentene, ring (Co) polymers of olefins, oxidation, acid (derivative) of glycidylated, oxazolyl, halogenation, sulfonation, can be exemplified various polyolefins obtained by (meth) acrylated. Among these, a polyethylene polymer, a polypropylene polymer, or a mixture thereof can be preferably used from the viewpoint of the balance of cost and physical properties of the thermoplastic elastomer resin composition.

  Maintains excellent heat resistance, oil resistance, heat stability, etc. of isobutylene block copolymer, and improves molding processability, flexibility during heat and oil resistance, cushioning, sealing, and impact resistance For this purpose, in particular, a melt flow rate of 10 g / 10 min or higher, in particular 30 g / 10 min or higher (isotactic or syndiotactic) polypropylene, and / or in particular a melting point of 135 to 170 ° C. Preference is given to polypropylene at 145 to 160 ° C. (isotactic or syndiotactic). If monomers other than propylene are 5 weight% or less, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-ethylene-butene-1 copolymer, etc. can also be used. These copolymers may be random copolymers, block copolymers, or a mixture of two or more.

  The amount of component (b) polyolefin polymer is 5.0 to 70 parts by weight, preferably 7.5 to 50 parts by weight, more preferably 100 parts by weight of component (a) isobutylene block copolymer. Is 10 to 25 parts by weight. When the amount is less than 5.0 parts by weight, the mechanical strength / molding processability of the resulting thermoplastic elastomer resin composition is lowered, and when it exceeds 70 parts by weight, the rubbery feel of the obtained thermoplastic elastomer resin composition is reduced. It will decline.

  In the present invention, as the component (b), a component that mainly undergoes a decomposition reaction by heat treatment in the presence of peroxide may be included, and rubber dispersion in the resulting composition is improved, and molding is performed. The characteristics can be adjusted, such as improving the appearance of the product. On the other hand, as the component (b), a component that mainly undergoes a crosslinking reaction by heat treatment in the presence of peroxide may be included, and the characteristics can be adjusted such that the fluidity is lowered.

  Furthermore, the thermoplastic elastomer resin composition of the present invention can be blended with a filler from the viewpoint of improving physical properties or economic merit. Suitable fillers include clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, mica, graphite, aluminum hydroxide, magnesium hydroxide, natural silicic acid, synthetic silicic acid (white carbon), metal oxidation Examples thereof include inorganic fillers such as materials (titanium oxide, magnesium oxide, zinc oxide). Of these, calcium carbonate, magnesium oxide, zinc oxide, and mica are particularly preferable.

  Preferably used as a thermal conductivity imparting material, various metal powders such as iron and iron oxide, wood chips, glass powder, ceramics powder, carbon black, granular or powdered solid filler such as powdered polymer, and other various kinds Examples thereof include natural or artificial short fibers and long fibers. Moreover, weight reduction can be attained by mix | blending the hollow filler, for example, inorganic hollow fillers, such as a glass balloon and a silica balloon, and the organic hollow filler which consists of a polyvinylidene fluoride and a polyvinylidene fluoride copolymer. Furthermore, various foaming agents can be mixed in order to improve various physical properties such as weight reduction and impact absorption, and it is also possible to mix gas mechanically during mixing. Thermally expandable microcapsules may be mixed.

  The blending amount of the filler is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the component (a) isobutylene block copolymer. If it exceeds 50 parts by weight, the mechanical strength of the resulting thermoplastic elastomer resin composition is lowered, and the flexibility is also impaired.

  Hereinafter, it describes about an arbitrary component. First, a small amount of a softening agent may be used in a range that does not impair the effects of the present invention, that is, a range that does not bleed out. Usually, a liquid or liquid material is suitably used at room temperature. Both hydrophilic and hydrophobic softeners can be used. Examples of such softeners include various rubber or resin softeners such as mineral oils, vegetable oils, and synthetics. As mineral oils, aromatic, naphthenic, paraffinic and other process oils, and as vegetable oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, Examples of synthetic systems include wax, pine oil, olive oil and the like, and polybutene, low molecular weight polybutadiene, and the like. Among these, paraffinic process oil or polybutene (having less aromatic ring components) is preferably used from the viewpoint of compatibility with the component (a) or balance of physical properties of the thermoplastic elastomer resin composition. These softening agents can be used alone or in combination of two or more in order to obtain an effect of improving the viscosity, moldability, physical properties, appearance and the like.

  In the present invention, an organic peroxide may be used as a crosslinking agent or for a decomposition reaction. As necessary, other than organic peroxides, for example, organic nitroso compounds such as azo compounds, sulfur, organic sulfur compounds, aromatic nitroso compounds, oxime compounds, metal oxides such as zinc oxide and magnesium oxide, Examples include polyamines, compounds such as selenium and tellurium, and resin crosslinking agents such as alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins.

  In the method for producing the thermoplastic elastomer resin composition of the present invention, a crosslinking aid which is a monomer having an ethylenically unsaturated group can be blended in the treatment with the organic peroxide. Other crosslinking aids can also be used. Other crosslinking aids include, for example, guanidine compounds such as diphenylguanidine, aldehyde amine compounds, aldehyde ammonium compounds, thiazole compounds, sulfenamide compounds, thiourea compounds, thiuram compounds, dithiocarbamate compounds. And so on.

  Furthermore, together with the above-mentioned crosslinking agent and crosslinking aid, etc., if necessary, zinc white, N, N-m-phenylenebismaleimide, metal halide, organic halide, maleic anhydride, glycidyl methacrylate, hydroxypropyl methacrylate, Compounds such as stearic acid can also be used.

  If necessary, the thermoplastic elastomer resin composition of the present invention includes an aromatic vinyl-conjugated diene-based thermoplastic elastomer such as a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer. A polymer (SIS), or a hydrogenated styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), or the like may be blended. .

  Furthermore, the thermoplastic elastomer resin composition of the present invention can be blended with an antioxidant and / or an ultraviolet absorber as necessary, and in addition to them, as other additives, flame retardant, antibacterial agent, heat Add stabilizers, light stabilizers, colorants, fluidity improvers, processing aids (preferably acrylic processing aids), crystal nucleating agents, lubricants, antiblocking agents, sealability improvers, antistatic agents, etc. These can be used alone or in combination of two or more. Furthermore, as long as the performance of the thermoplastic elastomer resin composition of the present invention is not impaired, various thermoplastic resins such as vinyl aromatic polymers, thermoplastic elastomers such as polyesters, polyamides, and polyurethanes, heat A curable resin, further a hydrogenated petroleum resin, a silicone oil, a silicone compound, a fluorine compound, an electron donating compound, and the like may be blended.

  There is no restriction | limiting in particular in the manufacturing method of the thermoplastic elastomer resin composition of this invention, A well-known method is applicable. For example, each of the above components and optionally the additive components are melt-kneaded using a heating kneader, such as a single screw extruder, twin screw extruder, roll, Banbury mixer, Brabender, kneader, high shear mixer, etc. Can be manufactured. The order of kneading the components is not particularly limited, and can be determined according to the equipment used, workability, or physical properties of the resulting thermoplastic elastomer resin composition.

  The thermoplastic elastomer resin composition of the present invention can be molded using a thermoplastic elastomer composition or a molding method and molding apparatus generally employed for a thermoplastic resin composition. For example, extrusion molding, injection molding, It can be melt molded by press molding, blow molding, or the like.

  The thermoplastic elastomer resin composition of the present invention can be suitably used as various packings.

  Moreover, the hardness as used in the field of this invention is the value obtained based on JISK6352, and the impact resilience is the value obtained based on JISK6255.

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, the test piece was a 12.0 mm thick press sheet.

  (Breaking strength) In accordance with JIS K 6251, the test piece was a 2 mm thick press sheet punched into a No. 3 shape with a dumbbell. The tensile speed was 500 mm / min.

  (Tensile elongation at break) In accordance with JIS K 6251, a 2 mm thick press sheet was used as a test piece punched out into a No. 3 shape with a dumbbell. The tensile speed was 500 mm / min.

  (Rebound resilience) In accordance with JIS K 6255, a 12.0 mm thick press sheet was used as a test piece.

  (Bleed-out) The test piece used was a 50 mm × 50 mm × 2 mm thick press sheet, immersed in 100 cc of methanol in an atmosphere at 25 ° C. for 24 hours, and then taken out and dried, and the change in weight was observed. The case where the change in weight was 10% or less was evaluated as ◯, and the case where the change in weight was 10% or more was rated as x.

As each component, the following were used.
Component (a-1): Block copolymer (SIBS1) weight average molecular weight 90000. Styrene content 21.5% by weight.
Component (a-2): Block copolymer (SIBS2) weight average molecular weight 106000. Styrene content 30% by weight.
Hydrogenated isoprene block copolymer (SEPS): SEPTON 4033 manufactured by Kuraray Co., Ltd. Styrene content 30% by weight.
Component (b-1): Random PP Grand Polymer B241 (MFR: 0.5 g / 10 min)
Component (b-2): J709W manufactured by Homo PP Grand Polymer (MFR: 55 g / 10 min)
Inorganic filler (CaCO3): Shiroishi Calcium Co., Softon 3200
Paraffin oil (non-aromatic rubber softener): Idemitsu Kosan Diana Process Oil PW-90.

  (Production example: SIBS1) 525 mL of 1-chlorobutane (dried with molecular sieves), 365 mL of hexane (dried with molecular sieves), and 0.49 g of p-dicumulyl chloride were added to a 2 L reaction vessel equipped with a stirrer. After cooling the reaction vessel to −70 ° C., 0.93 g of dimethylacetamide and 244 mL of isobutylene were added. Further, 6.57 mL of titanium tetrachloride was added to initiate polymerization, and the reaction was allowed to proceed for 1.5 hours while stirring the solution at -70 ° C. Next, 70 g of styrene was added to the reaction solution, and the reaction was continued for another 60 minutes, and then the reaction solution was poured into a large amount of water to stop the reaction.

  When the separation state of the organic layer and the aqueous layer was visually confirmed, the separability was good and could be easily separated with a separatory funnel. After washing twice with water, after confirming that the aqueous layer was neutral, the organic layer was poured into a large amount of methanol to precipitate a polymer, and the resulting polymer was allowed to stand at 60 ° C. for 24 hours. The isobutylene block copolymer (SIBS1) was obtained by vacuum drying.

  When the GPC analysis of this isobutylene type block copolymer (SIBS1) was conducted, the weight average molecular weight was 90000. The styrene content determined by 1H-NMR was 21.5% by weight. Similarly, SIBS2 (weight average molecular weight 106000, styrene content 30% by weight) was produced.

  (Example 1) 90 parts by weight of SIBS1 as component (a-1) and 10 parts by weight of random PP as component (b-1), and 15 minutes by Toyo Seiki Co. plastmill (rotation speed 100 rpm, temperature 170 ° C.) Kneaded. The obtained kneaded material was pressed at 200 ° C. to produce 2 mm and 12 mm thick sheets. The 2 mm thick sheet had a smooth surface. Further, it was flexible enough to be easily bent by hand. On the other hand, the 12 mm thick sheet had a hardness of 32, a maximum tensile strength of 11 MPa, a breaking elongation of 660%, a rebound resilience of 16%, and a bleedout of 10% by weight or less. The results are also shown in Table 1.

  Examples 2 to 7 In the same manner as in Example 1, the component (a-1) or (a-2), the component (b-1) or (b-2), and the inorganic filler depending on the case are shown in Table 1. And the hardness, the maximum tensile strength, the elongation at break, the resilience, and the bleed out were measured. The results are shown in Table 1.

  (Comparative Examples 1 and 2) Similarly to Example 1, hydrogenated isoprene block copolymer, component (b-1), and optionally paraffin oil were kneaded as shown in Table 1, and the hardness, tensile maximum strength, fracture Elongation, impact resilience, and bleed out were measured. The results are shown in Table 1.

  Comparative Example 3 In the same manner as in Example 1, the components (a-1) and (b-1) were kneaded as shown in Table 1, and the hardness, maximum tensile strength, elongation at break, rebound resilience, and bleed out were measured. did. The results are shown in Table 1.

以上のように、特定量の成分（ａ）、成分（ｂ）がそろってはじめて、外観（表面の平滑さ）、柔軟性（折り曲げたときの柔軟さ、硬度の低さ、反発弾性の低さ）、機械的強度（引張強度、破断伸び）、成形加工性（シート成形可能）、ブリードアウトのなさ等のバランスのとれた熱可塑性エラストマー樹脂組成物が得られる。

As described above, the appearance (smoothness of the surface), flexibility (flexibility when bent, low hardness, low rebound resilience) only after a specific amount of the component (a) and the component (b) are provided. ), Mechanical strength (tensile strength, elongation at break), moldability (sheet molding is possible), and a balanced thermoplastic elastomer resin composition such as lack of bleed-out.

Claims (4)

  (A) Polymer block having aromatic vinyl compound as monomer main component-Polymer block having isobutylene as monomer main component-Polymer block having aromatic vinyl compound as monomer main component A thermoplastic elastomer resin composition comprising 100 parts by weight of an isobutylene triblock copolymer, (b) 10 to 25 parts by weight of a polyolefin polymer, and 0.1 to 50 parts by weight of a filler.   2. The thermoplastic elastomer resin composition according to claim 1, wherein the impact resilience obtained by using a 12.0 mm thick press sheet in accordance with JIS K 6255 is 40% or less.   The thermoplastic elastomer resin composition according to claim 1 or 2, wherein the rebound resilience is 30% or less.   The thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein (b) is a polypropylene-based polymer.