JPWO2006046408A1 - Thermoplastic resin composition - Google Patents

Abstract

To provide a thermoplastic resin composition having excellent flexibility, vibration damping properties, sound insulation properties and appearance, and having adhesiveness and melting characteristics suitable for multilayer molding. (A) 10 to 100% by weight of an isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component, and (b) (D) 0.1 to 600 parts by weight of filler with respect to 100 parts by weight of a composition comprising 0 to 90% by weight of a composition obtained by crosslinking an isobutylene-based polymer having an alkenyl terminal with (c) a hydrosilyl group-containing polysiloxane. And (e) It is set as the thermoplastic resin composition characterized by containing 0.1-200 weight part of tackifiers.

Description

  The present invention relates to a thermoplastic resin composition used for multilayer molding applications and a multilayer molded body using the same.

  In recent years, thermoplastic elastomers that are rubber-like soft materials that do not require a vulcanization step and that have the same moldability as thermoplastic resins have attracted attention. As such thermoplastic elastomers, various polymers such as polyolefin-based, polyurethane-based, polyester-based, polystyrene-based, and polyvinyl chloride-based are currently being developed and marketed. These thermoplastic elastomers may be used alone, but thermoplastic elastomer resin compositions in combination with other thermoplastic resins have been studied in order to meet various needs of users.

  In particular, a thermoplastic elastomer resin composition in which a polyolefin resin and a polystyrene elastomer such as styrene / butadiene block copolymer (SBS) or styrene / isoprene block polymer (SIS) are mixed with a softening agent has hardness, flexibility and cushion. Has been widely used as a material having a good balance of properties, impact resistance, rubber elasticity, moldability, and the like.

  However, in a thermoplastic elastomer resin composition obtained by melt-kneading a polyolefin resin and a polystyrene thermoplastic elastomer, each resin is mixed in small particle units to form a composition. For this reason, some of the properties of each resin can be diluted by kneading. For example, surface properties, workability, vibration damping properties, etc. may rather decrease depending on the type of resin, mixing state, and processing conditions.

  As a method for obtaining the characteristics of each resin by combining two or more resins, for example, there is a multicolor molding method. Among the multicolor molding methods, in the two-color molding method, after a specific resin (primary material) is molded to obtain a primary molded body, the primary molded body is covered or laminated on the primary molded body. By molding another resin (secondary material), it is possible to obtain a molded body in which two types of resins are in close contact with each other. In recent years, it is also possible to perform multilayer molding (simultaneous molding) while moving the mold by the DSI method (die slide molding method), the DRI method (die rotary molding method) or the like. In addition, by using two-layer and three-layer dies to extrude different types of resins, it is possible to form two-layer and three-layer sheets, films, tubes, and the like in a single step.

  For example, appearance, surface properties, and vibration control properties can be achieved by performing multilayer molding using a resin with excellent surface properties, chemical resistance, heat resistance, and weather resistance for the surface layer and a thermoplastic elastomer with flexibility for the inner layer. It is possible to obtain a molded body having soundproofing properties.

Patent Document 1 discloses an isobutylene block copolymer composed of a polymer block containing isobutylene as a monomer main component, a polymer block containing an aromatic vinyl compound as a monomer main component, and a thermoplastic resin. A multilayer molded body is described. However, the isobutylene block copolymer comprising a polymer block mainly composed of isobutylene as a monomer main component and a polymer block mainly composed of an aromatic vinyl compound as a monomer main component is In some cases, the viscosity is not always sufficient for multilayer formability. There was also a problem in terms of sound insulation.
Japanese Patent Laid-Open No. 2004-034445

  An object of the present invention is to provide a thermoplastic resin composition having excellent vibration damping properties and having adhesiveness and melt viscosity suitable for multilayer molding.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a thermoplastic resin composition containing an isobutylene block copolymer having a predetermined composition. This is the headline and the present invention.

  That is, the present invention provides (a) 10 to 100% by weight of an isobutylene block copolymer comprising a polymer block containing isobutylene as a main monomer component and a polymer block containing an aromatic vinyl compound as a main monomer component. And (b) 100 parts by weight of a composition comprising (b) a composition obtained by crosslinking an isobutylene polymer having an alkenyl terminal with (c) a hydrosilyl group-containing polysiloxane. The present invention relates to a thermoplastic resin composition comprising 1 to 600 parts by weight and (e) 0.1 to 200 parts by weight of a tackifier.

  A preferred embodiment includes a thermoplastic resin composition characterized by further containing (f) a processing aid.

  A preferable embodiment includes a thermoplastic resin composition characterized in that (d) at least one filler is talc, barium sulfate, or silica.

  Preferred embodiments include (e) an alicyclic petroleum resin and a hydride of an alicyclic petroleum resin having a number average molecular weight of 300 to 3000 and a softening point based on the ring and ball method of 60 to 150 ° C. And a thermoplastic resin composition characterized by being either an aliphatic petroleum resin, a hydrogenated aromatic petroleum resin, or a polyterpene resin.

  Another embodiment of the present invention is characterized by having one or more of the first resin layer composed of the above thermoplastic resin composition and the second resin layer composed of a different kind of thermoplastic resin composition. The present invention relates to a multilayer molded body.

  Furthermore, the present invention relates to a vibration damping component comprising the multilayer molded body.

  Furthermore, the present invention relates to a sound deadening material comprising the multilayer molded body.

  The thermoplastic resin composition of the present invention is excellent in flexibility, vibration damping properties and sound insulation properties, and has adhesiveness and melting characteristics suitable for multilayer molding. Furthermore, the molded product obtained from the thermoplastic resin composition of the present invention is excellent in appearance. Therefore, a multilayer molded article formed by laminating the thermoplastic resin composition of the present invention and another resin composition is suitably used, for example, as various damping members, particularly those whose appearance is important. be able to.

  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, any of a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock copolymer, etc. having a linear, branched, star-like structure, etc. It is also possible to select one or two or more types that meet the requirements of viscoelastic properties and other physical properties and moldability.

  (A) As a preferred structure of the isobutylene block copolymer, a polymer block-isobutylene mainly composed of an aromatic vinyl monomer is used from the viewpoint of physical properties and processability of the resulting composition. Polymer block mainly composed of a monomer-triblock copolymer formed from a polymer block composed mainly of an aromatic vinyl monomer and a polymer block composed mainly of isobutylene -Polymer block mainly composed of aromatic vinyl monomer as monomer main component-Triblock copolymer formed from polymer block composed mainly of isobutylene as monomer main component, aromatic vinyl monomer Polymer block mainly composed of monomer-Diblock copolymer formed from polymer block composed mainly of isobutylene and monomer composed mainly of aromatic vinyl monomer Heavy Body block - at least one can be mentioned the di-block 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.

  Aromatic vinyl monomers include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl. -O-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4 -Dimethylstyrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m- Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or p- t-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene And vinyl naphthalene. These may be used alone or in combination of two or more.

  The polymer block having the aromatic vinyl monomer as the main component of the component (a) may contain a monomer other than the aromatic vinyl monomer.

  The monomer that is not the main component is not particularly limited as long as it is a monomer component capable of cationic polymerization, but aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene, acenaphthylene, and the like. The monomer of can be illustrated. 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, isobutylene 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 aromatic vinyl monomer constituting the aromatic vinyl polymer block of the component (a) is 60% by weight or more in the aromatic vinyl polymer block from the balance between physical properties and polymerization characteristics. Preferably, it is 80% by weight or more, and more preferably 95% or more. As the aromatic vinyl monomer, 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 It is particularly preferred to use methylstyrene or a mixture thereof.

  The polymer block mainly composed of isobutylene as component (a) may or may not contain a monomer other than isobutylene, but is usually 60% by weight or more, preferably 80% by weight or more. Preferably, it is composed of 95% or more of isobutylene. The monomer other than isobutylene is not particularly limited as long as it is a monomer that can be cationically polymerized. For example, an aromatic vinyl monomer of a polymer block containing the above aromatic vinyl monomer as a main component of the monomer. Examples include monomers other than monomers, and the like.

  (A) The ratio of the polymer block mainly composed of isobutylene monomer and the polymer block mainly composed of aromatic vinyl monomer is not particularly limited, but the balance between workability and physical properties is not limited. From the total amount of the above two polymer blocks, the polymer block containing isobutylene as the main monomer component is 98 to 40% by weight, and the polymer block containing aromatic vinyl as the main monomer component is 2%. It is preferably ˜60% by weight, the polymer block mainly containing isobutylene as a monomer main component is 95 to 60% by weight, and the polymer block mainly containing an aromatic vinyl monomer as 5 to 40% by weight. More preferably, the polymer block containing isobutylene as the main monomer component is 90 to 70% by weight, and the polymer block containing aromatic vinyl as the main monomer component is 10 to 30% by weight. Especially Masui.

The molecular weight of the isobutylene block copolymer of component (a) is not particularly limited, but is 5,000 to 1,500,000 in terms of weight average molecular weight in terms of moldability, processability, physical properties, and the like. Is more preferably 10,000 to 500,000, particularly preferably 20,000 to 250,000, and particularly preferably 40,000 to 125,000. If the weight average molecular weight of the isobutylene block copolymer is lower than the above range, the physical strength, heat resistance, and vibration damping properties are not sufficiently expressed. It is disadvantageous in terms of balance. Within the above range, an appropriate molecular weight can be selected according to the molding method such as injection molding, extrusion molding, etc. Molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)) From the viewpoints of moldability, workability, physical properties, etc., it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

Although there is no restriction | limiting in particular about the manufacturing method of the isobutylene type block copolymer of (a) component, (a) Isobutylene type block copolymer is in presence of the compound represented by following General formula (1), for example. It can be obtained by polymerizing a monomer containing isobutylene as a main component and a monomer component not containing isobutylene as a main component.
(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 1-6. ]
Examples of the halogen atom include chlorine, fluorine, bromine, iodine and the like. 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- (t-butyl) benzene [1,3- (C (CH ₃ ) ₂ Cl) ₂ -5 (C (CH ₃ ) ₃ ) C ₆ H ₃ ]
Among these, particularly preferred are 1,4-bis (1-chloro-1-methylethyl) benzene [1,4-Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1, 3,5-tris (1-chloro-1-methylethyl) benzene [1,3,5- (ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ]. [Note that 1,4-bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, 3,5-Tris (1-chloro-1-methylethyl) benzene is also referred to as tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene or tricumyl chloride.

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

  In the polymerization of the component (a) 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 grown carbon cation during cationic polymerization, and the addition of the electron donor produces a polymer with a narrow molecular weight distribution and a controlled structure. 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 amount of the electron donor component used is not particularly limited, and can be set as appropriate in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it is preferable to use 0.5-10 mol equivalent with respect to the compound represented by General formula (1), and use 1-8 mol equivalent.

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

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

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

  Further, a star-shaped polymer having a diblock copolymer formed of a polymer block containing an aromatic vinyl monomer as a monomer main component and a polymer block containing isobutylene as a monomer main component as an arm. The method is not particularly limited, but for example, in the presence of a compound having three or more cationic polymerization initiation points, a monomer mainly composed of an aromatic vinyl monomer and isobutylene A monomer component mainly composed of a monomer, a monomer composed mainly of an aromatic vinyl monomer, and a monomer component composed mainly of isobutylene to polymerize a diblock copolymer And a method of coupling (bonding) the diblock copolymer using a polyfunctional compound as a coupling 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 , Diepoxides 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, calixarene, and the like. 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 resulting star polymer, and the like, and 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3- It is at least one selected from the group consisting of diisopropenylbenzene and 1,4-diisopropenylbenzene. The above compound is usually commercially available as a mixture with, for example, ethyl vinyl benzene, etc., and can be used as it is if the above divinyl aromatic compound is the main component, and can be purified as necessary to purify it. You may raise and use.

  (B) The isobutylene polymer having an alkenyl group at the terminal used in the present invention is a monomer component derived from isobutylene of 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. It refers to the occupying polymer. (B) The monomer other than isobutylene in the isobutylene-based polymer having an alkenyl group at the terminal is not particularly limited as long as it is a monomer component capable of cationic polymerization. For example, the above-described aromatic vinyls, Examples thereof include 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.

  (B) Although there is no restriction | limiting in particular in the molecular weight of the isobutylene type polymer which has an alkenyl group at the terminal, 1,000-500,000 are preferable at a weight average molecular weight, and 5,000-200,000 are especially preferable. When the weight average molecular weight is less than 1,000, mechanical properties and the like are not sufficiently exhibited, and when it exceeds 500,000, the decrease in moldability and the like is large.

  (B) The alkenyl group at the terminal of the isobutylene polymer is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for the crosslinking reaction for achieving the object of the present invention. Absent. Specifically, 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

  (B) Examples of the method for introducing an alkenyl group into the terminal of an isobutylene polymer having an alkenyl group at the terminal include hydroxyl groups as described in JP-A-3-152164 and JP-A-7-304909. The method which introduce | transduces an unsaturated group into a polymer by making the compound which has an unsaturated group react with the polymer which has these functional groups is mentioned. In order to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with an alkenylphenyl ether, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols, etc. Examples include a method in which a Friedel-Crafts reaction with a group is introduced to introduce a hydroxyl group, and then the alkenyl group introduction reaction is further performed. Further, as disclosed in U.S. Pat. No. 4,316,973, JP-A 63-105005, and JP-A 4-288309, it is possible to introduce an unsaturated group 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.

  (B) The number of alkenyl groups at the end of the isobutylene polymer can be arbitrarily selected according to the required properties. From the viewpoint of the properties after crosslinking, at least 0.2 alkenyl groups per molecule are used. It is preferably a polymer having at the end. If the number is less than 0.2, the improvement effect due to crosslinking may not be sufficiently obtained.

(C) Although there is no limitation in particular about hydrosilyl group containing polysiloxane, various things can be used. Among them, a hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 to 500 siloxane units is preferable, and a polysiloxane having 3 or more hydrosilyl groups and 10 to 200 siloxane units is preferred. More preferred are polysiloxanes having 3 or more hydrosilyl groups and 20 to 100 siloxane units. If the content of hydrosilyl groups is less than 3, sufficient network growth due to crosslinking cannot be achieved, and sufficient rubber elasticity cannot be obtained. On the other hand, when the number of siloxane units is more than 500, the viscosity of the polysiloxane is high, and (b) the dispersion into the isobutylene polymer having an alkenyl group at the terminal is not sufficiently performed, and unevenness occurs in the crosslinking reaction. On the other hand, it is preferable that the number of polysiloxane units is 100 or less because (c) hydrosilyl group-containing polysiloxane 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)
(C) As a hydrosilyl group-containing polysiloxane, 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, 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, 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.

  (B) The isobutylene polymer having an alkenyl group at the terminal and the (c) hydrosilyl group-containing polysiloxane can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the hydrosilyl group to 1 mol of the alkenyl group Is preferably 0.5 to 10, more preferably 1 to 5. When the molar ratio is less than 0.5, only a cured product with insufficient tackiness and low strength can be obtained, and when the molar ratio is greater than 10, 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.

  (B) The cross-linking reaction between the isobutylene polymer having an alkenyl group at the terminal and the (c) hydrosilyl group-containing polysiloxane proceeds by mixing and heating the two components. 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. For example, 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, peroxyesters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate, 1,1-di ( Examples thereof include peroxyketals such as (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Also, the transition metal catalyst is not particularly limited. For example, a 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 complex, 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 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 (b) 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. Further, since the hydrosilylation catalyst is expensive, it is preferable to use a catalyst of 10 ⁻¹ mol or less.

  (B) When an isobutylene polymer having an alkenyl group at the terminal is crosslinked with (c) a hydrosilyl group-containing polysiloxane, (a) a polymer block containing isobutylene as a main monomer and an aromatic vinyl compound (C) adding a hydrosilyl group-containing polysiloxane at the time of melt-kneading an isobutylene block copolymer comprising a polymer block as a main component of a monomer and (b) an isobutylene polymer having an alkenyl group at the terminal It is preferable to perform the crosslinking dynamically from the viewpoint of the uniformity of the crosslinked product of the isobutylene polymer having an alkenyl group at the terminal (b).

  (B) By adding a composition obtained by crosslinking an isobutylene polymer having an alkenyl group at the terminal with (c) a hydrosilyl group-containing polysiloxane, the melt viscosity is increased while maintaining vibration damping properties, flexibility and gas barrier properties. It is possible to prevent the resin pressure of the component (g) from being pushed at the time of co-extrusion with the thermoplastic resin of the component (g).

  (A) an isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component; and (b) isobutylene having an alkenyl group at the terminal. The amount of the composition obtained by crosslinking the polymer based on (c) the hydrosilyl group-containing polysiloxane is 100/0 to 10/90, more preferably 90/10 to 10/90, and still more preferably 80/20 to The ratio is 30/70. This is because if the amount of component (a) is less than 10%, the moldability becomes poor.

  (D) The filler is not particularly limited. For example, clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, mica, graphite, aluminum hydroxide, magnesium hydroxide, natural silicic acid, synthetic silicic acid ( Inorganic fillers such as white carbon) and metal oxides (titanium oxide, magnesium oxide, zinc oxide) can be used. 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. Of these, talc, mica, silica, and barium sulfate are particularly preferable from the viewpoint of vibration damping properties.

  Further, when talc or silica is used, the viscosity of the thermoplastic resin composition of the present invention is increased, and (g) it is preferable that it is prevented from being pressed by the resin pressure during co-extrusion with the thermoplastic resin.

  When barium sulfate is used, it is possible to increase the specific gravity of the thermoplastic resin composition of the present invention, which is preferable from the viewpoint of improving sound insulation.

  The blending amount of the filler (d) is 0.1 to 600 parts by weight, more preferably 1 to 200 parts by weight, and still more preferably 50 to 100 parts by weight with respect to the total of 100 parts by weight of the components (a) and (b). 200 parts by weight. When the amount is less than 0.1 parts by weight, the physical properties of the obtained molded body are not improved. When the amount exceeds 600 parts by weight, the mechanical strength of the obtained molded body is lowered and the flexibility is impaired.

  (E) The tackifier is a low molecular resin having a number average molecular weight of 300 to 3,000 and a softening point of 60 to 150 ° C. based on the ring and ball method defined in JIS K-2207, and includes rosin and rosin Derivatives, polyterpene resins, aromatic modified terpene resins and their hydrides, terpene phenol resins, coumarone and indene resins, aliphatic petroleum resins, alicyclic petroleum resins and their hydrides, aromatic petroleum resins and their hydrogen And a low molecular weight polymer of an aliphatic aromatic copolymer-based petroleum resin, a dicyclopentadiene-based petroleum resin and a hydride thereof, styrene or substituted styrene. Such a tackifier has an effect of moving Tg of a polymer block containing isobutylene as a main component of monomer to a high temperature side, and in order to achieve such an object, in the isobutylene block copolymer, It is desirable to add a tackifier that is compatible with a polymer block containing isobutylene as a main component of the monomer, such as an alicyclic petroleum resin and a hydride thereof, an aliphatic petroleum resin, an aromatic petroleum. Resin hydrides, polyterpene resins and the like are preferably used. Moreover, even in the same kind of tackifier, the higher the softening point, the higher the effect of moving the Tg of the polymer block containing isobutylene as a main component of the isobutylene block copolymer to the high temperature side. When it is desired to reduce the blending amount of the imparting agent, the one with a high softening point may be selected.

  (E) The compounding quantity of a tackifier is 0.1-200 weight part with respect to a total of 100 weight part of (a) component and (b) component, More preferably, you may be 1-100 weight part. When the amount is less than 0.1 parts by weight, the physical properties of the obtained molded body are not improved. When the amount exceeds 200 parts by weight, the mechanical strength of the obtained molded body is lowered and workability is also impaired.

  The resin composition of the present invention may further contain (f) a processing aid. (F) Examples of processing aids include processing aids for vinyl chloride resins, acrylonitrile-styrene resins, methyl methacrylate-styrene resins, ABS resins, polycarbonate resins, polyethylene resins, and polyester resins. For example, a copolymer mainly composed of methyl methacrylate and polytetrafluoroethylene can be mentioned. Among these, fibrillated polytetrafluoroethylene is preferable from the viewpoint of the effect of improving the molten state.

  (F) The blending amount of the processing aid is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 20 parts per 100 parts by weight in total of the components (a) and (b). Weight part. When the amount is less than 0.001 part by weight, the physical properties of the obtained molded body are not improved, and when it exceeds 50 parts by weight, the flexibility of the obtained molded body is lost, which is not preferable.

  Furthermore, the composition of the present invention includes (f) a processing aid, as well as a softening agent, an antioxidant and / or an ultraviolet absorber, a flame retardant, an antibacterial agent, a heat stabilizer, and a light stabilizer as necessary. , Colorants, fluidity improvers, processing aids (preferably acrylic processing aids), crystal nucleating agents, lubricants, antiblocking agents, sealability improving agents, antistatic agents, and the like can be added. These can be used alone or in combination of two or more.

  Further, the composition of the present invention may optionally contain an aromatic vinyl-conjugated diene-based thermoplastic elastomer such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer. A combination (SIS), or hydrogenated styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), or the like may be blended.

  (G) The thermoplastic resin composition that forms a multilayer molded body with the thermoplastic resin composition containing the above components is not particularly limited, and examples thereof include polyolefin resins, aromatic vinyl compound resins, poly Vinyl chloride resin, polycarbonate resin, polyphenylene ether resin, poly (meth) acrylate resin, poly (meth) acrylamide resin, poly (meth) acrylonitrile resin, polyamide resin, polyester resin, polyacetal resin, Thermoplastic elastomers such as polysulfone resin, polyarylene sulfide resin, fluorine resin, polyimide resin, thermoplastic urethane resin, styrene thermoplastic elastomer, olefin thermoplastic elastomer, vinyl chloride thermoplastic elastomer, etc. Containing a composition It can gel.

  Among these, from the viewpoints of moldability and cost in multilayer molding with thermoplastic resin compositions containing the components (a) to (f), polyolefin resins, aromatic vinyl compound resins, polyvinyl chloride resins Styrenic thermoplastic elastomers, olefinic thermoplastic elastomers, and vinyl chloride thermoplastic elastomers are preferable, and polyolefin resins and polyvinyl chloride resins are more preferable.

  Polyolefin resins include ethylene or α-olefin homopolymers, or random copolymers, block copolymers and mixtures thereof, or random of ethylene or α-olefin and other unsaturated monomers. Copolymers, block copolymers, graft copolymers and modified products of these polymers can be used alone or in combination of two or more. 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, may be mentioned various polyolefin or the like (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.

  Furthermore, if necessary, aromatic vinyl-conjugated diene-based thermoplastic elastomers such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and You may mix | blend at least 1 sort (s), such as a hydrogenated styrene-ethylene butylene-styrene block copolymer (SEBS) and a styrene-ethylene propylene-styrene block copolymer (SEPS).

  The structure of the multilayer molded body of the present invention is not particularly limited as long as the thermoplastic resin composition containing the components (a) to (e) and (g) the thermoplastic resin composition are molded in layers. The thermoplastic resin composition layer (first resin layer) containing the components (a) to (e) and (g) the thermoplastic resin composition layer (second resin layer) are laminated one by one. It may be a two-layer molded body or a molded body having a structure in which one resin layer is interposed between the other resin layers. Or the layer (1st resin layer) which consists of a thermoplastic resin composition containing (a)-(e) component, and the multilayer (layer) (g) which consists of (g) thermoplastic resins laminated | stacked alternately The molded body may be a molded body composed of a layer (first resin layer) composed of a thermoplastic resin composition containing at least one component (a) to (e) and at least one (g) thermoplastic resin. The molded body part composed of the layers (second resin layer) may be integrated by multilayer molding to constitute the molded body. Among these, since a multilayer molded article having excellent surface properties and appearance can be obtained, the thermoplastic resin composition layer containing the components (a) to (e) is the core layer, and (g) the thermoplastic resin layer is the skin layer. A molded body having a sandwich structure in which is formed is preferable.

  By extruding the resin containing the components (a) to (e) and the component (g) with a multilayer extruder, for example, a molded body having a two-layer or three-layer structure can be obtained. Moreover, it is good also as a molded object which used the other resin composition further as needed. Moreover, a multilayer sheet-like molded object and a tube-shaped molded object can be obtained by changing the shape of die | dye into a slit die and a tube die.

  The volume ratio of the thermoplastic composition containing the components (a) to (e) constituting the multilayer molded body of the present invention and the (g) thermoplastic resin composition may be arbitrary, but preferably (a) to (e ) The thermoplastic composition containing the component preferably occupies 5 to 95% by volume, more preferably 10 to 80% by volume, based on the multilayer molded body. In the case of 5% by volume or less, the vibration damping property of the obtained multilayer molded article becomes insufficient, and in the case of 95% by volume or more, the rigidity of the obtained multilayer molded article is lowered.

  The multilayer molded body can be produced by a conventional multilayer molding method, for example, a core rotation type, a core back type, a core slide type, or the like, and a DSI (die slide molding method) or DRI (die die) for sliding or rotating a mold. The same can be done by a rotary molding method.

  In the production method of the present invention, the molding temperature of the resin composition containing the components (a) to (e) is preferably 150 to 230 ° C., more preferably 170, from the viewpoints of moldability, fluidity, and thermal stability. ~ 210 ° C. About the molding temperature of (g) component, optimal conditions are selected by the kind of resin. For example, in the case of polyolefin, the same conditions as the molding conditions of the resin composition containing the components (a) to (e) can be selected.

  The multilayer molded article of the present invention obtained as described above is excellent in vibration damping properties, and further excellent in flexibility, fluidity, gas barrier properties, and appearance. For this reason, it can be used suitably for automobiles, office automation equipment, home electrical appliances, machine tools, building material damping members, silencers, and the like.

  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.

(Melt viscosity)
The melt viscosity of the resin composition was measured at a test temperature of 200 ° C., a shear rate of 12.16, 1216 sec-1 and a die radius of 1 mm using a capillary rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). did.

(specific gravity)
The specific gravity of the resin composition was measured by the JIS K7100A method underwater substitution method.

(Flexibility)
Hardness / specific gravity was used as an index. The lower the number, the higher the flexibility.

(Dynamic viscoelasticity)
The dynamic viscoelastic property is formed into a sheet by hot press molding, and the obtained sheet is subjected to a test of 40 mm × 5 mm × 2 mm in accordance with JIS K-6394 (Method for testing dynamic properties of vulcanized rubber and thermoplastic rubber). One piece was cut out and used in a shear mode under the conditions of a frequency of 10 Hz and a strain of 0.05%. The apparatus used is a dynamic viscoelasticity measuring apparatus DVA-200 (made by IT Measurement Control Co., Ltd.).

(Adhesiveness)
The material of the present invention and (g) component thermoplastic resin (polypropylene or polyvinyl chloride) 50 mm × 20 mm × 2 mm thick sheets are stacked and pressed at 190 ° C. (made by Shindo Metal Industry Co., Ltd.) After 5 minutes of preheating, pressing was performed to a thickness of 3 mm at 50 kg / cm3 pressure. The state when the formed body was peeled by hand was evaluated.

(Extruded surface properties)
When the thermoplastic resin of the present invention is extruded under the conditions of a die head temperature of 180 ° C. and 50 rotations using a conical biaxial screw and a slit die having a width of 30 mm and a thickness of 1 mm in a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) The surface property was evaluated.

As each component, the following were used.
Component (a-1): Block copolymer (SIBS1) (Production Example 1)
Component (a-2): Block copolymer (SIBS2) (Production Example 2)
Component (a-3): Block copolymer (SIBS3) (Production Example 3)
Component (b): Polyisobutylene (APIB) having an allyl group at the terminal (Production Example 4)
Component (c): 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, valent 3,3-tetramethyl-1,3-dialkenyldisiloxane complex of zerovalent platinum, 3% by weight xylene solution component (d-1): SW manufactured by Talc Nippon Talc
Ingredient (d-2): Barium sulfate Takehara Chemical Co., Ltd. W-1
Component (d-3): Silica Nippon Silica Co., Ltd. VN3
Ingredient (e-1): Hydrogenated petroleum resin Arakawa Chemical Co., Ltd. P-100
Ingredient (e-2): Hydrogenated petroleum resin Arakawa Chemical Co., Ltd. P-140
Ingredient (f-1): Kane Ace PA100 manufactured by Kaneka Corporation
Component (f-2): Processing aid Mitsubishi Rayon Co., Ltd. METABLEN A3000.

(Production Example 1: SIBS1)
In a 2 L reaction vessel equipped with a stirrer, 452 mL of 1-chlorobutane (dried with molecular sieves), 319 mL of hexane (dried with molecular sieves), 0.55 g of 1,4-bis (1-chloro-1-methylethyl) benzene Was added. After cooling the reaction vessel to −75 ° C., 0.42 g of dimethylacetamide and 182 mL of isobutylene were added. Further, 6.53 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 -75 ° C. Next, 51 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 the polymer, and the resulting polymer was allowed to stand at 60 ° C. for 24 hours. The isobutylene block copolymer (SIBS) was obtained by vacuum drying.
When the GPC analysis of this isobutylene type block copolymer (SIBS) was conducted, the weight average molecular weight was 72,000 and content of styrene calculated | required by < ¹ > H-NMR was 29 weight%.

(Production Example 2: SIBS2)
In a 2 L reaction vessel equipped with a stirrer, 452 mL of 1-chlorobutane (dried with molecular sieves), 319 mL of hexane (dried with molecular sieves), 0.55 g of 1,4-bis (1-chloro-1-methylethyl) benzene Was added. After cooling the reaction vessel to −75 ° C., 0.42 g of dimethylacetamide and 242 mL of isobutylene were added. Further, 6.53 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 -75 ° C. Next, 68 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 the polymer, and the resulting polymer was allowed to stand at 60 ° C. for 24 hours. The isobutylene block copolymer (SIBS) was obtained by vacuum drying.
When the GPC analysis of this isobutylene type block copolymer (SIBS) was conducted, the weight average molecular weight was 10,300 and content of styrene calculated | required by < ¹ > H-NMR was 29 weight%.

(Production Example 3: SIBS3)
In a 2 L reaction vessel equipped with a stirrer, 452 mL of 1-chlorobutane (dried with molecular sieves), 319 mL of hexane (dried with molecular sieves), 0.55 g of 1,4-bis (1-chloro-1-methylethyl) benzene Was added. After cooling the reaction vessel to −75 ° C., 0.42 g of dimethylacetamide and 293 mL of isobutylene were added. Further, 6.53 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 -75 ° C. Next, 34 g of styrene was added to the reaction solution, and the reaction was further continued for 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 the polymer, and the resulting polymer was allowed to stand at 60 ° C. for 24 hours. The isobutylene block copolymer (SIBS) was obtained by vacuum drying.
When the GPC analysis of this isobutylene type block copolymer (SIBS) was conducted, the weight average molecular weight was 10,200 and content of styrene calculated | required by < ¹ > H-NMR was 15 weight%.

(Production Example 4) [Production of isobutylene polymer (APIB) 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 to 80 degreeC), the organic solvent was removed at 80 degreeC under pressure reduction, and APIB was obtained. A polymer having a number average molecular weight (Mn) of 45,500, 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.

(Example 1)
100 parts by weight of (a-1) as component (a), 50 parts by weight of (d-1) as component (d), and 20 parts by weight of (e-1) as component (e) A thermoplastic resin composition was obtained by kneading with a plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 160 ° C. and 50 rpm. The obtained thermoplastic resin composition could be easily formed into a sheet with a pressure press (manufactured by Shinfuji Metal Industry Co., Ltd.) at 160 ° C. The dynamic viscoelasticity, density, adhesiveness, and melt viscosity of the sheet thus obtained were measured according to the above methods. Table 1 shows the physical properties of each sheet.

(Example 2)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), and 20 parts by weight of (e-1) as component (e) A thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 3)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 20 parts by weight of (e-1) as component (e), and as component (f) 10 parts by weight of (f-1) was blended, a thermoplastic resin composition was produced in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The physical properties are shown in Table 1.

Example 4
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 20 parts by weight of (e-1) as component (e), and as component (f) 2 parts by weight of (f-2) was blended, a thermoplastic resin composition was produced in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 5)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 14 parts by weight of (e-2) as component (e), and as component (f) 2 parts by weight of (f-2) was blended, a thermoplastic resin composition was produced in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 6)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

(Example 7)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 10 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

(Example 8)
100 parts by weight of (a-2) as component (a), 50 parts by weight of (d-1) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 7 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

Example 9
100 parts by weight of (a-2) as component (a), 90 parts by weight of (d-1) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The physical property measurement results are shown in Table 1.

(Example 10)
100 parts by weight of (a-2) as component (a), 100 parts by weight of (d-2) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

(Example 11)
100 parts by weight of (a-2) as component (a), 150 parts by weight of (d-2) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

(Example 12)
100 parts by weight of (a-2) as component (a), 600 parts by weight of (d-1) as component (d), 5 parts by weight of (d-3), (e-2) as component (e) 14 parts by weight and 2 parts by weight of (f-2) as component (f) were prepared, a thermoplastic resin composition was prepared in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. It was. The measurement results are shown in Table 1.

(Example 13)
[Step 1]
Laboplast mill (manufactured by Toyo Seiki Seisakusyo Co., Ltd.) was formulated as component (a) by mixing (a-1) and component (b) at a ratio shown in Table 2 so as to be 40 g in total. And then melt kneaded for 3 minutes, then 1.2 parts by weight of component (c) is added to 100 parts by weight of component (b), and 0.05 parts by weight of cross-linked After the addition of the catalyst, it 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]
The ratio shown in Table 2 for the composition, component (a-3), component (d-1), component (d-3), component (e-2), and component (f-2) obtained in step 1 The total amount was 40 g, and the mixture was melt-kneaded for 10 minutes using a lab plast mill (manufactured by Toyo Seiki Seisakusho) set at 170 ° C. and then taken out. The obtained thermoplastic resin composition could be easily formed into a sheet with a pressure press (manufactured by Shinfuji Metal Industry Co., Ltd.) at a heating temperature of 170 ° C. The hardness, dynamic viscoelasticity, density, adhesiveness, and melt viscosity of the obtained sheet were measured according to the above methods. Table 2 shows the physical property measurement results of each sheet.

(Example 14)
The ratio shown in Table 2 for the composition, component (a-3), component (d-1), component (d-3), component (e-2), and component (f-2) obtained in step 1 The thermoplastic resin composition was produced in the same manner as in Example 13 and various physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

(Example 15)
The ratio shown in Table 2 for the composition, component (a-3), component (d-1), component (d-3), component (e-2), and component (f-2) obtained in step 1 The thermoplastic resin composition was produced in the same manner as in Example 13 and various physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

(Example 16)
The ratio shown in Table 2 for the composition, component (a-3), component (d-2), component (d-3), component (e-2), and component (f-2) obtained in step 1 The thermoplastic resin composition was prepared in the same manner as in Example 13 and the physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

(Example 17)
The ratio shown in Table 2 for the composition, component (a-3), component (d-2), component (d-3), component (e-2), and component (f-2) obtained in step 1 The thermoplastic resin composition was prepared in the same manner as in Example 13 and the physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

(Example 18)
The ratio shown in Table 2 for the composition, component (a-3), component (d-2), component (d-3), component (e-2), and component (f-2) obtained in step 1 The thermoplastic resin composition was prepared in the same manner as in Example 13 and the physical properties were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

(Example 19)
The composition, component (a-3), component (d-2), component (e-1), and component (f-2) obtained in step 1 are adjusted to a total of 40 g in the proportions shown in Table 2. A thermoplastic resin composition was prepared in the same manner as in Example 13 and the physical properties were measured in the same manner as in Example 1. Table 2 shows the physical property measurement results.

(Example 20)
The composition obtained in step 1, the component (a-3), the component (d-2), the component (e-2), and the component (f-2) at a ratio shown in Table 2 so that the total amount becomes 40 g. A thermoplastic resin composition was prepared in the same manner as in Example 13 and the physical properties were measured in the same manner. Table 2 shows the physical property measurement results.

(Comparative Example 1)
Using (a-1) as the component (a) and no other components, a thermoplastic resin composition was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. Table 3 shows the measurement results.

(Comparative Example 2)
A thermoplastic resin composition was prepared in the same manner as in Example 1 using (a-2) as the component (a) and no other components, and the physical properties were measured in the same manner as in Example 1. Table 3 shows the physical property measurement results.

(Comparative Example 3)
100 parts by weight of (a-2) as component (a) and 20 parts by weight of (e-1) as component (e) were prepared, and a thermoplastic resin composition was prepared in the same manner as in Example 1. Physical properties were measured. Table 3 shows the physical property measurement results.

(Comparative Example 4)
100 parts by weight of (a-1) as component (a) and 50 parts by weight of (d-2) as component (d) are blended to prepare a thermoplastic resin composition in the same manner as in Example 1. Physical properties were measured. Table 3 shows the physical property measurement results.

(Comparative Example 5)
100 parts by weight of (a-1) as component (a) and 20 parts by weight of (e-2) as component (e) were prepared, and a thermoplastic resin composition was prepared in the same manner as in Example 1. Physical properties were measured. Table 3 shows the physical property measurement results.

(Comparative Example 6)
Lab Plast Mill (Toyo Seiki Seisakusho Co., Ltd.) was prepared by blending component (a-1), component (b), and component (d-2) in the proportions shown in Table 3 to a total of 40 g and setting to 170 ° C. For 3 minutes, then 1.2 parts by weight of component (c) is added to 100 parts by weight of component (b) and 0.05 parts by weight of 100 parts by weight of component (b). After adding a part of the cross-linking catalyst, dynamic cross-linking was performed by further melt-kneading at 170 ° C. until the torque value reached the maximum value. It was taken out after kneading for 5 minutes after the torque value reached the maximum value. About the taken-out resin composition, it carried out similarly to Example 1, and measured the physical property. Table 2 shows the physical property measurement results.

(Comparative Example 7)
Lab Plast Mill (Toyo Seiki Seisakusho Co., Ltd.) was prepared by blending component (b), component (d-2), and component (e-2) in the proportions shown in Table 3 so that the total amount was 40 g. For 3 minutes, then 1.2 parts by weight of component (c) is added to 100 parts by weight of component (b) and 0.05 parts by weight of 100 parts by weight of component (b). After adding a part of the cross-linking catalyst, dynamic cross-linking was performed by further melt-kneading at 170 ° C. until the torque value reached the maximum value. After kneading for 5 minutes after the torque value reached the maximum value, the resin composition was taken out. However, this resin composition could not be molded.

  The height of the sound insulating property is such that the specific gravity of the composition is 1 or more. Examples 1 to 8, 13 to 15 and 20 have a specific gravity of 1.15 to 1.21 and Examples 9 to 12. 16-19 showed high specific gravity of 1.328-2.35, suggesting that high sound insulation can be exhibited. Further, from Examples 6 and 8, and 16 to 18, the peak temperature of tan δ of dynamic viscoelasticity changes according to the amount of component (e) added, and by adjusting the amount of component (e) added, It can be seen that the vibration control can be controlled. In Examples 1 and 2, it can be seen that the melt viscosity can be controlled while maintaining the same vibration damping property, specific gravity and hardness depending on the type of component (a) used. Examples 13 to 20 contain a composition obtained by crosslinking the alkenyl-terminated isobutylene polymer as the component (b) with the hydrosilyl group-containing polysiloxane as the component (c). Compared with Examples 1 to 12 Then, high melt viscosity is shown, and it can be seen that the workability is greatly improved without impairing flexibility, sound insulation and vibration control. Further, in Examples 13 to 15, the melt viscosity is greatly different depending on the content of the Step 1 composition although it is substantially the same tan δ peak temperature. From this, the content of the Step 1 composition is controlled. It can be seen that the melt viscosity can be controlled while maintaining the peak temperature of tan δ. At this time, the hardness, specific gravity, dynamic viscoelasticity, adhesiveness, and extrusion surface properties were hardly affected.

  In Examples 13 to 20, which contain a composition obtained by crosslinking the component (b) with the component (c), the value of (hardness) / (specific gravity), which is a measure of flexibility, is 28.1 to 41.0. It can be seen that flexibility can be improved by including a composition obtained by crosslinking the component (b) with the component (c). When a filler having a high specific gravity is added, the hardness increases as the specific gravity increases. The resin composition containing the composition obtained by crosslinking the component (b) with the component (c) has little influence on the increase in hardness due to the increase in specific gravity, indicating that a highly flexible composition can be obtained.

  Further, it can be seen that Comparative Examples 1, 2, and 4 to which no component (e) is added have poor adhesion and are not suitable for multilayer molding. In Comparative Example 7 in which component (a) was not blended, the thermoplasticity was lost and molding was impossible. Moreover, about the comparative example 3 which does not contain a component (d), specific gravity is less than 1 and sufficient sound-insulating property is not acquired.

  From the above, the thermoplastic resin of the present invention is a composition having high vibration damping properties, adhesiveness, flexibility, and sufficient sound insulation properties, and the melt viscosity is also adapted to each molding method. It was shown that it can be appropriately controlled and can be suitably used for various molding methods.

Claims (8)

  (A) 10 to 100% by weight of an isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component, and (b) (D) 0.1 to 600 parts by weight of filler with respect to 100 parts by weight of composition comprising 0 to 90% by weight of composition obtained by crosslinking an isobutylene polymer having an alkenyl terminal with (c) hydrosilyl group-containing polysiloxane. And (e) a thermoplastic resin composition comprising 0.1 to 200 parts by weight of a tackifier.   The thermoplastic resin composition according to claim 1, further comprising (f) a processing aid.   (D) The thermoplastic resin composition according to claim 1 or 2, wherein at least one of the fillers is talc, barium sulfate, or silica.   (E) An alicyclic petroleum resin, a hydride of an alicyclic petroleum resin, an aliphatic petroleum resin having a number average molecular weight of 300 to 3000 and a softening point based on the ring and ball method of 60 to 150 ° C. The thermoplastic resin composition according to any one of claims 1 to 3, which is any one of hydrides of aromatic petroleum resins, and polyterpene resins.   It has 1 or 2 or more each of the 1st resin layer which consists of a thermoplastic resin composition in any one of Claims 1-4, and the 2nd resin layer which consists of a different kind of thermoplastic resin composition, It is characterized by the above-mentioned. Multi-layer molded product.   5. The multilayer according to claim 1, wherein the thermoplastic resin composition according to any one of claims 1 to 4 forms a core layer, and a different kind of thermoplastic resin (g) forms a skin layer. Molded body.   A vibration damping component comprising the multilayer molded article according to claim 5 or 6.   A muffler comprising the multilayer molded article according to claim 5.