JP2015168748A - thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition that is excellent in physical properties of the composition, is easy to handle a raw material, is easily produced, and causes no unintended coloration.SOLUTION: The thermoplastic elastomer composition is produced by dynamically crosslinking (a) an isobutylene polymer having an aryl group at a terminal in the coexistence of (b) a platinum vinylsiloxane complex supported on calcium carbonate, (c) a hydrogen siloxane compound (Si-H compound) and (d) a thermoplastic resin.

Description

  The present invention relates to a thermoplastic elastomer composition containing an isobutylene polymer, and more specifically, a heat obtained by dynamically crosslinking an isobutylene polymer in the presence of a platinum catalyst supported on calcium carbonate. The present invention relates to a plastic elastomer composition.

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 a high temperature and a high pressure, and have problems in terms of productivity.
In addition, since 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.

  Examples of such thermoplastic elastomers include olefins, urethanes, esters, styrenes, vinyl chlorides and the like. Of these, styrenic thermoplastic elastomers are widely used because of their high flexibility and excellent rubber elasticity.

  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, the thermoplastic elastomer having high flexibility, excellent rubber elasticity, and excellent gas barrier properties includes a polymer block mainly composed of isobutylene and a polymer block mainly composed of an aromatic vinyl compound. Although isobutylene block copolymers (SIBS) are known, SIBS is also a thermoplastic elastomer that essentially does not contain crosslinks, so there are problems of deformation rate (compression set) during heating and reduction in rubber elasticity. there were.

  Patent Document 1 discloses a thermoplastic elastomer composition obtained by dynamically crosslinking an isobutylene polymer in the presence of a thermoplastic resin as a solution to the above problem. 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, among the raw materials used in the above composition, the 1,1,3,3-tetramethyl-1,3-diallyldisiloxane complex of zerovalent platinum is a liquid because the 1% xylene solution is a liquid. For contractors, it may be necessary to install a new liquid component addition facility, and since the addition amount itself is extremely small, it is difficult to guarantee the quantitativeness of the addition amount, and a larger amount than the intended addition amount is added. In the case where the composition is applied or only a small amount is added, a composition having the desired performance may not be obtained.

  In addition, as disclosed in Patent Documents 1 to 5, a platinum catalyst in which a platinum complex is supported on some solid may be used. For example, when silica is used as a carrier, silica is used in comparison with other carriers. Not only is it relatively expensive per se, but the viscosity may rise drastically when preparing a composition, and it has not always been easy to handle.

  When carbon black is used as a carrier, the resulting composition may unintentionally be colored gray to black.

  On the other hand, compounds such as zero-valent platinum metal and platinum black may have low catalytic ability, and a thermoplastic elastomer composition that is satisfactory in terms of physical properties may not be obtained.

  Therefore, in terms of physical properties, workability, and coloring of products, it is not always possible to obtain a satisfactory composition, the composition is excellent in physical properties, easy to handle raw materials, easy to manufacture, There has been a demand for a thermoplastic elastomer composition having no unintentional coloring.

JP 2003-55528 A JP 2006-152030 A JP 2011-21074 A Japanese Patent Application Laid-Open No. 11-166075 JP 2000-336239 A

  The present invention has been made in view of the above problems, and is to provide a thermoplastic elastomer composition that is excellent in the physical properties of the composition, is easy to handle raw materials, is easy to manufacture, and has no unintentional coloring. .

  The present inventor has found that the above problems can be solved by a thermoplastic composition obtained by dynamically crosslinking an isobutylene polymer having an allyl group at its terminal using a platinum vinylsiloxane complex supported on calcium carbonate. The present invention has been completed.

  That is, the present invention comprises (a) an isobutylene polymer having an allyl group at its end, (b) a platinum vinylsiloxane complex supported on calcium carbonate, (c) a hydrogensiloxane compound (Si-H compound), and (D) The present invention relates to a thermoplastic elastomer composition characterized by being dynamically crosslinked in the presence of a thermoplastic resin.

  In a preferred embodiment, the vinylsiloxane ligand in the platinum vinylsiloxane complex supported on calcium carbonate is 1,3-divinyl-1,1,3,3-tetraalkyldisiloxane or 2,4,6,8. -It relates to a thermoplastic elastomer composition, which is tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane.

  In a preferred embodiment, the vinylsiloxane ligand in the platinum vinylsiloxane complex supported on calcium carbonate is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane or 2,4,6,8. -It relates to a thermoplastic elastomer composition characterized by being tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane.

  As a preferred embodiment, the present invention relates to a thermoplastic elastomer composition, wherein the isobutylene polymer having an allyl group at the terminal is an isobutylene block copolymer having an allyl group at the terminal.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic elastomer composition which is excellent in the physical property of a composition, is easy to handle a raw material, is easy to manufacture, and also has no unintentional coloring is provided.

  (A) The isobutylene polymer having an allyl group at the end of the present invention may be any polymer as long as it has an allyl group at the end and contains an isobutylene unit in the main chain, What contains 60 weight% or more of isobutylene units is preferable from the point which can express favorable gas barrier property and heat resistance.

  The structure of the polymer may be random or block, but is preferably a block body from the viewpoint of obtaining an industrially useful polymer, such as the production of a high molecular weight thermoplastic elastomer. . Further, as the block body, (1) in addition to the polymer in which the allyl group is directly bonded to the terminal of the polymer block mainly composed of isobutylene, (2) at the terminal of the polymer block mainly composed of isobutylene, A polymer in which a polymer block mainly composed of an aromatic vinyl monomer is bonded, and an allyl group is bonded to the other end of the polymer block mainly composed of the aromatic vinyl monomer, that is, an allyl group Is preferably used as the isobutylene block copolymer. Among these, the latter isobutylene block copolymer having an allyl group at the end can not only exhibit rubber elasticity without undergoing a crosslinking step, but also is easy to handle because it is provided in the form of a pellet, and further, a thermoplastic elastomer. It is preferable because it is a material that can be reused even after being molded once.

<< Isobutylene block copolymer having an allyl group at its end >>
The isobutylene block copolymer having an allyl group at the end produced in the present invention comprises a block mainly composed of an aromatic vinyl compound and a block mainly composed of isobutylene.

<Polymer block mainly composed of aromatic vinyl compounds>
The polymer block mainly composed of an aromatic vinyl compound is a polymer block composed of 60% by weight or more, preferably 80% by weight or more of units derived from an aromatic vinyl compound.

  Aromatic vinyl compounds 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-dimethyl Styrene, 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. Among these, styrene, p-methylstyrene, α-methylstyrene, indene, or a mixture thereof is preferable from the viewpoint of industrial availability and glass transition temperature, and styrene is particularly preferable because of availability. Is preferred.

<Polymer block mainly composed of isobutylene>
The polymer block containing isobutylene as a main component is excellent in mechanical properties as an elastomer of the copolymer to be obtained. Therefore, the unit derived from isobutylene is composed of 60% by weight or more, preferably 80% by weight or more. It is a polymer block.

  Moreover, the block formed only from isobutylene may be sufficient, and if it is a range which does not impair the effect of this invention, monomers other than isobutylene may be contained. The monomer other than isobutylene is not particularly limited as long as it is a monomer capable of cationic polymerization with isobutylene. For example, aliphatic olefins, aromatic vinyl compounds, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene. And monomers such as acenaphthylene. These may be used alone or in combination of two or more.

  Moreover, in any of the above polymer blocks, a mutual monomer can be used as a copolymer component, and other cationic polymerizable monomer components can be used. Examples of such monomer components include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, and acenaphthylene. These can be used alone or in combination of two or more.

<Isobutylene block copolymer>
The isobutylene block copolymer having an allyl group at the end of the present invention is a polymer block mainly composed of isobutylene, or a polymer block mainly composed of isobutylene and a polymer block mainly composed of an aromatic vinyl compound. As long as it is configured, the structure is not particularly limited. For example, a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock having a linear, branched, or star structure. Any copolymer or the like can be selected.

  In the case where it is desired that a polymer block mainly composed of an aromatic vinyl compound typified by polystyrene or the like is not necessary or rather not present in expressing desired physical properties, a preferable structure is mainly composed of isobutylene. Polymer block to be used.

  On the other hand, as a preferable structure from the viewpoint of physical property balance and molding processability, a block mainly composed of an aromatic compound at both ends and a polymer block mainly composed of an isobutylene compound between them. And an AB type diblock copolymer in which a polymer block mainly composed of an aromatic compound and a polymer block mainly composed of isobutylene are bonded to each other.

  The content of the polymer block mainly comprising isobutylene in the total weight of the isobutylene block copolymer having an allyl group is preferably 20 to 95% by weight, more preferably 50 to 90% by weight. If it exceeds 95%, handling as pellets becomes difficult, and the copolymer becomes veiled, which is not preferable in terms of deterioration in handleability during processing. On the other hand, if it is less than 20%, the hardness of the copolymer becomes too high, the flexibility becomes poor, and the performance as an elastomer material cannot be sufficiently exhibited.

  The number average molecular weight of the isobutylene block copolymer having an allyl group at the terminal of the present invention is not particularly limited, but is preferably from 10,000 to 500,000 in terms of polystyrene equivalent molecular weight measured by gel permeation chromatogram, 000 to 300,000 is particularly preferred. If it is less than 10,000, mechanical properties are not sufficiently exhibited, and the performance as an elastomer material may be inferior. On the other hand, if it exceeds 500,000, the moldability is greatly deteriorated and handling may be difficult.

  The molecular weight distribution (number represented by the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn) of the isobutylene block copolymer having an allyl group at the end of the present invention is 1.0 to 3.0. Is preferable, and 1.0 to 2.0 is more preferable. If it exceeds 3.0, the molecular weight uniformity is low and the viscosity of the polymer tends to be high when molding using a molten state or a solvent or the like, and workability may deteriorate. Therefore, in particular, it is preferably less than 1.8 because the melt viscosity of the resin can be lowered.

<Allyl group>
The allyl group of the isobutylene block copolymer having an allyl group at the end of the present invention is a group that is active for a crosslinking reaction with a hydrosilyl group-containing compound.
The amount of allyl group in the isobutylene block copolymer having an allyl group at the terminal is averaged per molecule from the viewpoint of heat resistance, solvent resistance, compatibility improvement effect with other resins, and compression set improvement effect. And a polymer having at least 1.0 alkenyl group at the terminal. If it is less than 1.0, desired effects may not be sufficiently obtained in terms of heat resistance, solvent resistance, compatibility improvement effect, and compression set improvement effect.

As a method for introducing an allyl group into the terminal of an isobutylene block copolymer, a polymer having a functional group such as a hydroxyl group as disclosed in JP-A-3-152164 and JP-A-7-304909 is disclosed. And a method of introducing an unsaturated group into the polymer by reacting with a compound having an unsaturated group. In order to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with an alkenyl phenyl ether, a method of performing a substitution reaction with an allylsilane compound in the presence of a Lewis acid, various phenols, etc. And the like, a method in which the above-mentioned alkenyl group introduction reaction is carried out after introducing a hydroxyl group by performing a Friedel-Crafts reaction with alkenyl.
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, in the present invention, an allylsilane compound is used as an allylating agent, and an allyl group is introduced at the terminal by a substitution reaction between the allylsilane compound and chlorine. This is preferable from the viewpoint of reactivity to the crosslinking reaction.

  Examples of allylsilane compounds that can be used in the present invention include allyldimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltripropylsilane, allyltriisopropylsilane, allyltributylsilane, allyltriphenylsilane, allyldimethoxysilane, allyltrisilane. Methoxysilane, allyltriethoxysilane, allyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, allyl (chloropropyl) dichlorosilane, allyltrichlorosilane, diallyldimethylsilane, diallyldiethylsilane, diallyldipropylsilane, diallyldibutylsilane , Diallyldiphenylsilane, triallylmethylsilane, tetraallylsilane and the like. These may be used alone or in combination of two or more. Among these silicon compounds, allyltrimethylsilane, allyltriethylsilane, diallyldimethylsilane, diallyldiethylsilane, triallylmethylsilane, and tetraallylsilane are preferable in terms of availability and reactivity.

  The amount of allylsilane compound used is a numerical value expressed by the ratio of the allyl group bonded to silicon to the number of functional groups in the initiator ((allyl group bonded to silicon) / (number of functional groups in the initiator)). ) Is preferably set to 1 or more from the viewpoint of increasing the allyl group introduction rate in the resin. That is, usually, it is preferable to charge allylsilanes in excess. A preferable range of the ratio represented by (allyl group bonded to silicon) / (number of functional groups in the initiator) is 1.0 to 30, and more preferably 1.1 to 10. When the amount is 1.0 equivalent or less, the allyl group introduction rate is decreased, and a polymer terminal to which no allyl group is introduced may remain, which is not preferable. On the other hand, 30 equivalents or more is not preferable because it is economically disadvantageous.

<Polymerization solvent>
The polymerization reaction and the allylation reaction of the polymer in the present invention can be carried out in an organic solvent as necessary.

  Such a polymerization solvent is not particularly limited as long as it is a solvent generally used in cationic polymerization, and is a solvent composed of a halogenated hydrocarbon, a non-halogen solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon. Alternatively, a mixture thereof can be used. The halogenated hydrocarbon is not particularly limited, and is methyl chloride, methylene chloride, chloroethane, dichloroethane, 1-chloropropane, 1-chloro-2-methylpropane, 1-chlorobutane, 1-chloro-2-methylbutane, 1- Chloro-3-methylbutane, 1-chloro-2,2-dimethylbutane, 1-chloro-3,3-dimethylbutane, 1-chloro-2,3-dimethylbutane, 1-chloropentane, 1-chloro-2- Methylpentane, 1-chloro-3-methylpentane, 1-chloro-4-methylpentane, 1-chlorohexane, 1-chloro-2-methylhexane, 1-chloro-3-methylhexane, 1-chloro-4- Methylhexane, 1-chloro-5-methylhexane, 1-chloroheptane, 1-chlorooctane, 2-chloropropane, - chlorobutane, 2-chloro-pentane, 2-chloro-pentane, 2-chloro hexane, available 2-chloro-heptane, 2-chloro octane, chlorobenzene and the like, it can be used alone or in combination. Examples of aliphatic and / or aromatic hydrocarbons that can be used in the present invention include butane, pentane, hexane, heptane, octane, nonane, decane, 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2,2,5-trimethylhexane, cyclohexane, methylcyclohexane, ethylcyclohexane, paraffin oil, benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, etc. are used, and these are used alone or in combination of two or more. Is possible.

  Among these, it is preferable to use a mixed solvent of a monohalogenated hydrocarbon having 3 to 5 carbon atoms and an aliphatic hydrocarbon from the viewpoint of solubility and economical efficiency of the isobutylene block copolymer, and 1-chloropropane, 1 -A combination of chlorobutane, 1-chloropentane and pentane, hexane, heptane, cyclohexane, methylcyclohexane, and ethylcyclohexane is optimal in terms of solubility, economy, reactivity, and ease of distillation in post-treatment steps.

  The organic solvent is set so that the concentration of the resulting polymer is 1 to 50% by weight in consideration of the viscosity of the isobutylene polymer solution having an allyl group at the end of the present invention and ease of heat removal. It is preferably 3 to 35% by weight.

  In general, it is known that the above-described cationic polymerization is inhibited by mixing water. Therefore, it is desirable to remove the water in the solvent before using it for polymerization. As a method for dehydrating moisture, it is possible to remove by the addition and contact of a general dehydrating agent such as calcium chloride or molecular sieves.

  In order to purify the polymerization solvent to a higher degree, a distillation method can be used. By distillation, impurities having different boiling points can be almost removed. Distillation may be batch distillation or continuous distillation.

  For example, in the case of batch distillation, low boiling point impurities can be removed by extracting the column top distillate at the beginning of distillation, and high boiling point impurities can be removed by extracting the column bottom residual liquid after distillation. In the case of continuous distillation, impurities can be removed by one or more distillation towers depending on the type of impurities to be removed.

<Manufacturing method>
The polymerization method for producing the isobutylene block copolymer having an allyl group at the end of the present invention is not particularly limited. For example, isobutylene is mainly used in the presence of a compound represented by the following general formula (1). Examples thereof include a method of copolymerizing a monomer component as a component and a monomer component not containing isobutylene as a main component.

(CR ¹ R ² X) nY (1)
In formula, X represents the substituent selected from the group which consists of a halogen atom, a C1-C6 alkoxyl group, and a C1-C6 acyloxyl group. R ¹ and R ² each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different. A plurality of R ¹ and R ² may be the same or different. Y represents a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group that can have n substituents (CR ¹ R ² X). n represents a natural number of 1 to 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 acyloxy 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 a polymerization 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 ] and 1,3 - bis (1-chloro-1-methylethyl)-5-(tert-butyl) benzene _{[1,3- (C (CH 3)} 2 Cl) 2 -5- (C (CH 3) 3) C 6 H ₃ ].

Among these, more preferred are 1-chloro-1-methylethylbenzene [C ₆ H ₅ C (CH ₃ ) ₂ Cl], bis (1-chloro-1-methylethyl) benzene [C ₆ H ₄ (C (CH ₃ ) ₂ Cl) ₂ ] and tris (1-chloro-1-methylethyl) benzene [(ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ]. [Note that 1-chloro-1-methylethylbenzene is also called α-chloroisopropylbenzene, 2-chloro-2-propylbenzene, or cumyl chloride. Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride. Tris (1-chloro-1-methylethyl) benzene is also referred to as tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene or tricumyl chloride. ]
In the polymerization reaction, a Lewis acid catalyst can coexist. Such a Lewis acid catalyst is not particularly limited as long as it can be used for cationic polymerization. For example, TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₄ , SbCl ₅ , SbF _{5 are used.} , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ , FeBr ₃ , ZnCl ₂ , ZnBr ₂ , AlCl ₃ , AlBr _{3 and} other metal halides; or TiCl ₃ (OiPr), TiCl ₂ (OiPr) ₂ , TiCl ( metal compound _{OiPr) 3} or the like on the metal having both halogen and alkoxide _{groups; Et 2 AlCl, EtAlCl 2,} Me 2 AlCl, and organic metal halides such as MeAlCl ₂ and the like.

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 the Lewis acid catalyst used is not particularly limited, and can be arbitrarily set in view of the polymerization characteristics of the monomer used, the polymerization concentration, the desired polymerization time, the exothermic behavior in the system, and the like. Preferably, it is used in the range of 0.1 to 200 times mol, more preferably in the range of 0.2 to 100 times mol, with respect to the compound represented by the above formula (I).

  In the above polymerization reaction, an electron donor component can be allowed to coexist if necessary. The electron donor component is considered to have an effect of stabilizing the carbon cation at the growth end during cation polymerization, and a polymer having a narrow molecular weight distribution and a controlled structure can be obtained. The electron donor component 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.

  As the electron donor component, the number of donors defined as a parameter representing the strength as an electron donor (electron donor) of various compounds is usually 15 to 60. 6-di-t-butylpyridine, 2-t-butylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2-methylpyridine, pyridine, diethylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, hexamethyl phosphate triamide, titanium ( III) Methoxide, Titanium (IV) Methoxy Titanium alkoxides such as titanium (IV) isopropoxide and titanium (IV) butoxide; aluminum alkoxides such as aluminum triethoxide and aluminum tributoxide can be used, and 2,6-di-t-butyl is preferable. Pyridine, 2,6-dimethylpyridine, 2-methylpyridine, pyridine, diethylamine, trimethylamine, triethylamine, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, titanium (IV) isopropoxide, titanium (IV ) Butoxide and the like. The number of donors of the above various substances is described in “Donor and Acceptor”, by Goodman, Otsuki, Okada, and Academic Publishing Center (1983). Among these, 2-methylpyridine, which has a remarkable effect of addition, and titanium (IV) isopropoxide that makes the reaction system uniform are particularly preferable.

  The electron donor component is usually used in an amount of 0.01 to 100 times mol and preferably 0.1 to 50 times mol of the polymerization initiator.

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

  When producing the isobutylene block copolymer having an allyl group at the end of the present invention, the addition method and order of addition of Lewis acid, polymerization initiator, electron donor component, monomer component, etc. are particularly limited. However, as a preferred method, for example, (1) a monomer component (a) containing isobutylene as a main component in the presence of an initiator system composed of a polymerization initiator and a Lewis acid and an electron donor component is used. A step of polymerizing, (2) a step of polymerizing by adding the aromatic vinyl monomer component (b) to the reaction system, and (3) an allylsilane compound being added at the stage where the polymerization is substantially completed. A production method comprising a step of introducing an allyl group is recommended in terms of simple operation.

  In the production method, the aromatic vinyl-based monomer component (b) is added after the polymerization of the monomer component (a) containing isobutylene as a main component is substantially completed in the step (1). However, when a monomer having a cationic polymerization activity lower than that of isobutylene is used as the aromatic vinyl-based monomer component (b), in step (1), a single monomer having isobutylene as a main component is used. Even if the aromatic vinyl monomer component (b) is added before the polymerization of the monomer component (a) is substantially completed, the block copolymer can be synthesized. In the case where a monomer having a cationic polymerization activity substantially equal to that of isobutylene and copolymerizable is used as the aromatic vinyl monomer component (b), isobutylene is used in the step (1). If the aromatic vinyl-based monomer component (b) is added before the polymerization of the monomer component (a) containing as a main component substantially ends, a polymer having a random property in a part of the molecular chain It is possible to produce a block copolymer having a block.

In the reaction for introducing an allyl group, each component is mixed under cooling, for example, at a temperature of −100 ° C. or more and less than 0 ° C., similarly to the conditions for polymerizing each monomer. From the viewpoint of energy cost and stability of the polymerization reaction, a more preferable temperature range is -80 ° C to -30 ° C.
The reaction for introducing an allyl group can be carried out in an organic solvent as necessary in the same manner as the conditions for polymerizing each monomer, and the above-mentioned solvents are recommended as candidates for the recommended solvent. .

  The platinum vinylsiloxane complex contained in the calcium carbonate carrying the platinum vinylsiloxane complex (b) of the present invention has a zero-valent platinum atom as a central metal, and has the following general formula (2) and / or as a ligand. It refers to a metal complex having the vinylsiloxane compound represented by (3) as a ligand.

(In the formula, R ³ and R ⁴ each represent a monovalent hydrocarbon group having 1 to 10 carbon atoms. Moreover, a plurality of R ³ and R ⁴ may be the same or different. May be good.)
For example, platinum complexes having 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as a ligand are also known as Karstedt catalysts. It is a compound and is known to have the following structural formula (4).

(In the formula, the Me group represents a methyl group.)
The platinum complex having the vinylsiloxane compound as a ligand is preferable because it has a better balance of availability, catalytic ability, chemical and thermal stability than chloroplatinic acid H ₂ PtCl ₆ .

  The calcium carbonate contained in the calcium carbonate carrying the platinum vinyl siloxane complex of (b) of the present invention is not particularly limited, but weathered shells, weathered microbial shells, coarse crystal limestone, weathered calcite, natural marble products As a raw material, calcium carbonate obtained by a dry pulverization method or wet pulverization method, or calcium carbonate synthesized by a reaction generally known as a carbon dioxide reaction method or a soluble salt reaction method can be preferably used.

The particle shape of the calcium carbonate used in the present invention is not particularly limited, and calcium carbonate having any particle shape such as a cubic shape, a bell shape, a columnar shape, or a spherical shape can be used.
As a value of the BET specific surface area (m < ² > / g) of the calcium carbonate used by this invention, the thing of 1.0-200 is preferable and the thing of 2.0-100 is more preferable.

  A BET specific surface area of less than 1.0 is not preferable because the viscosity of the composition increases depending on the amount added, and may be difficult to handle during kneading and molding. In addition, those having a BET specific surface area of greater than 200 are generally difficult to produce, which is not preferable in terms of economic disadvantage.

  As an average primary particle diameter (micrometer) of the calcium carbonate used by this invention, 0.01-5.0 are preferable and it is preferable that it is 0.02-2.0. When the average particle size is smaller than 0.01, the primary particles are likely to aggregate and the dispersibility in the thermoplastic elastomer composition of the present invention may be inferior. When the average particle diameter is larger than 5.0, the specific surface area becomes small, the catalyst cannot be supported efficiently, and the catalyst efficiency may be low.

  The presence or absence of the surface treatment of the calcium carbonate used in the present invention is not particularly limited. For example, calcium carbonate having a small particle diameter generally tends to aggregate, and is dispersible in the thermoplastic elastomer composition of the present invention. Since it may be inferior, the catalytic activity of the hydrosilylation reaction may not be sufficient. In that case, a saturated or unsaturated fatty acid and its fatty acid ester, rosin acid, rosin acid ester, abietic acid, dehydroabietic acid, dehydroabietic acid ester and other resin acids and / or resin acid esters, vinyl silane, amino silane, You may process with surface treatment agents, such as high molecular compounds, such as silane coupling agents, such as a mercaptosilane, polyethylene, a polypropylene, and a urethane resin.

  On the other hand, when calcium carbonate having a relatively large particle size is used, the above-mentioned aggregation of calcium carbonate may not be a practical problem. That is, when a composition that is satisfactory in terms of reaction rate and catalytic activity in the hydrosilylation reaction of the present invention is obtained, the treatment on the calcium carbonate surface is not necessarily required.

The calcium carbonate catalyst carrying the platinum vinyl siloxane complex (b) of the present invention is a product name such as “Pt-VTS / CaCO ₃ ” or “Pt-CTS / CaCO ₃ ”. E. Those available from Chemcat can be suitably used.

These platinum catalysts may be used independently and may use 2 or more types together.
Although there is no restriction | limiting in particular as catalyst amount, (a) It is used in the range whose mole number of a platinum atom is 10 ^{<-1 > -10} <^-10> mol with respect to 1 mol of alkenyl groups of the isobutylene polymer which has an allyl group at the terminal. More preferably, it is the range of 10 ^<-2 > ^{-10 < -8>} mol. If it is less than 10 ⁻¹⁰ mol, curing may not proceed sufficiently, which is not preferable. Moreover, since it is economically disadvantageous to use ^10-1 mol or more, it is not preferable.

  Although there is no restriction | limiting in particular as (c) hydrogen siloxane type compound (Si-H compound) of this invention, Hydrosilyl group containing polysiloxane is preferable and 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. More preferred are polysiloxanes having 3 or more hydrosilyl groups and 20 to 100 siloxane units. When the content of hydrosilyl groups is less than 3, sufficient network growth due to crosslinking cannot be achieved and optimal rubber elasticity cannot be obtained. When there are 501 or more siloxane units, the viscosity of polysiloxane is high and alkenyl groups are present. This is not preferable because the styrene-isobutylene block copolymer is not well dispersed and unevenness occurs in the crosslinking reaction. Further, it is preferable that the number of polysiloxane units is 100 or less because hydrosilyl group-containing polysiloxane necessary for hydrosilylation can be reduced. The polysiloxane unit mentioned here refers to the following general formulas (5), (6) and (7).
[Si (R ⁵ ) ₂ O] (5)
[Si (H) (R ⁶ ) O] (6)
[Si (R ² ) (R ⁷ ) O] (7)
As the hydrosilyl group-containing polysiloxane, a linear polysiloxane represented by the general formula (8) or (9):
_{^{R 1 3 SiO- [Si (R}} 5) 2 O] a - [Si (H) (R 6) O] b - [Si (R 6) (R 7) O] c -SiR 5 3 (8)
_{^{HR 1 2 SiO- [Si (R}} 5) 2 O] a - [Si (H) (R 6) O] b - [Si (R 6) (R 7) O] c -SiR 5 2 H (9)
(In the formula, R ⁵ and R ⁶ represent an alkyl group having 1 to ⁶ carbon atoms or a phenyl group, and R ⁷ 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 (10);

(In the formula, R ⁸ and R ⁹ are each an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms or an aralkyl group. E is 3 ≦ b, d, e , F represents an integer satisfying d + e + f ≦ 500.) A compound such as

  Furthermore, among the compounds having the above hydrosilyl group (Si—H group), those represented by the following general formula (11) are particularly preferred 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 ¹¹ represents a hydrogen atom or a methyl group, and R ¹² is a carbon atom having 1 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.)
Examples of such compounds include trade names “KF-99” and “KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd., trade names “TSF484” manufactured by Momentive, and “SH1107” manufactured by Toray Dow Corning. It is done.

  Among these, chain polysiloxane is preferable from the viewpoint of availability, and examples thereof include methyl hydrogen siloxane (trade name: TSF484) manufactured by Momentive.

  The styrene-isobutylene block copolymer having an alkenyl group and the hydrosilyl group-containing polysiloxane can be mixed in an arbitrary ratio. From the viewpoint of curability, the number of moles of the alkenyl group and the hydrosilyl group-containing polysiloxane It is preferable that the ratio of the number of moles of the Si—H bond (alkenyl group / Si—H group) is in the range of 0.01 to 5. Furthermore, it is preferable that it is 0.02-2.5. When the ratio of the number of moles is 5 or more, there is a case where a composition having satisfactory physical properties in terms of stickiness and compression set is insufficient due to insufficient crosslinking. On the other hand, if it is less than 0.01, a hydrosilyl group capable of reacting in the composition remains after curing, cracks and voids are generated, and a uniform and strong cured product may not be obtained. It is not preferable.

  There is no restriction | limiting in particular as (d) thermoplastic resin of this invention, General purpose thermoplastic resin, general purpose thermoplastic elastomer, general purpose engineering plastic, special engineering plastic, etc. can be used conveniently.

  Examples of general-purpose thermoplastic resins include polyolefin resins, aromatic vinyl compound resins, polyvinyl chloride resins, polyacrylic resins, and polyether resins.

  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.

  General-purpose thermoplastic elastomers include aromatic vinyl compound-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and ionomer-based heat. Examples thereof include a plastic elastomer and a liquid crystalline thermoplastic elastomer. Among these, aromatic vinyl compound-based thermoplastic elastomers can be suitably used in terms of availability and physical properties.

  Examples of the aromatic vinyl compound thermoplastic elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylenebutylene-styrene block obtained by hydrogenating them. Examples thereof include a copolymer (SEBS), a styrene-ethylenepropylene-styrene block copolymer (SEPS), and a styrene-isobutylene-styrene block copolymer (SIBS).

General-purpose engineering plastics include polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, polyphenylene ether resins, polymethylpentene, ultrahigh molecular weight polyethylene, and the like.
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.

  Special engineering plastics include polysulfone resins, polysulfide resins, polyimide resins, polyamideimide resins, polyetherimide resins, fluorine resins, thermoplastic polyurethane resins, polyethersulfone resins, polyetherketone resins. And thermotropic liquid crystal resin.

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

  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.

  Among these, aromatic vinyl thermoplastic elastomers and olefin resins are preferable from the viewpoint of compatibility, and styrene-isobutylene-styrene block copolymers, polypropylene, and polyethylene are particularly preferable.

  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.

  If it is a range which does not impair the effect of this invention, the softening agent can be further added to the thermoplastic elastomer composition of this invention in order to improve a moldability and a softness | 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. Dibasic acid dialkyl esters such as dibutyl phthalate, dioctyl phthalate, and dibutyl adipate are also used.

  Among these, polybutene oil is preferable in terms of compatibility and gas barrier properties. From the viewpoint of hygiene, it is preferable to use polybutene having a number average molecular weight of 20000 or more because the extractability is extremely low. 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 softener is preferably 1 to 300 parts by weight with respect to 100 parts by weight of (a) an isobutylene polymer having an allyl group at the end. If the blending amount exceeds 300 parts by weight, stickiness or mechanical strength tends to decrease.

  As long as the effects of the present invention are not impaired, a lyotropic liquid crystal resin, a liquid resin, a thermosetting resin, a crosslinked rubber, and the like may be further blended. 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.

  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.

  Furthermore, as long as the effects of the present invention are not impaired, a filler and a reinforcing material can be blended in the thermoplastic elastomer composition of 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, diatomaceous earth, pumice powder, slate powder, dry or wet silica, amorphous silica, wollastonite, synthetic or natural zeolite, talc , Barium sulfate, lithopone, 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, water Flour-like inorganic fillers such as aluminum oxide, various metal powders, wood chips, glass powder, ceramic powder, carbon black, granular or powdered solid fillers such as granular or powdered polymers, and other various natural or artificial shorts Examples thereof include fibers and long fibers. These fillers and reinforcing materials may be treated with a silane compound for the purpose of enhancing dispersibility, improving compatibility with other compounds, or chemically forming bonds. 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.

  These fillers may be anything as long as they do not impair the effects of the present invention, and two or more kinds can be used in combination. For example, in applications where transparency is not required, the inclusion of an inorganic filler may improve the blocking property and may be advantageous in terms of cost, and may provide concealment. Moreover, when metal hydroxides, such as magnesium hydroxide, are used as an inorganic filler, the outstanding flame retardance may be provided by using a flame retardant together.

  The blending amount of the filler is 0 to 500 parts by weight with respect to 100 parts by weight of the isobutylene polymer having (a) an allyl group at the terminal. If the amount exceeds 500 parts by weight, the resulting thermoplastic elastomer composition may be significantly deteriorated in physical properties, which is not preferable. Preferably it is 0-100 weight part.

  In addition, as long as the effect of the present invention is not impaired, the thermoplastic elastomer composition in the present invention includes, as necessary, hindered phenol-based, phosphate ester-based, amine-based, sulfur-based antioxidants, And / or ultraviolet absorbers such as benzothiazole, benzotriazole, and benzophenone, and a light stabilizer can be blended.

  The recommended blending amount of the antioxidant, the ultraviolet absorber and the light stabilizer is (0001) 0.000001 to 50 parts by weight with respect to 100 parts by weight of the isobutylene polymer having an allyl group at the end, Preferably it is 0.00001-10 weight part.

  Furthermore, a plasticizer can be added to the thermoplastic elastomer composition in the present invention as long as the effects of the present invention are not impaired. 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 tackifying resin can be added to the thermoplastic elastomer composition in the present invention as long as the effects of the present invention are not impaired. Examples of tackifying resins include alicyclic petroleum resins and their hydrides, aliphatic petroleum resins, hydrides of aromatic petroleum resins, polyterpene resins, and more specifically, rosin, gum rosin, and tall. Rosin resin such as oil rosin, hydrogenated rosin, maleated rosin; terpene phenol resin; terpene resin mainly composed of α-pinene, β-pinene, limonene, etc .; aromatic hydrocarbon-modified terpene resin; aliphatic, fat Examples thereof include cyclic and aromatic petroleum resins; coumarone and indene resins; styrene resins; phenolic resins such as alkylphenol resins and rosin-modified phenolic resins; xylene resins and the like. These may be used singly or two or more may be appropriately selected so as to obtain desired tack, adhesive strength and holding strength.

  The compounding quantity of the said tackifier is 1-500 weight part with respect to 100 weight part of (a) isobutylene polymer which has an allyl group at the terminal. If it is out of the above range, it is difficult to obtain a pressure-sensitive adhesive composition having balanced physical properties. Preferably, it is 30 to 300 parts by weight.

  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 thermoplastic elastomer composition in the present invention can be produced by the method exemplified 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 a Banbury mixer to (a) run an isobutylene polymer having an allyl group at the end. A cross-linking method and all components other than the cross-linking 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 cylinder of the extruder to further melt-knead (a) Examples thereof include a method of dynamically crosslinking an isobutylene polymer having an allyl group at the terminal. The (a) isobutylene polymer having an allyl group at the end of the present invention is a solid at room temperature and can be handled in the form of pellets, crumbs, powders, etc. Can be used.

  In carrying out the melt-kneading, a temperature range of 140 to 240 ° C is preferable, and a temperature range of 150 to 230 ° C is more preferable. When the melt kneading temperature is lower than 140 ° C., the thermoplastic resin component does not melt and tends to be insufficiently mixed. When the temperature is higher than 240 ° C., (a) an isobutylene polymer having an allyl group at the terminal is obtained. Thermal decomposition tends to occur.

  The molded product and the modifier of the present invention are rich in gas barrier properties and flexibility, and are excellent in molding processability, rubber-like properties, mechanical strength, and compression set properties. Therefore, it can be used for the following purposes.

  (1) Modifiers: Resin modifiers (impact modifiers for thermoplastic resins such as impact modifiers, damping modifiers, gas barrier modifiers, softeners, etc.) Texture agent, stress reducing agent, etc.), asphalt modifier (road asphalt modifier, waterproof sheet asphalt modifier, bridge floor slab waterproof material), tire modifier (tire wet grip property improver) ), Rubber modifier.

  (2) Adhesive or pressure-sensitive adhesive: hot-melt adhesive, water-based adhesive, solvent-based adhesive, pressure-sensitive adhesive.

  (3) Viscosity modifier: a viscosity modifier added to oil, lubricating oil, and the like.

  (4) Coating agent: Base resin and sealant used for paints.

  (5) Materials used for PVC replacement: Wire 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 hoods, agricultural films (for house cultivation), erasers, commercial aprons (tarpaulins), building interior materials such as floor and ceiling materials, raincoats, umbrellas, shopping bags, skin materials such as chairs and sofas , Skin materials such as belts and baskets, garden hoses, gaskets (packings) for refrigerators, flexible hoses for washing machines and vacuum cleaners, automotive interior materials.

  (6) Damping material, damping material, cushioning material: Damping material, especially damping material, damping material, cushioning material laminated together with aluminum and steel plate (building use, automotive use, floor damping use, flooring Use, play equipment use, precision equipment use, electronic equipment use), shoe soles, grips for stationery / toy supplies, daily goods / carpenter's grips, golf clubs / bat grips and heartwood, tennis rackets / table tennis Rubber and grips such as rackets.

  (7) Soundproofing material, sound absorbing material: automotive interior and exterior materials, automotive ceiling materials, railcar materials, piping materials.

  (8) Sealing material: Gasket, architectural gasket, plug, glass sealing material for laminated glass and multilayer glass, packaging material, sheet, multilayer sheet, container, multilayer container and other gas barrier materials, civil engineering sheet, waterproofing Sheets, packaging transport materials, sealants, medical plugs, syringe gaskets.

  (9) Tube: Medical tube, ink tube, food tube, tire tube.

  (10) Foam: Foaming agent carrier in bead foaming, slow pressure foaming, foam by extrusion foaming (pipe coating material, synthetic wood, wood powder foam, etc.), chemical foaming and physical foaming.

  (11) Others: Apparel, flame retardant applications, closures, caps, bags, gaskets, hoses, shoes, exercise equipment, foam fireproof sheets, airbag covers, bumpers, interior parts (instruments such as instrument panels and shift knobs) Materials), weather strips, roof moldings, moldings under the doors, 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, food containers such as polystyrene-based mesh foam, frozen dessert cups, transparent beverage cups, IC trays, CD-ROM chassis, wheel caps, elastic yarns, nonwoven fabrics, wire harnesses, back sheets of disposable diapers, two-color molding compounds Wood, underwater goggles, computer mouse, cushion Stopper.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

(Molecular weight measurement)
In the following examples, “number average molecular weight”, “weight average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” are calculated by a standard polystyrene conversion method using size permeation chromatography (SEC). did. As a measuring device, a 510 type GPC system manufactured by Waters was used, and measurement was performed by injecting a sample solution having a polymer concentration of 4 mg / ml into GPC using chloroform as a mobile phase and a column temperature of 35 ° C. did. Polystyrene was used as a standard sample.

(Number of allyl groups introduced)
From the integral ratio of isobutylene group and integral ratio of allyl group in the proton NMR spectrum (measurement apparatus: AVANCE series manufactured by Bruker, 400 MHz nuclear magnetic resonance apparatus, measurement solvent: chloroform) of the obtained polymer, one molecule of polymer The number of allyl groups introduced per unit was determined.

(Break strength: Tb)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into No. 7 with a dumbbell was prepared and used for measurement. The tensile speed was 200 mm / min.

(Elongation at break: Eb)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into No. 7 with a dumbbell was prepared and used for measurement. The tensile speed was 200 mm / min.

(hardness)
In accordance with JIS K6253, the hardness (hereinafter abbreviated as JIS-A hardness) was measured with a spring type A durometer. For the hardness, a value immediately after measurement was adopted. The test piece used was a 12.0 mm thick press sheet.
(Compression set)
In accordance with JIS K 6262, a 12.0 mm thick press sheet was used as a test piece. The measurement was carried out under the conditions of 70 ° C. × 22 hours and 25% deformation.

(Production example)
After replacing the inside of the 5 L separable flask with nitrogen, 2353 mL of butyl chloride (dried with molecular sieves) and 262 mL of hexane (dried with molecular sieves) were added using a syringe, and the polymerization vessel was -75 ° C. After being immersed in a dry ice / acetone bath and cooled, a Teflon (registered trademark) feeding tube was connected to a pressure-resistant glass liquefied collection tube with a three-way cock containing 855 mL (10.5 mol) of isobutylene monomer, The isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. Next, 3.51 g (15.2 mmol) of p-dicumyl chloride and 0.849 g (9.11 mmol) of α-picoline were added. Next, 7.04 mL (64.5 mmol) of titanium tetrachloride was added to initiate polymerization. After stirring at the same temperature for 60 minutes from the start of polymerization, the consumption rate of isobutylene was determined by gas chromatography, and it was confirmed that it reached 99%. Thereafter, 215 ml (2.02 mmol) of styrene monomer was added. Thereafter, the consumption of styrene monomer was measured over time by gas chromatography, and when it was confirmed that 85% of the styrene monomer was consumed, diallyldimethylsilane 8.3 mL (45.6 mmol), 14.2 mL (129 mmol) of titanium tetrachloride was added. Thereafter, stirring was continued for 3 hours at the same temperature. Next, the entire reaction solution was poured into 5 L of pure water heated to 60 degrees, and the polymerization was stopped by vigorously stirring for 30 minutes using a mechanical stirrer. Next, washing with 5 L of pure water was repeated three times. Then, 720 g of a styrene-isobutylene-styrene block copolymer (P-1) having an allyl group at the terminal was obtained by distilling off volatile components such as a solvent under heating and drying.

  The number average molecular weight of the obtained polymer was 68,100, and the molecular weight distribution was 1.39. Furthermore, the number of allyl groups introduced at the terminal was 1.8.

Example 1
Next, a dynamic cross-linking composition was prepared using the styrene-isobutylene-styrene block copolymer having an allyl group at the terminal obtained in Production Example, and the physical properties were evaluated. That is, in accordance with the number of parts by weight shown in Table 1, styrene-isobutylene having an allyl group at the end when 5.3 g of polypropylene (manufactured by Prime Polymer Co., Ltd., grade name J-215W) is kneaded at 180 degrees and 100 rpm. -21 g of styrene block copolymer (P-1) and 0.11 g of antioxidant (manufactured by Ciba Specialty Chemicals, grade name Irganox 1010) were added, and kneading was continued at the same temperature. Next, 12.6 g of polybutene oil (manufactured by Idemitsu Kosan Co., Ltd., grade name 100R) was slowly added. Next, 0.315 g of a crosslinking agent (manufactured by Momentive Performance Materials, grade name TSF484) and 0.022 g of platinum catalyst supported on calcium carbonate (manufactured by NE Chemcat, grade name “MX CAT-VTS”, Platinum content: 0.7% by weight, calcium carbonate used in the present catalyst has a BET specific surface area of 4.0-7.0 m ² / g, a primary particle diameter of 1,500 nm (major axis), a surface Using a screw feeder in this order was carefully added so that there was no adhesion to the surroundings from the vent port of the plastmill. Stirring was continued at the same temperature and rotation speed, and stirring was continued until the indicated torque of Laboplast Mill (manufactured by Toyo Seiki Seisakusho) reached the maximum value. After confirming that the indicated torque showed the maximum value, defoaming was performed at 230 degrees / vacuum in the next 1 minute. Thereafter, the resin composition was dispensed. Next, the obtained resin composition was pressed at 200 degrees to prepare a 2 mm thick sheet-like test piece and a 12 mm thick cylindrical test piece. A dumbbell-shaped test piece was punched from the obtained 2 mm-thick sheet-shaped test piece, and the tensile physical properties of the dynamically crosslinked composition were measured using this. Furthermore, compression set was evaluated using a 12 mm thick cylindrical test piece. The results are shown in Table 1.

(Examples 2 to 6)
In Examples 2 and 3, the platinum catalyst “MX CAT-VTS (manufactured by NE Chemcat Corp., platinum content: 0.7 wt%)” supported on calcium carbonate is in parts by weight as shown in Table 1. A composition was prepared in the same manner as in Example 1 except that it was added as described above, and the physical properties of the obtained composition were measured. In Examples 4 to 6, as a platinum catalyst supported on calcium carbonate, “MX CAT-CTS (manufactured by NE Chemcat, platinum content: 0.68% by weight, calcium carbonate used in the present catalyst” In Table 1, the BET specific surface area is 4.0-7.0 m ² / g, the primary particle diameter is 1,500 nm (long diameter), and the surface treatment with a surface treatment agent is not used). A composition was prepared in the same manner as in Example 1 except that it was added according to the stated weight parts, and the physical properties of the obtained composition were measured.

(Reference example)
In the reference example, “Pt-VTSC-3.0X (manufactured by Umicore, platinum content: 3.0% by weight)”, which is a xylene solution, was added as a platinum catalyst so as to have the parts by weight shown in Table 1. At this time, in order to accurately add the platinum catalyst to the composition being kneaded, the operator carefully added it using a micropipette so as not to adhere to the inlet and the vicinity thereof. Further, a composition was prepared in the same manner as in Example 1, and the physical properties of the obtained composition were measured.

(Comparative Example 1)
In Comparative Example 1, as a platinum catalyst, “Pt-VTSC-3.0X (manufactured by Umicore, platinum content: 3.0 wt%)” which is a xylene solution was added so as to have the parts by weight shown in Table 1. A composition was prepared in the same manner as in Example 1 except that the physical properties of the obtained composition were measured.

(Comparative Example 2)
In Comparative Example 2, the platinum catalyst “PL-CAT 100M (manufactured by NE Chemcat, platinum content: 0.78 wt%)” supported on silica as the platinum catalyst was expressed in parts by weight as shown in Table 1. A composition was prepared in the same manner as in Example 1 except that it was added, and the physical properties of the obtained composition were measured.

  By comparing the results of Examples 1 to 6 and Reference Example, according to the composition of the present invention, the same physical properties as those of the composition using a conventionally used platinum vinylsiloxane complex xylene solution as a catalyst are shown. It can be seen that a composition is obtained.

  Further, as shown in Comparative Example 1, when “Pt-VTSC-3.0X (manufactured by Umicore)” in the form of a solution is used, various physical properties of the obtained composition are lower than those of the reference example. There are occasions. This is because the amount of the catalyst added is very small, so that it adheres to the edge of the catalyst inlet or is not kneaded well due to the difference in viscosity from the composition even if the whole amount is correctly charged, making the dynamic cross-linking reaction efficient. This is thought to be due to the fact that the catalyst could not be catalytically produced. Compared with the reference example, in Examples 1 to 6, it is understood that the desired physical properties can be obtained by being efficiently kneaded by being supported on calcium carbonate.

  On the other hand, by comparing the results of Examples 1 to 6 and Comparative Example 2, according to the composition of the present invention, the compression set, compared with the case where the platinum vinylsiloxane complex supported on silica is used as a catalyst, It can be seen that a composition having excellent physical properties such as hardness and tensile strength can be obtained. Although the cause of this result is not necessarily clear, the silica used as the carrier used in Comparative Example 2 has some reaction with the platinum complex and / or the crosslinking agent (hydrogen silicone). This is thought to have occurred as a result of the inhibition of the crosslinking reaction. That is, when a dynamic cross-linking composition is obtained using a platinum catalyst using silica as a carrier, physical properties that are considered to be due to inhibition of the cross-linking reaction are observed. Furthermore, while the maximum torque at the time of kneading in Examples 1 to 6 was 25 to 26 N · m, when a platinum vinylsiloxane complex supported on silica was used as a catalyst, a high value of 29 N · m was shown. It was. This indicates that the viscosity of the composition is increased, and it can be seen that the composition is difficult to produce by adding silica.

  Therefore, according to the composition of this invention, it turns out that the thermoplastic elastomer composition which is excellent in the physical property of a composition, is easy to handle a raw material, is easy to manufacture, and also does not have unintentional coloring.

Claims (4)

(B) a platinum vinylsiloxane complex supported on calcium carbonate, (c) a hydrogensiloxane compound (Si-H compound), and (d) a thermoplastic. A thermoplastic elastomer composition which is dynamically crosslinked in the presence of a resin. (B) The vinylsiloxane ligand in the platinum vinylsiloxane complex supported on calcium carbonate is 1,3-divinyl-1,1,3,3-tetraalkyldisiloxane or 2,4,6,8-tetra The thermoplastic elastomer composition according to claim 1, which is alkyl-2,4,6,8-tetravinylcyclotetrasiloxane. (B) The vinylsiloxane ligand in the platinum vinylsiloxane complex supported on calcium carbonate is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane or 2,4,6,8-tetra The thermoplastic elastomer composition according to claim 1 or 2, which is methyl-2,4,6,8-tetravinylcyclotetrasiloxane. The thermoplastic resin according to any one of claims 1 to 3, wherein the isobutylene polymer having an allyl group at the terminal (a) is an isobutylene block copolymer having an allyl group at the terminal. Elastomer composition.