JP2005187509A - Molded item and modifier comprised of resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded item and a modifier which are each comprised of a resin composition highly flexible and excellent in molding processability, rubber properties, mechanical strength, permanent compression set property and vibration-damping property. <P>SOLUTION: The molded item and the modifier are each comprised of the resin composition obtained by dynamic crosslinking of an isobutylene polymer bearing an alkenyl group on its end using a hydrosilyl group-bearing compound by melt-kneading in the presence of at least one selected from the group consisting of aromatic vinyl thermoplastic elastomers and olefin resins. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a molded article and a modifier comprising a resin composition obtained by dynamically crosslinking a specific isobutylene copolymer.

  Conventionally, as a polymer material having elasticity, a material obtained by blending a rubber such as natural rubber or synthetic rubber with a crosslinking agent or a reinforcing agent and crosslinking under high temperature and high pressure has been widely used. However, such rubbers require a process of crosslinking and molding for a long time under high temperature and pressure, and are inferior in processability. Moreover, since the crosslinked rubber does not exhibit thermoplasticity, it is generally impossible to perform recycle molding like a thermoplastic resin. For this reason, various thermoplastic elastomers have recently been developed that can be used to easily produce molded products using general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding in the same way as ordinary thermoplastic resins. ing.

  Moreover, a soft vinyl chloride compound is widely used as a flexible material. Although this is used for various uses as a flexible material at room temperature, substitution with other materials is requested | required from the request | requirement of devinylation in recent years. As an alternative material for this, a thermoplastic elastomer composition is used.

  As such thermoplastic elastomers, various types of polymers such as olefins, urethanes, esters, styrenes, and vinyl chlorides have been developed and are commercially available.

  Of these, the styrene thermoplastic elastomer is rich in flexibility and excellent in rubber elasticity at room temperature. Styrenic thermoplastic elastomers include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers obtained by hydrogenating them. (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) have been developed. However, these block copolymers have insufficient compression set characteristics.

  On the other hand, thermoplastic elastomers with excellent flexibility, excellent rubber elasticity at room temperature, and excellent gas barrier properties and sealing properties are mainly composed of polymer blocks mainly composed of isobutylene and aromatic vinyl compounds. An isobutylene block copolymer containing a polymer block is known. However, this isobutylene block copolymer also has problems in the pressure deformation rate (compression set) during heating and the rubber elasticity at high temperatures.

  Patent Document 1 discloses a thermoplastic polymer composition comprising an isobutylene block copolymer containing a polymer block mainly composed of isobutylene and a crosslinked rubber. This composition had improved compression set properties but was inadequate.

  Patent Documents 2 and 3 disclose a thermoplastic elastomer composition obtained by dynamically crosslinking an isobutylene polymer in the presence of an aromatic vinyl-based thermoplastic elastomer or an olefin-based resin as a solution to the above problem. Yes. This composition is excellent in vibration damping, which is a characteristic of an isobutylene polymer, and has improved flexibility, molding processability, and rubber-like characteristics, and improved compression set characteristics. However, since Patent Documents 2 and 3 hardly disclose additives and fillers added to the thermoplastic elastomer composition, what kind of molded product the composition can be used for and what modifications At present, it is not well known whether it can be used as a quality agent.

Republished patent WO98 / 14518 Republished patent WO03 / 2654 JP 2003-55528 A

  An object of the present invention is to provide a molded article and a modifier comprising a resin composition which is rich in flexibility and excellent in molding processability, rubber-like characteristics, mechanical strength and compression set characteristics in view of the above-mentioned problems of the prior art. Is to provide.

  As a result of intensive research to solve the above problems, the present inventors have solved the above problems by using a molded article and a modifier comprising a resin composition obtained by dynamically crosslinking a specific isobutylene copolymer. The present invention has been found and the present invention has been achieved.

  That is, in the present invention, the isobutylene polymer having an alkenyl group at the terminal is melt kneaded with the hydrosilyl group-containing compound in the presence of at least one selected from the group consisting of an aromatic vinyl thermoplastic elastomer and an olefin resin. The present invention relates to a molded article and a modifier comprising a resin composition dynamically crosslinked below.

  It is preferable that the resin composition further contains a thermoplastic resin.

  It is preferable that the resin composition further contains a softening agent.

  The aromatic vinyl-based thermoplastic elastomer is preferably a block copolymer comprising a unit mainly composed of an aromatic vinyl-based compound and a unit mainly composed of isobutylene.

  The isobutylene polymer having an alkenyl group at the terminal is preferably a polymer having a number average molecular weight of 1,000 to 500,000 and at least 0.2 alkenyl groups per molecule per terminal.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object and modifier which are rich in a softness | flexibility and are excellent in a moldability, rubber-like characteristic, mechanical strength, and a compression set characteristic can be provided.

  In the present invention, an isobutylene polymer having an alkenyl group at a terminal is melt kneaded with a hydrosilyl group-containing compound in the presence of at least one selected from the group consisting of an aromatic vinyl thermoplastic elastomer and an olefin resin. And a modifier comprising a dynamically crosslinked resin composition.

  The isobutylene polymer having an alkenyl group at the terminal used in the present invention is a polymer in which isobutylene accounts for 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. The monomer other than isobutylene in the isobutylene polymer is not particularly limited as long as it is a monomer component capable of cationic polymerization, but aromatic vinyls, aliphatic olefins, dienes, vinyl ethers, silanes. , Β-pinene, vinylcarbazole, acenaphthylene and the like. These may be used alone or in combination of two or more.

  Aliphatic olefins include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane, octene, Examples include norbornene.

  Aromatic vinyls include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-. Methyl styrene, α-methyl-m-methyl styrene, α-methyl-p-methyl styrene, β-methyl-o-methyl styrene, β-methyl-m-methyl styrene, 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-m-alkyl Rollostyrene, 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 pt -Butyl styrene, o-, m- or p-methoxy styrene, o-, m- or p-chloromethyl styrene, o-, m- or p-bromomethyl styrene, styrene derivatives substituted with silyl groups, indene, Vinylnaphthalene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine Etc.

  Examples of dienes include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene.

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

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

  The number average molecular weight of the isobutylene polymer having an alkenyl group at the terminal is not particularly limited, but is preferably from 1,000 to 500,000, particularly preferably from 5,000 to 200,000. When the number average molecular weight is less than 1000, mechanical properties are not sufficiently exhibited, and when the number average molecular weight exceeds 500,000, the moldability is greatly deteriorated.

  The alkenyl group of the isobutylene polymer having an alkenyl group at the terminal is not particularly limited as long as it is a group containing an active carbon-carbon double bond with respect to a crosslinking reaction by a hydrosilyl group-containing compound. Specific examples include aliphatic unsaturated hydrocarbon groups such as vinyl group, allyl group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group. And cyclic unsaturated hydrocarbon groups such as

  As a method for introducing an alkenyl group into the terminal of an isobutylene polymer, the polymer having a functional group such as a hydroxyl group is unsaturated as disclosed in JP-A-3-152164 and JP-A-7-304909. Examples thereof include a method of introducing an unsaturated group into a polymer by reacting a group-containing compound. 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. And the like, and the above-described alkenyl group-introducing reaction is further performed after introducing a hydroxyl group. Further, as disclosed in US Pat. No. 4,316,973, Japanese Patent Application Laid-Open No. 63-105005, and Japanese Patent Application Laid-Open No. 4-288309, an unsaturated group can be introduced during the polymerization of the monomer. Among these, those in which an allyl group is introduced at the terminal by a substitution reaction of allyltrimethylsilane and chlorine are preferable from the viewpoint of reactivity.

  The amount of the alkenyl group at the end of the isobutylene polymer can be arbitrarily selected depending on the required properties, but from the viewpoint of compression set after crosslinking, at least 0.2 alkenyl groups per molecule are terminated. It is preferable that it is a polymer which has. If the number is less than 0.2, the effect of improving the compression set due to crosslinking may not be sufficiently obtained.

  The structure of the aromatic vinyl-based thermoplastic elastomer used in the present invention is not particularly limited, whether it is a random copolymer or a block copolymer, but is mainly composed of units mainly composed of an aromatic vinyl compound and isobutylene. It is preferable that it is a block copolymer which consists of a unit to do. The aromatic vinyl-based thermoplastic elastomer is a block copolymer composed of a unit mainly composed of an aromatic vinyl compound and a unit mainly composed of a conjugated diene compound, and a block copolymer obtained by hydrogenating the block copolymer. Preferably there is. Among these, a triblock copolymer consisting of a unit mainly composed of an aromatic vinyl compound, a unit mainly composed of isobutylene, and a unit mainly composed of an aromatic vinyl compound is particularly preferred from the viewpoint of high tensile strength.

  As the aromatic vinyl compound, the above-mentioned aromatic vinyl compound can be used, but among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferable from the balance of cost, physical properties, and productivity. .

  Conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5 -Diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc. are mentioned. To obtain a hydrogenated diene polymer having industrial properties and excellent physical properties, 3-butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene and isoprene are particularly preferred.

  The unit mainly composed of isobutylene means a block in which isobutylene occupies 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. The monomer other than isobutylene in the unit mainly composed of isobutylene is not particularly limited as long as it is a monomer component capable of cationic polymerization, but aromatic vinyls, aliphatic olefins, dienes, vinyl ethers, silanes. And monomers such as β-pinene, vinylcarbazole, and acenaphthylene. These may be used alone or in combination of two or more.

  The ratio of the aromatic vinyl compound in the aromatic vinyl-based thermoplastic elastomer is not particularly limited, but is preferably 5 to 80% by weight, and preferably 10 to 40% by weight from the balance between physical properties and processability. Particularly preferred.

  The number average molecular weight of the aromatic vinyl-based thermoplastic elastomer is not particularly limited, but is preferably 15,000 to 500,000, particularly preferably 40,000 to 200,000. If the number average molecular weight is less than 15,000, mechanical properties such as tensile properties tend to be insufficient, and if it exceeds 500,000, the moldability tends to deteriorate significantly.

  The olefin resin used in the present invention is a homopolymer or copolymer having as a main component a monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of such include polyethylene (high density polyethylene, low density polyethylene, linear low density polyethylene), polypropylene (isotactic-homopolypropylene, random polypropylene, block polypropylene, syndiotactic-homopolypropylene), poly- Examples thereof include 1-butene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Among these, from the viewpoint of heat resistance, polypropylene and polyethylene having crystallinity are preferable. Further, from the viewpoint of mechanical properties, random polypropylene is most preferable, and from the viewpoint of compression set properties, high-density polyethylene is most preferable.

  In the present invention, the isobutylene polymer having an alkenyl group at the terminal is melt kneaded with a hydrosilyl group-containing compound in the presence of at least one selected from the group consisting of an aromatic vinyl thermoplastic elastomer and an olefin resin. A composition is formed which is dynamically cross-linked underneath. Dynamic crosslinking differs from normal chemical crosslinking (static crosslinking) in that the crosslinking reaction proceeds under melt-kneading, resulting in the polymer network being broken by shearing force and exhibiting thermoplasticity after crosslinking. It is. Originally, the isobutylene-based polymer has no crosslinkable functional group, and the radical reaction generally used as a crosslinking reaction tends to cause a decomposition reaction. In the present invention, by introducing an alkenyl group at the end of the isobutylene polymer, a hydrosilylation reaction is possible, and a crosslinking reaction using a hydrosilyl group-containing compound as a crosslinking agent is possible. This hydrosilylation reaction has advantages such as no generation of by-products and no unnecessary side reactions.

In the present invention, the hydrosilyl group-containing compound for obtaining a crosslinked product of an isobutylene polymer having an alkenyl group at the terminal is not particularly limited, and various compounds can be used. That is, a linear polysiloxane represented by the general formula (I) or (II);
_{^{R 1 3 SiO- [Si (R}} 1) 2 O] a - [Si (H) (R 2) O] b - [Si (R 2) (R 3) O] c -SiR 1 3 (I)
_{^{HR 1 2 SiO- [Si (R}} 1) 2 O] a - [Si (H) (R 2) O] b - [Si (R 2) (R 3) O] c -SiR 1 2 H (II)
(Wherein R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c satisfying 0 ≦ c ≦ 100.)
A cyclic siloxane represented by the general formula (III);

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

(In the formula, g and h are integers, and 2 ≦ g + h ≦ 50, 2 ≦ g, and 0 ≦ h. R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents carbonization having 2 to 20 carbon atoms. (It may be a hydrogen group and may have one or more aromatic rings. I is an integer of 0 ≦ i ≦ 5.)
The isobutylene polymer having an alkenyl group at the terminal and the hydrosilyl group-containing compound can be mixed at an arbitrary ratio, but from the viewpoint of reactivity, the molar ratio of the alkenyl group to the hydrosilyl group is in the range of 5 to 0.2. It is preferable that the ratio is 2.5 to 0.4. When the molar ratio is 5 or more, the crosslinking is insufficient and sticky, and the compression set tends to deteriorate. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain even after crosslinking. Hydrogen gas is generated by hydrolysis and tends to cause cracks and voids.

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

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

Also, the transition metal catalyst is not particularly limited. For example, platinum solid, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. Complex, platinum-olefin complex, and 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, such as NiCl _2, TiCl ₄ and the like. These catalysts may be used alone or in combination of two or more. Of these, platinum vinyl siloxane is most preferred in terms of compatibility, crosslinking efficiency, and scorch stability.

Although there is no restriction | limiting in particular as a catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of an isobutylene type polymer, Preferably it is the range of 10 ^{< -3} > ^-10 <^-6> mol. It is good to use. When the amount is less than 10 ⁻⁸ mol, crosslinking tends not to proceed sufficiently. Moreover, since a clear effect is not seen even if it uses 10 ^<-1 > mol or more, it is preferable that it is less than 10 ^{< -1} > mol from the surface of economical efficiency.

  In the present invention, the blending amount of at least one selected from the group consisting of an aromatic vinyl-based thermoplastic elastomer and an olefin resin is 0.5 to 100 parts by weight with respect to 100 parts by weight of an isobutylene-based polymer having an alkenyl group at the terminal. 900 parts by weight, preferably 5 to 100 parts by weight. When the blending amount exceeds 900 parts by weight, compression set characteristics tend to deteriorate. Further, the case of 100 parts by weight or less is preferable because the concentration of the alkenyl group is sufficiently high, and the reaction rate of the crosslinking reaction is increased. On the other hand, if the amount is less than 0.5 parts by weight, the moldability tends to be significantly reduced.

  In the present invention, it is preferable that the dynamically crosslinked resin composition further contains a thermoplastic resin. Examples of the thermoplastic resin include (i) general-purpose thermoplastic resin, (ii) general-purpose engineering plastic, and (iii) special engineering plastic.

  (i) Examples of the general-purpose thermoplastic resin include polyolefin resin, aromatic vinyl compound resin, polyvinyl chloride resin, polyacrylic resin, and polyether resin.

  Examples of polyolefin resins include α-olefin homopolymers, random copolymers, block copolymers and mixtures thereof, or random copolymers of α-olefins and other unsaturated monomers, block copolymers. Examples thereof include polymers, graft copolymers and oxidized, halogenated or sulfonated polymers of these polymers. Specifically, polyethylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, other ethylene- α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyethylene resin such as chlorinated polyethylene, polypropylene, propylene-ethylene random copolymer, Examples thereof include propylene-ethylene block copolymers, polypropylene resins such as chlorinated polypropylene, polybutene, polyisobutylene, polymethylpentene, and cyclic olefin (co) polymers. Among these, a polyethylene resin, a polypropylene resin, or a mixture thereof can be preferably used from the viewpoint of cost and physical property balance of the resin composition.

  Examples of the aromatic vinyl compound resin include polystyrene, high impact polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, and styrene-maleic anhydride copolymer.

  Examples of the polyvinyl chloride resin include polyvinyl chloride, polyvinylidene chloride, and chlorinated polyvinyl chloride.

  Examples of polyacrylic resins include acrylonitrile-styrene resin (AS), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-butadiene-α-methylstyrene (heat-resistant ABS), polymethyl methacrylate, and methyl methacrylate-styrene copolymer. Can be given.

  Examples of the polyether resin include polyethylene oxide, polypropylene oxide, and polytetrahydrofuran.

  (ii) Examples of general-purpose engineering plastics include polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, polyphenylene ether resins, polymethylpentene, and ultrahigh molecular weight polyethylene.

  Examples of the polyamide-based resin include nylon-6, nylon-66, nylon-11, nylon-12, nylon-46, nylon-610, nylon-612, and the like.

  Examples of polyester resins include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, amorphous polyethylene terephthalate, and crystalline polyethylene terephthalate.

  Polycarbonate resins include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), those in which a part or all of the aromatic hydrogen of bisphenol A is substituted with an alkyl group or a halogen atom, hydroquinone, bis ( Examples thereof include polycarbonate resins formed on the basis of 4-hydroxyphenyl) sulfone and the like.

  Examples of the polyacetal resin include polyoxymethylene.

  Examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2,6-dibutyl-1 , 4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4) -Phenylene) ether and the like.

  (iii) Special engineering plastics include polysulfone resins, polysulfide resins, polyimide resins, polyamideimide resins, polyetherimide resins, fluorine resins, thermoplastic polyurethane resins, polyethersulfone resins, polyethers Examples thereof include ketone-based resins and thermotropic liquid crystal resins.

  Examples of the polysulfone resin include poly (ether sulfone) and poly (4,4'-bisphenol ether sulfone).

  Examples of the polysulfide resin include polyphenylene sulfide and poly (4,4'-diphenylene sulfide).

  Examples of the polyether ketone resin include polyether ether ketone.

  Examples of thermotropic liquid crystal resins include p-hydroxybenzoic acid, a copolymer of biphenol and terephthalic acid, a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, polyethylene terephthalate (PET), and p-hydroxy. Examples include benzoic acid copolymers.

  The blending amount of the thermoplastic resin is preferably 5 to 200 parts by weight, and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the total amount of the dynamically crosslinked resin composition. When the amount exceeds 200 parts by weight, the compression set characteristic tends to be remarkably deteriorated. When the amount is less than 5 parts by weight, the moldability tends to be remarkably lowered.

  In order to melt-knead the thermoplastic resin to the dynamically crosslinked resin composition of the present invention, a known method may be employed, and the above-described batch kneader or continuous kneader can be used. For example, there is a method in which each component is weighed and mixed with a tumbler, a Henschel mixer, a riboblender or the like and then melt kneaded with an extruder, a Banbury mixer, a roll or the like. Although the kneading | mixing temperature at this time does not have limitation in particular, the range of 100-250 degreeC is preferable, and the range of 150-220 degreeC is more preferable. When the kneading temperature is lower than 100 ° C., melting tends to be insufficient, and when it is higher than 250 ° C., deterioration due to heating tends to start.

  A softener can be further added to the resin composition of the present invention in order to improve moldability and flexibility. Although it does not specifically limit as a softening agent, Usually, a liquid or liquid material is used suitably at room temperature. Both hydrophilic and hydrophobic softeners can be used. Such softeners include various rubber or resin softeners such as mineral oils, vegetable oils, and synthetics.

  Mineral oils include paraffinic oils, naphthenic oils, and aromatic high-boiling petroleum components. Of these, paraffinic oil that does not inhibit the crosslinking reaction is preferred. Examples of vegetable oils include castor oil, cottonseed oil, ramie oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine oil, olive oil and the like. Synthetic systems include liquid or low molecular weight synthetic oils such as polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, and liquid poly α-olefins. These softeners can be used in an appropriate combination of two or more in order to obtain the desired viscosity and physical properties.

  The blending amount of the softening agent is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the isobutylene polymer having an alkenyl group at the terminal. If the blending amount exceeds 300 parts by weight, stickiness or mechanical strength tends to decrease.

  Furthermore, a thermoplastic elastomer, a lyotropic liquid crystal resin, a liquid resin, a thermosetting resin, a cross-linked rubber, or the like may be added as long as the performance of the molded article and the modifier of the present invention is not impaired.

  Thermoplastic elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene. / Propylene-styrene block copolymer (SEPS) and their hydrogenated elastomers, polyolefins, polydienes, polyvinyl chlorides, polyurethanes, polyesters, polyamides, fluorines, silicones, ionomers, etc. Examples include various elastomers.

  Examples of the lyotropic liquid crystal resin include aramid, poly p-phenylene benzobisthiazole, polyterephthaloyl hydrazide, and the like.

  Examples of liquid resins include silicone resins, modified silicone (MS) resins, polyisobutylene (PIB) resins, polysulfide resins, modified polysulfide resins, polyurethane resins, polyacrylic resins, and polyacrylurethane resins. can give.

  Examples of thermosetting resins include unsaturated polyester resins, epoxy resins, hydrosilylated crosslinking resins, phenol resins, alkyd resins, diallyl phthalate resins, urea resins, polyurethane resins, melamine resins, and the like. It is done.

  Cross-linked rubbers include natural rubber, polybutadiene rubber (PBD), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, chlorinated butyl rubber, chloroprene rubber, acrylic. Examples thereof include rubber, urethane rubber, isoprene rubber, ethylene-propylene rubber, fluorine rubber, and silicone rubber.

  Furthermore, a filler and a reinforcing material can be blended with the resin composition in the present invention from the viewpoint of improving physical properties or economic advantages. Suitable fillers and reinforcements include hard clay, soft clay, kaolin clay, diatomaceous earth, silica sand, pumice powder, slate powder, dry or wet silica, amorphous silica, wollastonite, synthetic or natural zeolite, talc, sulfuric acid Barium, light or heavy calcium carbonate, magnesium carbonate, calcium sulfate, aluminum sulfate, molybdenum disulfide, magnesium hydroxide, calcium silicate, alumina, titanium oxide, other metal oxides, mica, graphite, aluminum hydroxide, etc. Flour-like inorganic filler, various metal powders, wood chips, glass powder, ceramic powder, carbon black, granular or powdered solid filler such as granular or powdered polymer, other various natural or artificial short fibers, long fibers Etc. can be exemplified. These fillers and reinforcing materials may be silane treated. Moreover, weight reduction can be achieved 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 shock absorption, and it is also possible to mix gas mechanically during mixing.

  The blending amount of the filler and the reinforcing material is 0 to 200 parts by weight, preferably 0 to 100 parts by weight with respect to 100 parts by weight of the resin composition. If it exceeds 200 parts by weight, the mechanical strength of the resulting resin composition is lowered, and the flexibility is also impaired.

  In addition, the resin composition in the present invention may include hindered phenol-based, phosphate ester-based, amine-based, sulfur-based antioxidants, and / or benzothiazole-based, benzosotriazole-based, benzophenone as necessary. An ultraviolet absorber such as a system and a light stabilizer can be blended. A compounding quantity is 0.000001-10 weight part with respect to 100 weight part of resin resin compositions, Preferably it is 0.00001-5 weight part.

  Furthermore, a plasticizer can be added to the resin composition in the present invention. Examples of the plasticizer include phthalic acid ester, adipic acid ester, phosphoric acid ester, trimellitic acid ester, citric acid ester, epoxy, and polyester.

  Furthermore, a tackifier resin can be added to the resin composition in the present invention. Examples of the tackifying resin include alicyclic petroleum resins and hydrides thereof, aliphatic petroleum resins, hydrides of aromatic petroleum resins, polyterpene resins, and the like.

  Still other additives include flame retardants, antibacterial agents, light stabilizers, colorants, fluidity improvers, lubricants, anti-blocking agents, antistatic agents, cross-linking agents, cross-linking aids, modifiers, pigments, dyes, conductive A filler, various chemical foaming agents, physical foaming agents and the like can be added, and these can be used alone or in combination of two or more. As the antiblocking agent, for example, silica, zeolite and the like are suitable, and these may be natural or synthetic, and true spherical crosslinked particles such as crosslinked acrylic true spherical particles are also suitable. As the antistatic agent, N, N-bis- (2-hydroxyethyl) -alkylamines and glycerin fatty acid esters having an alkyl group having 12 to 18 carbon atoms are preferable. Furthermore, as the lubricant, fatty acid metal salt lubricants, fatty acid amide lubricants, fatty acid ester lubricants, fatty acid lubricants, aliphatic alcohol lubricants, partial esters of fatty acids and polyhydric alcohols, paraffin lubricants and the like are preferably used. Two or more of these may be selected and used.

  The resin composition in this invention can be manufactured by the method illustrated below.

  For example, when manufacturing using a closed or open batch kneader such as a lab plast mill, brabender, banbury mixer, kneader, roll, etc., all components other than the premixed crosslinking agent are kneaded. And then kneading and kneading until uniform, then adding a cross-linking agent to the cross-linking reaction and then stopping the melt-kneading.

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

  In performing melt-kneading, a temperature range of 140 to 210 ° C is preferable, and a temperature range of 150 to 200 ° C is more preferable. If the melt kneading temperature is lower than 140 ° C., the aromatic vinyl-based thermoplastic elastomer and olefin resin do not melt and tend not to be mixed sufficiently. Tends to occur.

The molded article and modifier of the present invention are rich in flexibility and excellent in molding processability, rubber-like characteristics, mechanical strength, and compression set characteristics. Therefore, it can be used for the following purposes.
(1) Modifiers Resin modifiers (impact modifiers for thermosetting resins such as thermoplastic resin impact modifiers, damping modifiers, gas barrier modifiers, softeners, etc. Agents, low stress agents, etc.), asphalt modifiers (asphalt modifiers for roads, asphalt modifiers for waterproof sheets, waterproof materials for bridge decks), tire modifiers (wet grip improvers for tires) , Rubber modifier

(2) Adhesive or adhesive Hot-melt adhesive, water-based adhesive, solvent-based adhesive, adhesive

(3) Viscosity modifier Viscosity modifier added to oil, lubricating oil, etc.

(4) Coating agents Base resins and sealants used for paints, etc.

(5) Materials used for PVC replacement Cable covering materials such as cables, connectors and plugs, toys such as dolls, curing tapes, logo marks (for sportswear and sports shoes), carry bags, clothing packaging materials, Truck tops, agricultural films (for house cultivation), erasers, commercial aprons (tarpaulins), building interior materials such as flooring and ceiling materials, raincoats, umbrellas, shopping bags, skin materials such as chairs and sofas, Cover materials such as belts and bags, garden hoses, refrigerator gaskets (packing), flexible hoses for washing machines and vacuum cleaners, automotive interior materials

(6) Damping materials, anti-vibration materials, shock-absorbing materials Damping materials, especially vibration-damping materials, anti-vibration materials and shock-absorbing materials laminated together with aluminum and steel sheets (building applications, automotive applications, floor vibration-damping applications, flooring applications) , Used for play equipment, precision equipment, electronic equipment)
Gloves for shoe soles, stationery and toy supplies, grips for daily goods and carpenter supplies, grips and heartwood for golf clubs and bats, rubber and grips for tennis rackets and table tennis rackets, etc.

(7) Soundproofing materials, sound absorbing materials Automotive interior / exterior materials, automotive ceiling materials, railcar materials, piping materials

(8) Sealing materials such as packing materials and sealing materials, packaging materials Gaskets, architectural gaskets, plugs Glass sealing materials for laminated glass and multilayer glass Gases for packaging materials, sheets, multilayer sheets, containers, multilayer containers, etc. Barrier materials Civil engineering sheets, tarpaulins, packaging transport materials, sealants

(9) Foam Foam by bead foaming, slow pressure foaming, extrusion foaming (pipe coating material, synthetic wood, wood powder foam, etc.)
Carrier of blowing agent in chemical and physical foaming

(10) Others For clothing, flame retardant,
Tubes, closures, caps, bags, gaskets, hoses, shoes, sports equipment for medical use Foamable fireproof seats Airbag covers, bumpers, interior parts (skin materials such as instrument panels and shift knobs), weather strips, roof moldings, Automotive parts such as moldings under the door Food trays for microwave ovens, food containers for potions, laminated films for food containers, polystyrene sheets for food containers (sashimi containers / chicken egg packs), cup ramen containers, polystyrene-based reticulated foams, frozen desserts Cups, transparent beverage cups and other food containers IC trays, CD-ROM chassis, wheel caps, elastic yarns, non-woven fabrics, wire harnesses, backsheets for disposable diapers, compound materials for 2-color molding, underwater goggles, PC mice, cushions, stopper

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by these Examples, In the range which does not change the summary, it can change suitably.

First, various measurement methods and evaluation methods will be described.
(hardness)
In accordance with JIS K 6352, a 12.0 mm pressure press sheet was used as a test piece.

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

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

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

(Dynamic viscoelasticity)
In accordance with JIS K-6394 (Method for testing dynamic properties of vulcanized rubber and thermoplastic rubber), a test piece having a length of 6 mm, a width of 5 mm, and a thickness of 2 mm was cut out and a dynamic viscoelasticity measuring apparatus DVA-200 (IT Loss tangent tan δ was measured using Measurement Control Co., Ltd. The measurement frequency was 0.5 Hz.

Moreover, the symbol of the material used by the Example and the comparative example and its specific content are as follows.
SIBS: Styrene-isobutylene-styrene triblock copolymer APIB: Polyisobutylene having an allyl group introduced at the terminal EP600A (manufactured by Kaneka Chemical Co., Ltd.)
IIR: Butyl rubber (Butyl065, manufactured by JSR)
Thermoplastic resin: Polyphenylene ether resin Noryl EFN4230 (manufactured by GE Plastics)
Crosslinking agent 1: Chain siloxane crosslinking agent containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule 2: Reactive brominated alkylphenol formaldehyde compound (Tactrol 250-1, Taoka Chemical Industries ( Made by)
Crosslinking aid 1: Triethylene glycol dimethacrylate (NK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Crosslinking aid 2: Zinc oxide crosslinking catalyst: 1,1,3,3-tetramethyl-1,3-diallyldisiloxane complex of zerovalent platinum 1% xylene solution

Production Example 1 (Manufacture of SIBS)
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 456.4 mL of n-hexane and 656.3 mL of butyl chloride (both dried with molecular sieves) were added using a syringe, and the polymerization vessel was kept at -70 ° C. In a dry ice / methanol bath. A liquid feeding tube made of Teflon (registered trademark) was connected to a liquefied collection tube made of pressure resistant glass with a three-way cock containing 232 mL (2871 mmol) of isobutylene monomer, and the isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.647 g (2.8 mmol) of p-dicumyl chloride and 1.22 g (14 mmol) of N, N-dimethylacetamide were added. Next, 8.67 mL (79.1 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 2.5 hours from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, a mixed solution of 77.9 g (748 mmol) of styrene monomer, 14.1 mL of n-hexane and 20.4 mL of butyl chloride, which had been cooled to −70 ° C. in advance, was added to the polymerization vessel. Two hours after the addition of the mixed solution, the reaction was terminated by adding a large amount of water.

  The reaction solution was washed twice with water, the solvent was evaporated, and the resulting polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the desired block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. A block copolymer having a block copolymer Mw of 101000 was obtained.

Example 1
SIBS and APIB were melt-kneaded for 5 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 150 ° C. in the ratio shown in Table 1, and then a crosslinking agent was added in the ratio shown in Table 1. The kneading was continued for 5 minutes. A cross-linking catalyst was added, and melt kneading was further performed for dynamic cross-linking. The obtained thermoplastic elastomer composition could be easily formed into a sheet at 180 ° C. The hardness, tensile breaking strength, tensile breaking elongation, compression set, and dynamic viscoelasticity of the obtained sheet were measured according to the above methods. The results are shown in Table 1.

Example 2
SIBS, APIB, and a thermoplastic resin were mixed in the proportions shown in Table 1, and dynamic crosslinking was performed in the same manner as in Example 1. The obtained thermoplastic elastomer composition could be easily formed into a sheet at 180 ° C. The hardness, tensile breaking strength, tensile breaking elongation, and compression set of the obtained sheet were measured according to the above methods. The results are shown in Table 1.

Comparative Example 1
After melt-kneading for 10 minutes using a Laboplast mill with SIBS set at 180 ° C., it was molded into a sheet at 180 ° C. The hardness, tensile breaking strength, tensile breaking elongation and compression set of the obtained sheet were measured according to the above methods. The results are shown in Table 1.

Comparative Example 2
SIBS and IIR were melt kneaded for 5 minutes using a lab plast mill set at 180 ° C. in the proportions shown in Table 1, and then crosslinking agent 2, crosslinking assistants 3 and 4 were added in the proportions shown in Table 1. Further, the mixture was further melt-kneaded at 180 ° C. until the torque value reached the maximum value (3 to 7 minutes) to perform dynamic crosslinking. The obtained thermoplastic elastomer composition could be easily formed into a sheet at 180 ° C. The hardness, tensile breaking strength, tensile breaking elongation, and compression set of the obtained sheet were measured according to the above methods. The results are shown in Table 1.

Comparative Example 3
Using only APIB, a crosslinking agent and a crosslinking catalyst were blended in the ratios shown in Table 1, and a composition was obtained in the same manner as in Example 1. A sheet-like molded product could not be obtained using this composition.

Comparative Example 4
Sheets were prepared using Lavalon SJ5400N (manufactured by Mitsubishi Chemical Corporation), and the hardness, tensile breaking strength, tensile breaking elongation, compression set and dynamic viscoelasticity were measured according to the above methods. The results are shown in Table 1.

The sheet obtained in the example has a lower compression set value than the sheet composed only of the isobutylene block copolymer shown in Comparative Example 1, and is excellent in compression set while maintaining the characteristics of the isobutylene block copolymer. ing. Compared with the case where IIR is used for the cross-linked product shown in Comparative Example 2, the hardness is comparable, but the compression set is excellent. Further, it can be seen that the sheet of Example 1 has a high tan δ value and excellent vibration damping properties as compared with Comparative Example 4.

Claims (10)

In the presence of at least one selected from the group consisting of an aromatic vinyl thermoplastic elastomer and an olefin resin, the isobutylene polymer having an alkenyl group at the terminal is dynamically cross-linked under melt kneading with a hydrosilyl group-containing compound. A molded body made of the resin composition. In the presence of at least one selected from the group consisting of an aromatic vinyl thermoplastic elastomer and an olefin resin, the isobutylene polymer having an alkenyl group at the terminal is dynamically cross-linked under melt kneading with a hydrosilyl group-containing compound. The modifier which consists of a resin composition. The molded article according to claim 1, wherein the resin composition further contains a thermoplastic resin. The modifier according to claim 2, wherein the resin composition further comprises a thermoplastic resin. The molded article according to claim 1 or 3, wherein the resin composition further contains a softening agent. The modifier according to claim 2 or 4, wherein the resin composition further contains a softening agent. The molded article according to claim 1, 3 or 5, wherein the aromatic vinyl-based thermoplastic elastomer is a block copolymer comprising a unit mainly composed of an aromatic vinyl compound and a unit mainly composed of isobutylene. The modifier according to claim 2, 4 or 6, wherein the aromatic vinyl-based thermoplastic elastomer is a block copolymer comprising a unit mainly composed of an aromatic vinyl-based compound and a unit mainly composed of isobutylene. The isobutylene polymer having an alkenyl group at a terminal is a polymer having a number average molecular weight of 1,000 to 500,000 and having at least 0.2 alkenyl groups per molecule per terminal. The molded body described. The isobutylene polymer having an alkenyl group at the end is a polymer having a number average molecular weight of 1,000 to 500,000 and having at least 0.2 alkenyl groups per molecule per end. The modifier described.