WO2003097741A1 - Styrene elastomer composition - Google Patents

Abstract

A styrene elastomer composition comprising a styrene elastomer and a lamellar inorganic compound sufficiently finely dispersed therein. The gas-barrier properties of the styrene elastomer has been improved, and the composition has satisfactory mechanical properties. The styrene elastomer composition comprises (a) a styrene elastomer, (b) a lamellar inorganic compound to which an organic nature has been imparted with organic cations, and (c) a polar polymer having compatibility with the styrene elastomer (a) and having a polar functional group in the molecule, wherein the lamellar inorganic compound (b) to which an organic nature has been imparted has a sheet-to-sheet distance of 15 Å or longer.

Description

 Specification

 Styrene-based elastomer composition

 Technical field

 The present invention relates to a styrene-based elastomer composition containing a styrene-based elastomer and a layered inorganic conjugate.

 Background art

 In recent years, as the range of use of elastomers has further expanded, higher-performance elastomers have been required. Above all, there is a high demand for high performance with respect to the target characteristics and gas barrier properties.

 For example, a number of techniques have been reported for blending inorganic fillers with elastomers for the purpose of improving martial properties.

 1) Japanese Patent Application Laid-Open No. 8-3333114 discloses a method of improving the mechanical properties of an organic polymer material, in which a clay mineral organically formed by ion bonding of an organic onion has a polar group. Clay composites dispersed in guest molecules have been disclosed. 2) Japanese Patent Application Laid-Open No. H11-922677 discloses a process for obtaining a modified polymer having a functional group introduced by modifying a polymer in order to improve the mechanical properties of an organic polymer material. A process of kneading the modified polymer and the organic resin to form a composite of the two, which discloses a method for producing a resin composite material.

 3) Japanese Unexamined Patent Application Publication No. 2000-86882 discloses a method of providing a resin composite material having excellent heat resistance and excellent elasticity even at room temperature, from a plurality of types of segments. There is disclosed a resin composite material characterized in that organoid clay is dispersed in at least one kind of segment of a block copolymer type thermoplastic elastomer.

 4) Japanese Patent Application Laid-Open No. Hei 11-92595 discloses two or more types of resin composites that can be easily compounded and that can produce resin composites having a wide range of application. There is disclosed a resin composite material comprising a polymer and an organized clay, wherein at least one of the two or more polymers has a functional group.

5) JP-A-2002-37940 discloses crystalline polypropylene containing a predetermined amount of an elastomer as a paraxylene-soluble component at 23 ° C, and a carbohydrate containing an ethylenically unsaturated bond. A polypropylene resin composition comprising a crystalline polypropylene graft-modified with an acid, an anhydride or a derivative thereof, and an organized clay is disclosed.

 Among elastomers, styrene-based elastomers have excellent flexibility, cold resistance, moisture absorption resistance, etc., and can be easily formed into rubber molded articles. Rather, they have been put into practical use in various fields, such as automobiles, electrical products, construction, civil engineering, and other industrial products, medical and sports equipment, and various container parts (for example, cap liners).

 The following are known as medical uses of styrene-based elastomers.

 1) Japanese Patent Application Laid-Open No. 2001-137337 discloses that a thermoplastic elastomer such as a styrene elastomer is used for an elastic sliding portion of a sliding member of a piston for a syringe.

 2) Japanese Utility Model Application No. 5-533609 is a sealing plug for blood collection tubes using a resin obtained by blending a predetermined amount of naphthenic oil with a thermoplastic elastomer resin such as polystyrene-polyisoprene-polystyrene. Is disclosed.

 3) Japanese Patent Application Laid-Open No. 10-201742 discloses that a soft synthetic resin such as styrene-based elastomer is used for a needle sticking portion and a sealing portion of a vacuum blood collection tube.

 4) Japanese Patent Application Laid-Open No. 5-2112104 discloses thermoplastic and medical sealable articles for medical and medical use, such as rubber stoppers for pharmaceuticals, gaskets for syringes, rubber stoppers for decompression blood collection tubes, and gaskets for syringes that also serve as chemical liquid filling containers. It discloses that a block copolymer of an aromatic vinyl compound and isobutylene (eg, styrene-isobutylene-styrene block copolymer) is used as a substitute material for vulcanized rubber for production.

 The following are known as applications of styrenic elastomers to container parts:

1) Japanese Patent Application Laid-Open No. H11-3497953 discloses a composition for a cap liner material comprising an ethylene-α-olefin copolymer, a branched low-density polyethylene and a thermoplastic elastomer, Examples of thermoplastic elastomers include styrene copolymer elastomers such as styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, and hydrogenated styrene-ethylene-propylene copolymer rubber. 2) As a composition for a cap liner material, JP-A-11-130910 discloses a composition comprising a polypropylene resin, a hydrogenated styrene-isoprene copolymer rubber and liquid paraffin. No. 11-157568 discloses a composition comprising a polypropylene-based resin, a linear low-density polyethylene-based resin, a hydrogenated styrene-conjugated gemrock copolymer rubber and liquid paraffin.

 3) JP-A-2000-351880 and JP-A-2000-355352 disclose, as compositions for molded articles such as cap liners, compositions of thermoplastic elastomer and saponified ethylene-butyl acetate copolymer, A thermoplastic elastomer, a saponified ethylene-biel acetate copolymer and / or a polyamide resin composition are disclosed, and both documents describe styrene-butadiene block copolymer and styrene-one as thermoplastic elastomers. Styrene-based elastomers such as ethylene-butylene block copolymer, styrene-ethylene-propylene block copolymer, and styrene-isoprene block copolymer are exemplified.

4) Japanese Patent Application Laid-Open No. 2000-281117 discloses, as a material for a cap liner, a hydrogenated product of a styrene-conjugated gemrock copolymer, a softener for rubber, and a composition comprising Z or liquid paraffin and a polyethylene resin. As the styrene-conjugated gen-block copolymer, hydrogenated styrene-isoprene-styrene copolymer and hydrogenated styrene- (isoprene / butadiene) -styrene block copolymer are exemplified.

 Recently, in order to improve the mechanical properties, chemical resistance, and rubber elasticity of styrenic elastomers, swellable silicates are cleaved in a dispersion medium and mixed with an amino or silane compound. A styrene-based elastomer containing the layered inorganic conjugate prepared as described above has been proposed.

For example, JP-A-2000-129058 and JP-A-2000-159960 disclose a styrene containing a layered inorganic compound by mixing and polymerizing a monomer constituting a styrene-based elastomer and a layered inorganic compound. It is described to produce an elastomer. Another method for producing a styrene-based elastomer containing a layered inorganic compound includes a layered inorganic compound and a styrene-based elastomer. Is also described in an organic solvent.

 The operation of mixing the layered inorganic compound and the monomer while polymerizing the monomer is complicated. In addition, the living anion heavy-coordinated polymerization, which is generally used as a method for producing a styrene-based elastomer, is markedly inhibited in the presence of a compound having a polar functional group or water. It is known that a method of polymerizing a monomer in the presence of a layered inorganic compound having a high polarity and easily containing water does not allow a sufficient polymerization reaction to proceed.

 In addition, the method of mixing the layered inorganic compound and the styrene-based elastomer in an organic solvent is a method of mixing the layered inorganic compound and the styrene-based elastomer in an organic solvent capable of dissolving the styrene-based elastomer because the layered inorganic conjugate is inherently hydrophilic. The inorganic agglomerates are likely to undergo secondary aggregation. As a result, it is difficult to sufficiently finely disperse the layered inorganic compound in the styrene-based elastomer. As described above, it is difficult to sufficiently finely disperse the layered inorganic compound in the styrene-based elastomer even with the technology disclosed in the above-mentioned publication, and there is naturally a limit in improving the mechanical properties.

 The gas barrier properties of styrene-based elastomers can be improved to some extent by incorporating inorganic fillers, but none have yet been obtained that sufficiently satisfy the gas barrier properties.

 Thus, the present invention provides a styrene-based elastomer composition having a good mechanical property by improving the gas barrier properties of the styrene-based elastomer by sufficiently finely dispersing the layered inorganic conjugate in the styrene-based elastomer. The task is to provide

 Summary of the Invention

 According to the present invention, the above-mentioned object is to provide (a) a styrene-based elastomer, (b) a layered inorganic compound organically treated with an organic cation, and (c) a compatibility with the (a) styrene-based elastomer. A polar polymer having a polar functional group in the molecule (hereinafter, this may be abbreviated as a “resin-based compatibilizer”). The problem is solved by using a styrene-based elastomer composition characterized in that the distance is at least 15 angstroms.

That is, the present invention provides (a) a styrene-based elastomer, (b) a layered inorganic compound organically treated by an organic cation, and (c) the (a) styrene-based elastomer. A styrenic elastomer composition comprising a polar polymer having a polar functional group in the molecule and having compatibility with a polymer, wherein the (b) organically modified layered inorganic compound in the composition is A styrene-based elastomer composition, characterized in that the interlayer distance is 15 Å or more.

 BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a wide-angle X-ray diffraction pattern of a film made of a styrene-based elastomer composition obtained in Example 9 and Comparative Example 2 (2) described below. Of the two peaks of Comparative Example 2 (2) shown by dotted lines in FIG. 1, the left peak is the peak corresponding to the (001) plane of the layered inorganic compound, and the right peak is the layered inorganic compound. This is the peak corresponding to the (0 2) plane.

 FIG. 2 is a wide-angle X-ray diffraction pattern of a film made of the styrene-based elastomer composition obtained in Example 10 and Comparative Example 3 (2) described below. Among the two peaks of Comparative Example 3 (2) shown by the dotted lines in FIG. 2, the left peak is the peak corresponding to the (01) plane of the layered inorganic conjugate, and the right peak is the layered inorganic peak. This is a peak corresponding to the (002) plane of the compound.

 FIG. 3 is a photograph (top) of a cross section of an ultrathin section of a sheet made of the styrene-based elastomer composition obtained in Example 10 described later, which was observed with a transmission electron microscope, and the layer structure in the composition. FIG. 3 is a schematic diagram (lower) illustrating a dispersion state of an inorganic compound (synthetic mica). FIG. 4 is a photograph (top) of a cross section of an ultra-thin section of a sheet made of the styrene-based elastomer composition obtained in Comparative Example 3 (2) described below, which was observed with a transmission electron microscope (top). FIG. 2 is a schematic diagram (below) showing a dispersion state of the layered inorganic compound (synthetic mica) of FIG.

 FIG. 5 is a photograph obtained by observing a cross section of an ultrathin section of the sheet made of the styrene-based elastomer composition obtained in Example 10 described later and shown in FIG. 3 with a transmission electron microscope.

 FIG. 6 is a photograph obtained by observing the cross section of an ultra-thin section of the sheet made of the styrene-based elastomer composition obtained in Comparative Example 3 (2) described later with reference to FIG. 4 using a transmission electron microscope. .

Disclosure of the invention Each component of the styrenic elastomer composition of the present invention will be described in detail below.

 (a) Styrene-based elastomer [Component (a)]

 (a) As the styrene-based elastomer, a conventionally known styrene-based elastomer can be used without any particular limitation. Specific examples thereof include, for example, an aromatic bur compound, an olefin-based compound, and a: gen compound. Block copolymers and the like can be mentioned.

As such a block copolymer, when a polymer block composed of an aromatic bull compound is represented by A and a polymer block composed of an olefin compound or a conjugated gen compound is represented by B, the following formulas: A—B, ( A—B) _m —A (where m represents an integer of 1 to 10), (A—B) _n —X (where X is an n-valent residue derived from a coupling agent) And n represents an integer of 2 to 15]. A block polymer in which a polymer block composed of an aromatic butyl compound and a polymer block composed of an olefin compound or a conjugated gen compound are connected in a tapered shape can also be used as the styrene-based elastomer. Among these, a block copolymer in which two or more of the polymer blocks A composed of an aromatic vinyl compound and one or more of the polymer blocks B are linearly bonded, particularly the formula: A—B—A Is preferred.

 Examples of the aromatic vinyl conjugate which constitutes the above-mentioned block copolymer include styrene, α-methylstyrene, o—, m— or ρ-methinolestyrene, 2,3-dimethinolestyrene, 2,4 —Dimethylstyrene, Monochlorostyrene, Dichlorostyrene, p-Bromostyrene, 2,4,5-Tribromostyrene, 2,4,6-Tribromostyrene, o—, m— or p—tert-butylstyrene, ethylstyrene , Burnaphthalene, and bianthracene. Of these, styrene and / or α-methylstyrene are preferred. One kind of the aromatic vinyl compound may be used, or two or more kinds thereof may be used in combination.

The content of the aromatic butyl compound unit in the block copolymer is not particularly limited, but is preferably 5 to 75% by weight in view of the moldability and mechanical properties of the obtained styrene-based elastomer composition. And more preferably 10 to 65% by weight. On the other hand, examples of the olefin compound constituting the block copolymer include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, cyclopentene, 1-hexene, 2-hexene , Cyclohexene, 1-heptene, 2-heptene, cycloheptene, 1-otaten, 2-octene, cyclooctene, bulcyclopentene, bulcyclohexene, bulcycloheptene, bulcyclootatene and the like. Examples of the gen compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block B may be composed of one type of these compounds, or may be composed of two or more types, but may be composed of butadiene, isoprene or a mixture thereof. It is more preferable that the obtained styrene-based elastomer composition is composed of a mixture of butadiene and isoprene or isoprene in view of the gas barrier property.

 The polymer block B may contain an aliphatic carbon-carbon double bond in a side chain. For example, when a mixture of butadiene and isoprene or isoprene is used as the conjugated diene compound, the polymer block B has aliphatic carbon atoms in the side chain derived from 1,2-bonds and 3,4-bonds. May contain carbon double bonds. In this case, the ratio of 1,2-linkage and 3,4-linkage in the polymer block B is not particularly limited, but the sum of 1,2-linkage and 3,4-linkage constitutes a block copolymer. It is preferably contained in a proportion of at least 30 mol%, more preferably at least 40 mol%, based on the total amount of the structural units.

 In the polymer block B, an aliphatic carbon-carbon double bond derived from a conjugated diene compound may be hydrogenated. The hydrogenation rate of the aliphatic carbon-carbon double bond is appropriately selected depending on the composition, application, etc. of the styrene-based elastomer composition, but if heat resistance, weather resistance, etc. are required, 30 It is preferably at least 50 mol%, more preferably at least 50 mol%, even more preferably at least 80 mol%.

The hydrogenation rate of the aliphatic carbon-carbon double bond described above can be calculated by a commonly used method, for example, an iodine value measurement method, iH-NMR measurement, or the like. You.

 Preferred examples of the above-mentioned block copolymer include polystyrene-polybutadiene-polystyrene triplep copolymer or a hydrogenated product thereof, polystyrene-polyisoprene-polystyrene triblock copolymer or a hydrogenated product thereof, and polystyrene-polystyrene. (Isoprene / butadiene) Polystyrene triblock copolymer or its hydrogenated product, poly (α-methylstyrene) polybutadiene monopoly (α-methylstyrene) triblock copolymer or its hydrogenated product, poly (α- Methylstyrene) Polyisoprene monopoly (α-methylstyrene) triblock copolymer or hydrogenated product thereof, poly (α-methylstyrene) monopoly (isoprenebutadiene) monopoly (α-methylstyrene) tri Block copolymer or its And hydrogenated products thereof. In addition, a polystyrene-polyisobutene-polystyrene triblock copolymer, a poly (α-methylstyrene) -polyisobutene-poly (α-methylstyrene) triblock copolymer, and the like are also preferable examples.

In addition, these block copolymers may have a carboxyl group or a salt thereof, a hydroxyl group, an acid anhydride group, an amino group, It may contain a polar functional group such as an epoxy group, an ester group, an alkoxy group, an aryloxy group, a sulfonic acid group or a derivative thereof, an amide group, a mercapto group, and a halogen atom. The content of the polar functional group is not also the be particularly restricted, it is preferable that relative to the total molar amount of the repeating units constituting the block copolymer 0. 0 less than 5 mole _^0/0, 0. 0 4 mol _^0/0 and more favorable preferable or less.

 In the production process, the block copolymer having a polar functional group can be obtained by: i) a method of reacting a compound containing a polar functional group as a polymerization terminator; ϋ) a olefin compound containing a polar functional group and Z or a polar functional group. It can be produced by a method of copolymerizing or adding a conjugated diene compound having a group.

Examples of the above-mentioned polar functional group-containing olefin compound and / or polar functional group-containing conjugated diene compound include, for example, a, 3-unsaturated carboxylic acid such as acrylic acid and methacrylic acid; methyl acrylate, ethyl Atarilate, Prop Acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexino acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2 —Ethylhexyl methacrylate, cyclohexyl methacrylate, etc., α, 3-unsaturated carboxylic acids such as anolequinoleestenole; Imide compounds of α, β-unsaturated dicarboxylic acids such as N-cyclohexylmaleimide; unsaturated conjugates containing epoxy groups such as glycidyl methacrylate and arylidicyl ether; a, such as itaconic acid and maleic acid 3-unsaturated dicarboxylic acid; itaconic anhydride, maleic anhydride, anhydride Anhydrides of α, / 3-unsaturated dicarboxylic acids such as citraconic acid; unsaturated compounds containing amino groups such as acrylamine, aminoethyl methacrylate, aminopropyl methacrylate, and aminostyrene; 3-hydroxy-1--1-propene; —Hydroxy-1-butene, cis-1-4-Hydroxy-2-butene, trans-1-Hydroxy-1-2-butene, 3-Hydroxy_2-Methyl-1-propene, 2-Hydroxyshetinoleac Hydroxy group-containing unsaturated compounds such as relay and 2-hydroxyxethino methacrylate; atalylamido, buroxazoline and the like. As the olefin compound containing a polar functional group and the お よ び-or gen compound containing a polar functional group, one kind may be used, or two or more kinds may be used in combination.

 In addition, as the block copolymer, those dynamically crosslinked in the presence of an organic peroxide or the like can be used, if necessary.

 Although the number average molecular weight of the block copolymer is not particularly limited, it is usually in the range of 100, 000 to 1, 000, 0000, preferably 30,0. It is in the range of 00 to 500,000.

The styrenic elastomer used in the present invention exhibits a behavior as a rubber elastic body at room temperature, and if it is a polymer which undergoes plastic deformation by force and temperature rise, it may be an aromatic polymer other than the above-mentioned block copolymer. An aromatic butyl compound and an olefinic compound ヽ are also preferably used as a random copolymer of a conjugated diene compound (hereinafter, these may be abbreviated as “aromatic butyl compound-based copolymer”). The powerful copolymer may contain the aforementioned polar functional group, and its content is particularly limited. Without is preferably based on the total molar amount of the repeating units constituting the copolymer 0. 0 5 mol% is less than 0. 0 It is more preferably 4 mole _^0/0 or less. If necessary, a dynamically cross-linked copolymer in the presence of an organic peroxide or the like can also be used as the aromatic bully conjugate copolymer.

 The number average molecular weight of the aromatic butyl compound-based copolymer is not particularly limited, but is usually in the range of 100,000 to 1,000,000, preferably , 30, 0000 to 500, 000.

 The styrene-based elastomer used in the present invention includes a composition of the above-described block copolymer or aromatic Bürich compound-based copolymer and another resin such as a polyolefin-based resin, and further, if desired, a plasticizer or the like. A composition containing an additive is also suitably used.

 Here, examples of the polyolefin-based resin include polypropylene, polyethylene, ethylene Z-vinylinoleate copolymer, 4-methylpentene-11, polybutene-11, ethylene / acrylate copolymer, and among others, polypropylene Is preferred. The amount of the polyolefin-based resin used is preferably less than 100 parts by weight, and preferably not more than 80 parts by weight, based on 100 parts by weight of the block copolymer or the aromatic butyl compound-based copolymer. Is more preferred. If the amount of the polyolefin-based resin exceeds the above range, the mechanical properties of the styrene-based elastomer may be impaired.

 As the plasticizer, a softener for non-aromatic rubber is preferably used. Specific examples thereof include a paraffinic or naphthenic process oil, a white oil mineral oil, an oligomer of ethylene and α-olefin, a paraffin box and a liquid paraffin, and among them, a paraffinic process oil is preferable. The amount of the plasticizer to be used is preferably not more than 400 parts by weight based on 100 parts by weight of the above-mentioned block copolymer or aromatic vinyl compound compound-based copolymer. If the amount of the plasticizer exceeds the above range, the mechanical properties of the elastomer may be reduced or the plasticizer may bleed out in the same manner as described above.

The styrene-based elastomer used in the present invention includes, in addition to the polyolefin-based resin, an ethylene-propylene copolymer rubber, as long as the gist of the present invention is not impaired. Styrene resin such as polystyrene, styrene-acrylonitrile copolymer, ABS, etc. J! Gam; Polyphenylene ethereol resin; Polyester resin; Polyurethane resin; Polyamide resin; Polyacetal resin; Can be added. Further, if necessary, reinforcing materials (for example, carbon black, carbon ^ I, glass «, boron», aramid fiber, liquid crystal polyester fiber, etc.), fillers, antioxidants, light stabilizers, flame retardants, Colorants, antibacterial agents, antifungal agents, ultraviolet absorbers, heat stabilizers, foaming agents, crystal nucleating agents, lubricants, antistatic agents, colorants, crosslinkers, low shrinkage agents, thickeners, release agents, Fogging agents, blueing agents, silane coupling agents and the like can also be added.

 Commercially available styrene-based elastomers can also be used. For example, as styrene-conjugated genblock copolymers, “Septon” or “Hybra-1” (trade name; manufactured by Kuraray Co., Ltd.), “Clayton” (trade name; manufactured by Shell Co., Ltd.), “Tafprene” [Trade name; manufactured by Asahi Kasei Corporation], “Dynalon” [trade name; manufactured by JSR Corporation], etc., as “styrenenoethylene copolymer”, “indettas” [trade name: Dow Chemical ( Co., Ltd.], and as compositions, for example, “Aron AR” (trade name; column of Aron Kasei Co., Ltd.), “Ranokuron” [trade name; And the like.

 (b) Layered inorganic compound [Component (b)]

 Next, the layered inorganic compound (b), which is a component of the styrenic elastomer composition of the present invention, will be described.

 The layered inorganic compound used in the present invention is mainly composed of a clay mineral, and includes, for example, a swellable silicate, zirconium phosphate, etc., but is industrially versatile, easy to handle, and obtains a polymer composition. From the viewpoint of physical properties and the like, an I-type silicate is preferably used.

 The swellable silicate referred to herein is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of a metal hydroxide. The swellable silicate is water, a polar solvent which is miscible with water at an arbitrary ratio or water and the polar solvent. It is a silicate that has the property of lS in a mixed solvent of solvents. Examples include smectite clay, l-mica, and myriki.

Natural or synthetic products are used as smectite clays. The smecta Specific examples of the clays of the Ito group include, for example, montmorillonite, beidellite, nontronite, sabonite, iron sabonite, hectorite, sauconite, stibnite, bentonite or their substitutes, derivatives, or mixtures thereof. .

 Natural or synthetic products are used as the swellable mica. They have a property of swelling in water, a polar solvent miscible with water at an arbitrary ratio, or a mixed solvent of water and the polar solvent. Examples of the mica include lithium-type teniolite, sodium-type teniolite, lithium-type tetrasilicate mica, sodium-type tetrasilicate mica, and the like, and substituted substances, derivatives, and mixtures thereof.

 Some of the above-mentioned swelling mica have a structure similar to that of vermiculites, and such equivalents of vermiculites can also be used. Examples of permikilites include triotato hedral permicularite and diotato hedral permikilite.

 Examples of my powers include, for example, mascobite, phlogopite, bio-tit, levidolite, paragonite, and tetrasilicic my powers. In addition, there may be mentioned those obtained by performing a fluorine treatment on my strength to obtain a viscous my strength, or those obtained by hydrothermal synthesis.

 As the layered inorganic compound, one kind may be used, or two or more kinds may be used in combination.

 Among the above-mentioned layered inorganic compounds, montmorillonite, bentonite, hectorite, and mica with sodium ions between layers are easily available, and styrene-based elastomers are also available. It is excellent in dispersibility when used as one composition, and is preferable from the viewpoint of the effect of improving the physical properties of the obtained composition.

It is necessary that the layered inorganic compound be organically ligated by an organic cation. The organic cation is preferably an organic ion such as an organic ion having a positive charge such as ammonium ion, phosphonium ion, sulfonium ion or amino acid. Of these, ammonium ions or phosphonium ions are preferred from the viewpoint of industrial versatility and the like. As the ammonium ion or the phosphonium ion, for example, those represented by the following chemical formula (1) are preferable.

R 丄

(In the formula, M represents a nitrogen atom or a phosphorus atom, and RR ² , R ³ and R ⁴ represent a hydrogen atom, a benzyl group or a polar functional group which may have a polar functional group on a benzene ring, respectively. carbon atoms, which may be substituted with a group represents an alkyl group having 1 to 30 provided that ^ ¹ ^ ⁴ do not simultaneously represent a hydrogen atom ^{or, R 1 ~:.!!} . in R ^4, electrode 14 The number of benzyl groups which may have a functional group is preferably 2 or less.) In the above, examples of the alkyl group having 1 to 30 carbon atoms include a methyl group and an ethyl group. Group, propyl group, isopropyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, noninole group, decyl group, pendecinole group, dodecyl group (lauryl group), tridecyl group, tetradecyl group, pentadecyl group , Octadecyl group, etc. And the like.

 In addition, the benzyl group and the number of carbon atoms are: Examples of the polar functional group which may have an alkyl group of 30 to 30 include a hydroxyl group, an alkoxy group, an aryloxy group, a siloxy group, a mercapto group, an alkylthio group, an arylthio group, an acyl group, a carboxyl group, and an acyloxy group. , An alkoxycarbonyl group, an acid anhydride group, a nitro group, a halogen atom, an epoxy group, etc. Among them, a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, and an acid anhydride group are exemplified. preferable.

The pair Anion of Umuion or phosphonyl ©-ion, typically C l ^_, B r - - the _{ammoxidation, I-, NO 3 -, OH-} , CH 3 COO-, HS0 4 -, but like HC0 ₃ " , CI—, Br-1, I—, NO ₃ _ or OH— are preferred. Examples of ammonium ions are hexyl ammonium ion, octyla Ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, lauryl ammonium ion, stearinoremonium ion, dioctyldimethyl ammonium ion, trioctyl ammonium ion, distearyl Ammonia ion, distearyl dimethyl ammonium ion, butyl ammonium ion, dimethyl butyl ammonium ion, 1,2-dimethylpropyl ammonium ion, methylhexyl ammonium ion, 3-pentinoleammonium ion, dimethylinoammonium ion, Dimethyl dioctadecyl ammonium ion, 2-octyl ammonium ion, getinoleammonium ion, tetramethinoleetinolene ammonium Ummonium, dimethylpropylammonium ion, getylpropylammonium ion, dibutyl ^^ propylammonium ion, tetramethylpropylammonium ion, isoamylammonium ion, ethylisoamylammonium ion, 2-hexenylammonium ion ion, diisopropyl E chill ammoxidation - © ion, E chill dimethylpropyl ammonium Niu-ion, di iso Petit Ruan monitor Umuion, mono one C ₆ _ _2. Monoalkyltrimethylammonium ion, dialkylalkyldimethylammonium ion, cocoalkyldimethylbenzylammonium ion, trioctylmethylammonium ion, trilaurylmethylammonium ion, di-hardened tallowalkyldimethylammonium ion, benzyl Trimethylammonium ion, benzyltriptylammonium ion and the like can be mentioned.

 Specific examples of the phosphonium ion include trimethy ^^ dodecylphosphonium ion, trimethylhexadecylphosphonium ion, trimethyloctadecylphosphonium ion, tributyldodeciphosphonium ion, and tributylhexadecylphosphonium ion. Numerous ions and the like can be mentioned.

Specific examples of the sulfo-pium ion include trimethylsulfonium ion, dimethyldodecylsulfonium, dimethylhexadecylsulfonium ion, dimethyloctadecinoresulfonium ion, triethylsulfonium ion, and getyldodecylsulfonium ion. Sodium ion, getylhexadecylsulfonium ion, getyloctadecylsulfonium ion, tributylsulfonium ion, Examples include dibutyl dodecyl phosphonium ion, dibutylhexadecyl sulfonium ion, and triphenyl sulfonium ion.

 As an ammonium ion, a phosphonium ion or a sozolefonium ion, those having a polar functional group are also preferably used.

For example, as the ammonium ion having a hydroxyl group, the phosphonium ion having a hydroxyl group, or the sulfonium ion having a hydroxyl group, the ammonium ion, the phosphonium ion or the snorehonium ion exemplified above may be one of an alkyl group or a benzyl group. Specific examples thereof include an ion obtained by substituting 4 to 4 with a hydroxymethyl group, a hydroxyethyl group (for example, a 2-hydroxyethyl group), or a hydroxypropyl group (for example, a 3-hydroxypropyl group). Examples of the ammonium ion having an alkoxy group or an aryloxy group, the phosphonium ion having an alkoxy group or an aryloxy group, or the sulfonium ion having an alkoxy group or an aryloxy group include the ammonium ion, phosphonium ion or sulfonium ion exemplified above. In the ion, one to four alkyl groups or benzyl groups are (CH ₂ CH ₂₀ ) _PR groups, (CH ₂ CH (CH ₃ ) O) _PR groups or (CH ₂ CH ₂ CH ₂ O) _p Substituted with a polyoxyalkylene group represented by an R group (where p represents an integer of 1 to 50, and R represents a hydrogen atom or an alkyl group or an aralkyl group having 1 to 30 carbon atoms) An ion is mentioned as a specific example. Examples of the ammonium ion having an acyloxy group, the phosphonium ion having an acyloxy group or the sulfonium ion having an acyloxy group include, for example, the ammonium ion having a hydroxyl group, the phosphonium ion or the hydroxyl group having a hydroxyl group exemplified above. Specific examples thereof include those having a hydroxyl group protected by an acyl group such as an acetyl group or a benzoyl group.

 Examples of the ammonium ion having a carboxyl group, an acid anhydride group or an alkoxycarbonyl group include, for example, cations derived from amino acids.

The amino acids mentioned here are preferably those having 4 to 30 carbon atoms. Specifically, lysine, arginine, γ-aminocyclohexylcarboxylic acid, and ρ-aminohydroxy Examples include cinamic acid, leucine, phenylalanine, histidine, and tryptophan.

 In the above amino acids, the carboxyl group may be in a protected form such as methyl ester, ethanol ester, benzyl ester and the like.

 By adding the above-mentioned organic cation to the layered inorganic compound, an organic layered inorganic compound can be obtained.

 Prior to the addition of the organic cation, the layered inorganic conjugate is preferably swelled. In the swelling treatment, specifically, the layered inorganic compound is immersed in (i) water, (ii) a polar organic solvent that is miscible with water at an arbitrary ratio, or (iii) a mixed solvent of water and the polar organic solvent. Can be implemented. At this time, it is desirable to perform sufficient stirring. Examples of polar organic solvents include, for example, methanol, ethanol, and 2-propanol. Oleorecols such as phenol; ethylene glycolone, propylene glycol, dioneoles such as 1,4-butanediol; ketones such as acetone; etherenoles such as tetrahydrofuran, 1,4-dioxane; dimethylformamide, dimethylacetamide, dimethylsulfoxide, And aprotic polar solvents such as dimethoxyethane.

 The layered inorganic conjugate obtained by the organic tan can be obtained according to a conventional method such as filtration and centrifugation. The obtained layered inorganic compound is desirably dried after sufficiently removing excess organic cations by washing.

 The amount of organic cation to be added can be determined, for example, by the column permeation method (see “Clay Handbook”, pp. 576-577, published by Gijudo), and the method for measuring the amount of adsorbed methylene blue (Standard Test Method of Japan Bentonite Association, JBAS The cation exchange capacity (CEC) of the layered inorganic compound can be determined by a method such as —107-91) and determined based on the measured value. The amount of the organic cation to be added is preferably at least 1 equivalent to CEC, more preferably in the range of 1 to 10 equivalents.

 (c) resin-based compatibilizer [component (c)]

 Next, (c) a resin-based compatibilizer which is a constituent component of the styrene-based elastomer composition of the present invention will be described.

The (c) resin-based compatibilizer used in the present invention comprises the above component (a) styrene-based elastomer It is a polar polymer that is compatible with Toma I and has a polar functional group in the molecule.

 For example, when the component (a) which is not compatible with the styrene-based elastomer is used as the component (c), the above-mentioned (b) layered inorganic compound is used in the styrene-based elastomer composition. It is not preferable because it cannot be sufficiently dispersed and the gas barrier property of the obtained styrene-based elastomer composition cannot be improved.

 Examples of the polymer having compatibility with the styrene-based elastomer include styrene-based polymer such as polystyrene, styrene-conjugated gen-block copolymer or hydrogenated product thereof, polyester-based polymer, polyethylene, and polypropylene. Polyolefin-based polymers, polybutadienes, ethylene-propylene copolymers and the like can be mentioned. (C) A polar polymer having these polymers as the basic structure and having a polar functional group in the molecule can be used as the durable compatibilizer.

 Examples of the polyolefin-based polymer include ethylene, propylene, 1-butene, 2-butene, isopten, 1-pentene, 2_pentene, cyclopentene, 1-hexene, 2-hexene, cyclohexene, —Olefin compounds such as —heptene, 2-heptene, cycloheptene, 1-octene, 2-otaten, cyclooctene, vinylcyclopentene, bulcyclohexene, vinylinolecycloheptene, and vinylinolecyclooctene; 1,3-butadiene, isoprene And homo- or copolymers of gen-based compounds such as 1,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Further, those obtained by hydrogenating an aliphatic carbon-carbon double bond contained in a polyolefin polymer can also be used.

 Examples of the styrene-based polymer include styrene, α-methinolestyrene, ο-, m- or ρ-methylstyrene, 2,3-dimethinolestyrene, 2,4-dimethinolestyrene, monochlorostyrene, Dichlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene, 2,4,6-tribromostyrene, o-, m- or p-tert-butynolestyrene, ethi ^^ styrene, vinylinalephthalene And homopolymers or copolymers of aromatic bur compounds such as burantracene.

Further, as the styrene-conjugated gen block copolymer or a hydrogenated product thereof, For example, polystyrene-polybutadiene-polystyrene triblock copolymer or hydrogenated product thereof, polystyrene-polyisoprene-polystyrene triblock copolymer or hydrogenated product thereof, polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer Block copolymer or hydrogenated product thereof, poly (α-methylstyrene) monopolybutadiene poly (α-methylstyrene) Triblock copolymer or hydrogenated product thereof, poly (α-methylstyrene) polyisoprene monopoly (Α-methylstyrene) triblock copolymer or hydrogenated product thereof, poly (α-methylstyrene) -poly (isoprene-butadiene) -poly (α-methylstyrene) triblock copolymer or hydrogenated product thereof Is mentioned. Examples of the polyester polymer include polycondensation of a diol component such as ethanediol, propanediol, butanediol, and di (hydroxymethyl) benzene with a dicarboxylic acid component such as phthalic acid, isophthalic acid, and terephthalic acid. The obtained polymer is exemplified. In addition, an insect or copolycondensate of a hydroxycarboxylic acid such as lactic acid is also preferably used. Further, a ring-opened polymer of a cyclic esterified compound such as kyprolatatatone is also preferably used.

 (c) The polar functional group in the resin-based compatibilizer is to suppress aggregation and non-uniform dispersion of the layered inorganic compound in the obtained styrene-based elastomer composition, and to sufficiently disperse the layered inorganic compound. Further, it is preferable that the compound has affinity or reactivity with the layered inorganic compound. (c) Examples of the polar functional group in the resin compatibilizer include a hydroxyl group, an alkoxy group, an aryloxy group, a siloxy group, a mercapto group, an alkylthio group, an arylthio group, an acyl group, a carboxyl group or a salt thereof, and an acyloxy group. Group, alkoxycarbonyl group, aryloxycarbonyl group, acid anhydride group, aldehyde group, acetal group, amide group, imide group, nitro group, halogen atom, sulfonic acid group or derivative thereof, epoxy group, etc. However, a hydroxyl group, a carboxyl group or a salt thereof, an alkoxycarbonyl group, an acyloxy group, an acid anhydride group, and an epoxy group are preferred.

 (c) The resin-based compatibilizer may have only one type of polar functional group, or may have two or more types of polar functional groups.

(c) The content of the polar functional group in the resin compatibilizer is used as the resin compatibilizer. 0 relative to the total number of moles of repeating units constituting the polar polymer to be. 0 preferably from 5 mol ° / ₀ or more on, 0. 0 5 mol _^0/0 over 5 0 or less mol% Is more preferred. Depending on the type of (a) styrene-based elastomer used, (b) the type of layered inorganic compound and the amount used, (c) the content of polar functional groups in the resin-based compatibilizer depends on the resin-based phase. relative to the total number of moles of repeating units constituting the polar polymers used as solubilizer 0.0 5 mole _^0/0 less than ^, in (a) styrenic Erasutoma

(b) The effect of uniformly dispersing the layered inorganic compound may be insufficient. Conversely, (c) the content of the polar functional group in the resin-based compatibilizer is 50 mol% with respect to the total number of moles of the repeating units constituting the polar polymer used as the resin-based compatibilizer. If it exceeds, a gel or the like may be generated when the styrene-based elastomer composition is produced or processed.

 The polar functional group may be contained in (c) one end or both ends of the molecular chain of the polar polymer used as the resin-based compatibilizer, in the middle of the molecular chain, or at a side chain. There is no restriction on the distribution of the polar functional groups in the polar polymer.For example, a regular distribution, a block distribution, a random distribution, a tapered distribution, a distribution in which all or some of these are mixed, or the like. There may be.

 (c) The polar polymer used as the resin-based compatibilizer may be prepared by: i) a method of reacting a compound having a polar functional group as a polymerization terminator in the production process, and ii) a compound having a polar functional group. It can be produced by a method of polymerization or addition.

 Examples of the compound containing a polar functional group include acrylic acid and methacrylic acid.

(D a, monounsaturated carboxylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexino oleate, Monounsaturated alkyl esters of rubonic acid such as cyclohexyl acrylate, methyl methacrylate, methyl methacrylate, 2-ethylhexynole methacrylate, cyclohexynole methacrylate; maleimide, N- Imido compounds of α, β-unsaturated dicarboxylic acids such as methylmaleimide, N-ethylmaleimide, N-phenyl, remaleimide, N-cyclohexinolemaleimide; Daricidyl methacrylate, aryl Epoxy group-containing unsaturated compounds such as glycidyl ether; α,) 3-unsaturated dicarboxylic acids such as itaconic acid and maleic acid; _α , / 3-unsaturated dicarboxylic acids such as itaconic anhydride, maleic anhydride and citraconic anhydride Acid anhydrides; unsaturated compounds containing amino groups such as acrylamine, aminoethyl methacrylate, aminopropyl methacrylate, and aminostyrene; 3-hydroxy-11-propene, 4-hydroxy-11-butene, cis-1-hydroxy-1 Hydroxyl-containing unsaturated compounds such as 2-butene, trans-1-hydroxy-2-butene, 3-hydroxy-2-methynole-1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; Polyalkylene glycols such as polyethylene glycol; formaldehyde, tetrahydrofur Cyclic ethers such as orchid and 1,4-dioxane; acrylamide, vinyloxazoline, and butyl acetate; and the like, and one or more of these can be used.

 (c) The polar polymer used as the resin-based compatibilizer may be, if necessary, saponified, or in the form of a salt with an alkali metal or an alkaline earth metal. It's good. Further, (c) the polar polymer used as the resin-based compatibilizer may have an ionomer structure crosslinked by a polyvalent metal.

 (c) The number average molecular weight of the polar polymer used as the resin compatibilizer is usually in the range of 500 to 500,000, and 1,000 to 300,0. It is preferably within the range of 00.

 Specific examples of the polar polymer are shown below.

 (A) Polar polymer having a carboxyl group or a salt thereof

 Ethylenenoacrylic acid copolymer, propylene / acrylic acid copolymer, ethylene / propylenenoacrylic acid copolymer, ethylene methacrylic acid copolymer, propylene methacrylic acid copolymer, ethylene // propylene / methacrylic acid copolymer Copolymer, Ethylene knobene / acrylic acid copolymer, Ethylene / butene Methacrylic acid copolymer, Ethylene 、 hexene ΖAcrylic acid copolymer, Ethylene hexene methacrylic acid copolymer, Ethylene / Otatin / Acrylic acid copolymer , Ethylene / octene-methacrylic acid copolymer, or these metals

(Mouth) Electrodes with hydroxyl groups! Polymer Ethylene zaryl alcohol copolymer, propylene zaryl alcohol copolymer, ethylene / propylene / aryl alcohol copolymer, ethylene / methallyl alcohol copolymer, propylene / methallyl alcohol copolymer, ethylene / pro Pyrene z methallyl alcohol copolymer, ethylene / butene zaryl alcoholic copolymer, ethylene nobten / methallyl alcohol copolymer, ethylene Z hexene allyl alcohol copolymer, ethylene / hexene / methallyl alcohol Copolymer, ethylene ^ otene Zaryl alcohol copolymer, ethylene Z otaten methallyl alcohol copolymer.

 Ethylene 2-hydroxyethyl acrylate copolymer, Propylene 2-hydroxyethyl ^ acrylate copolymer, Ethylene Z propylene / 2-hydroxyethyl acrylate copolymer, Ethylene Z 2-hydroxyethyl methacrylate Copolymer, propylene // 2-hydroxyethyl methacrylate copolymer, ethylene propylene 2-hydroxyethyl methacrylate copolymer, ethylene buteno 2-hydroxyethyl acrylate copolymer, ethylene / buteno 2- Hydroxyl methacrylate copolymer, ethylene / hexene / 2-hydroxyethyl acrylate copolymer, ethylene / hexene / 2-hydroxyethyl methacrylate copolymer, ethylene / otaten 2-hydroxyethyl Acrylate copolymer, ethylene Z otaten / 2 Hydroxy E chill methacrylate copolymer. One end or both ends hydroxypolyethylene, One end or both ends hydroxypolypropylene, One end or both ends hydroxypolyethylene / propylene copolymer, One end or both ends hydroxypolyethylene propylene / butadiene copolymer, one end Or both ends hydroxypolystyrene.

 One or both terminal hydroxy polybutadiene, one or both terminal hydroxy polyisoprene, one or both terminal hydroxy poly (isoprene butadiene) or hydrogenated products thereof.

One end or both ends hydroxy (polystyrene-polybutadiene-polystyrene triblock copolymer), one end or both ^ hydroxy (polystyrene-polyisoprene-polystyrene triblock copolymer), one end or both ends hydroxy [polystyrene-one Poly (butadiene isoprene) Polystyrene Triblock copolymer] or a hydrogenated product thereof. Single or double hydroxy (polystyrene-polyisobutene-polystyrene triblock copolymer).

 (C) Polar polymer having acid anhydride group

 Ethylene z maleic anhydride copolymer, propylene / maleic anhydride copolymer, isobutylenno maleic anhydride copolymer, methylbutyl ether maleic anhydride copolymer, ethylbutyl ether Z maleic anhydride copolymer, Ethylene propylene / maleic anhydride copolymer, ethylene Z-butene / maleic anhydride copolymer, ethylene / hexene z maleic anhydride copolymer, ethylene / otaten / maleic anhydride copolymer, styrene / Maleic anhydride copolymer.

 Maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene // propylene copolymer, maleic anhydride-modified polyethyleneethylene propylene Z-butadiene copolymer, maleic anhydride-modified polystyrene. Maleic anhydride-modified (polystyrene-polybutadiene-polystyrene triblock copolymer), maleic anhydride-modified (polystyrene-polyisoprene-polystyrene triblock copolymer), maleic anhydride-modified [polystyrene-poly (isoprene z-butadiene) —Polystyrene triblock copolymer], modified with maleic anhydride (polystyrene-polyisobutene-polystyrene triblock copolymer).

 (D) Epoxy-containing polymer

 Ethylene noglycidyl acrylate copolymer, propylene Z glycidyl acrylate copolymer, ethylene / propylene / daricidyl acrylate copolymer, ethylenenoglycidyl methacrylate copolymer, propylene glycidyl methacrylate Copolymer, ethylene / propylene z-glycidyl methacrylate copolymer, ethylene Z-butene / daricidyl acrylate copolymer, ethylene / butene ^ daricidyl ^^ methacrylate copolymer, ethylene / hexene glycidyl acrylate copolymer Polymers, ethylene hexene / glycidyl methacrylate copolymer, ethylene octene Z glycidyl acrylate copolymer, ethylene / otatenodalicidinole methacrylate copolymer.

 (E) Polymer having an alkoxycarbonyl group

Ethylene / ethyl acrylate copolymer, propylene noethyl acrylate copolymer Polymer, ethylene / propylene noethyl acrylate copolymer, ethylene / ethyl methacrylate copolymer, propylene / ethyl methacrylate copolymer, ethylene / propylene z-ethyl methacrylate copolymer, ethylene z Butene / Ethynole acrylate copolymer, Ethylene Z-Butene / Ethyl methacrylate copolymer, Ethylene Z-hexene Z-Ethyl acrylate copolymer, Ethylene / Hexene / Ethynole methacrylate copolymer, Ethylene / / Othene / Ethyl acrylate copolymer, Ethylene Z-octene / Ethyl methacrylate copolymer.

 The polymer having a carboxyl group or a salt thereof can be obtained by neutralizing the above-mentioned polar polymer having an acid anhydride group of (c) with an alkali or the like. Further, the polar polymer having an acid anhydride group of the above (c) is neutralized with ammoniaamine and dehydrated as necessary to obtain a polymer having an amide group or a polymer having an imido group. Obtainable.

 (c) As the resin-based miscible agent, one or a mixture of two or more of the above polar polymers can be used.

 (A) a styrene-based elastomer (hereinafter, also referred to as a component (a)), (b) a layered inorganic compound (hereinafter, also referred to as a component (b)), which constitutes the styrene-based elastomer composition of the present invention; (C) The weight ratio of the resin-based compatibilizer (hereinafter also referred to as component (c)) is appropriately determined according to the type of each component used and the physical properties required for the obtained styrene-based elastomer composition. Is usually in the following range:

 Component (b) Z component (a) = 0.0 1/1 00 ~ 200 100 100, and

 Component (c) Z component (a) = 0.01 / 100-5000Z100.

 (b) When the amount of the layered inorganic compound used exceeds the above range, physical properties such as flexibility, rubber elasticity and moldability of the obtained styrene-based elastomer composition may be reduced. Conversely, if the amount of (b) the layered inorganic compound used is less than the above range, the effect of improving the mechanical properties and gas barrier properties due to the addition of the layered inorganic compound may not be exhibited.

 (b) The use amount of the layered inorganic compound is preferably within the following range.

Component (b) Z component (a) = 0.03 / 100 to: 150/100 (weight ratio) Also, (c) if the amount of the resin-based compatibilizer exceeds the above range, the obtained stainless steel When physical properties such as flexibility of rubber-based elastomer composition, rubber bullet '14, and moldability are deteriorated There is. Conversely, if the amount of the (C) resin-based compatibilizer is less than the above range, it becomes difficult to sufficiently finely disperse the layered inorganic compound in the styrene-based elastomer, and the addition of the layered inorganic compound causes a mechanical problem. The effect of improving the characteristics and gas barrier properties may not be exhibited. (C) The amount of the resin-based compatibilizer used is preferably within the following range.

 Component (c) Component (a) = 0.03 / 100 to 300/100 (weight ratio) The styrenic elastomer composition of the present invention contains the styrene-based elastomer composition as long as the purpose of the present invention is not impaired. However, various additives to be added to the usual styrenic elastomer composition may be added. The various additives mentioned here include ultraviolet absorbers, light stabilizers, heat stabilizers, plasticizers, various oils, various mineral oils, foaming agents, crystal nucleating agents, lubricants, antistatic agents, coloring agents, crosslinking agents, Flame retardants, antifungal agents, low shrinkage agents, thickeners, release agents, antifogging agents, bluing agents, silane coupling agents, reinforcing materials (for example, carbon black, carbon fiber, glass fiber, boron fiber, Aramide fibers, liquid crystal polyester fibers, etc.), fillers, antioxidants, antibacterial agents and the like.

 Further, the styrene-based elastomer composition of the present invention may be added with another polymer blended with a general styrene-based elastomer composition, as long as the gist of the present invention is not impaired. Examples of the polymer include ethylene-propylene copolymer rubber; polystyrene, styrene-acrylonitrile copolymer, styrene resins such as ABS; polyphenylene ether resins; polyester resins; polyurethane resins; polyamide resins. Polyacetal resin; ataryl-based resin and the like. The styrene-based elastomer composition of the present invention comprises: a styrene-based elastomer as the component (a), a layered inorganic compound as the component (b) and a resin-based compatibilizer as the component (c), and if necessary, various additives. And other polymers can be prepared by melt-kneading according to a conventional method. Melt kneading can be performed using, for example, a Banbury mixer, a plast mill, a single screw extruder, a twin screw extruder, or the like.

 In kneading, there is no particular limitation on the order of addition of each component,

 (1) A method in which styrene-based elastomer, (b) layered inorganic compound and (c) resin-based compatibilizer are mixed together and melt-kneaded, or

② A composition obtained by melt-kneading (a) a styrene-based elastomer and (c) a resin-based compatible agent And (b) adding a layered inorganic compound and melt-kneading,

(3) After melt-kneading the (b) layered inorganic compound and the (C) resin-based compatibilizer to form a composition,

(a) a method of adding a styrene-based elastomer and melt-kneading,

However, the method shown as ③ is preferable.

 In the method of (3), after the composition comprising (b) the layered inorganic compound and (c) the resin-based compatibilizer is once formed into pellets, (a) a styrene-based elastomer composition is added and melted. It may be kneaded, or (a) a styrene-based elastomer may be mixed with a molten composition comprising (b) a layered inorganic compound and (c) a resin-based compatibilizer prepared by melt-kneading. It may be added and kneaded.

 In addition to melt kneading, for example,

 方法 a method of mixing (a) a styrene-based elastomer, (b) a layered inorganic compound and (c) a resin-based compatibilizer in an organic solvent,

 方法 a method of adding (b) the layered inorganic compound dispersed in an organic solvent to (a) a styrene-based elastomer and (c) a resin-based compatibilizer,

The styrenic elastomer composition of the present invention can also be prepared by such methods. The above-mentioned various additives and other polymers used as necessary may be previously blended with (a) a styrene-based elastomer or (c) a resin-based compatibilizer,

(a) Styrene-based elastomer and (c) Resin-based compatibilizer may be blended as separate components.

 In the styrene-based elastomer composition of the present invention prepared as described above, it is necessary that the interlayer distance between the layered inorganic compound and the organic layer is 15 Å or more.

 In the present invention, in addition to (b) using a layered inorganic compound that has been subjected to organic cations with an organic cation, (c) using a resin-based compatibilizer, a styrene-based elastomer composition Only when the (b) layered inorganic compound has the above-mentioned interlayer distance in the product, it is possible to obtain a styrene-based elastomer composition having improved gas-palliability.

Further, it has been found that (b) the styrene-based elastomer composition of the present invention has a tendency to improve gas barrier properties as the interlayer distance of the layered inorganic compound increases. Was.

 In the styrenic elastomer composition of the present invention, the interlayer distance of the layered inorganic compound is preferably at least 20 angstroms, more preferably at least 25 angstroms, and even more preferably at least 30 angstroms. Les, very much preferred to be more than 4 4 angstroms.

 Here, (b) the interlayer distance of the layered inorganic compound can be determined based on a peak corresponding to the (01) plane of the layered inorganic compound, which is detected using wide-angle X-ray diffraction.

 In the present invention, the interlayer distance in the layered inorganic compound is specifically determined by the following method.

Measurement of interlayer distance of layered inorganic compound:

 Using a film (diameter: 4.5 mm, thickness: 0.1 mm) made from a styrene-based elastomer composition, a wide-angle X-ray diffraction (XRD) measuring device [RINT 2400 X-RAY DIFFRACTOMETER (Nippon Rigaku) The X-ray diffraction pattern is measured under the following conditions: measurement angle (20): 2 to 12 degrees, scan speed: 0.2 degrees / min.

Based on the peak corresponding to the (01) plane of the X-ray diffraction peak derived from the layered inorganic compound, the interlayer distance d (angstrom) is calculated using the following equation.

 λ = 1.54 (angstrom)

In the styrene-based elastomer composition of the present invention, it is highly preferable that each layer of the organically modified (b) layered inorganic compound is in a completely separated state. Therefore, in the present invention, (b) no upper limit is set for the interlayer distance of the layered inorganic compound. In the present invention, when the styrene-based elastomer composition is measured by wide-angle X-ray diffraction, (b) the peak derived from the layered inorganic compound completely disappears, It is determined that each layer of the layered inorganic compound has been completely separated. The styrene-based elastomer composition of the present invention in such a state is very preferable because the styrene-based elastomer has a very good gasparia property. In addition, the styrenic elastomer composition of the present invention in such a state is well dispersed in the composition even if the contained (b) layered inorganic compound is a small amount, so that the layered inorganic compound is Many There is no problem of impairing various properties such as flexibility and moldability of the styrenic elastomer when it is added to the composition in a small amount.

 The styrene-based elastomer composition of the present invention can be prepared by a molding method usually used in molding of a thermoplastic elastomer, such as injection molding, extrusion molding, compression molding, inflation molding, blow molding, calendar molding, and rotational molding. It can be processed into molded products such as sheets, molded containers and professional containers.

 In this case, the styrene-based elastomer composition prepared by melt-kneading may be used as it is for molding, or may be once pelletized and then molded.

 Further, the styrene-based elastomer composition of the present invention can be processed into various laminated structures by compounding with another material. Examples of other materials include various thermoplastic resins other than the styrenic elastomer composition of the present invention or their compositions, thermosetting resins, paper, cloth, metal, wood, ceramics, and the like. .

 The laminated structure obtained from the styrene-based elastomer composition of the present invention is not particularly limited. For example, one layer of the layer composed of the styrene-based elastomer composition of the present invention and another layer may be used. Two-layer structure in which one of the layers is laminated, and a three-layer structure in which a layer made of the styrene-based elastomer composition of the present invention exists as an intermediate layer between two surface layers (front and back layers) made of another material Examples of the structure include a three-layer structure in which a layer made of the styrene-based elastomer composition of the present invention is laminated on the front and back surfaces of one layer made of another material.

The laminated structure is produced by a known method, for example, (i) a method of producing a laminated structure by melt-coating the other material described above with the styrene-based elastomer composition of the present invention; A method in which the styrenic elastomer composition of the present invention is introduced under melting between other materials to bond and integrate them; (iii) the present invention with the other materials placed (inserted) in a mold; A method in which the styrenic elastomer composition of the present invention is filled into a mold while being melted, and bonded and integrated. (Iv) When the other material is thermoplastic, the styrenic elastomer composition of the present invention and the other are used. It can be manufactured by a method such as co-extrusion molding and bonding and integrating these materials. Further, the styrene-based elastomer composition of the present invention can be used as a hot-melt adhesive in the production of various products and the above-mentioned laminated structure, if necessary.

 The form of the hot menoleto adhesive using the styrenic elastomer composition of the present invention is not particularly limited, and examples thereof include granules such as pellets, rods, films, sheets, and plates. It can take any shape.

 In the styrenic elastomer composition of the present invention, (b) the layered inorganic compound is sufficiently finely dispersed, so that the gas barrier properties are significantly improved. Also, the mechanical properties are good.

The gas barrier property can be represented by, for example, an oxygen permeability coefficient. On the other hand, the oxygen permeation coefficient P of the styrenic elastomer composition of the present invention has a correlation with the dispersion state of the (b) layered inorganic compound, and can be regarded as an index indicating the dispersion state. Therefore, if the types, physical properties, and amounts of the components used are the same, the better the dispersion state of the (b) layered inorganic compound in the styrene-based elastomer composition, that is, the more the (b) layered The interlayer distance of the inorganic conjugate becomes large (preferably, each layer of the (b) layered inorganic conjugate is completely peeled off, and the (b) layered inorganic compound is finely dispersed in the composition. ), The smaller the value of P, the better the gas barrier property. Among these, in a desirable embodiment, the oxygen permeability coefficient P of the styrene-based elastomer composition of the present invention, (a) the oxygen permeability coefficient P _TPE of the styrene-based elastomer, and the layered inorganic material in the styrene-based elastomer composition The following relational expression is established between the compound and the weight fraction Φ F of the compound. Here, “Oxygen permeability coefficient P of styrene-based elastomer composition” and “(a) Oxygen permeability coefficient P _TPE of styrene-based elastomer” refer to “Method of measuring oxygen permeability coefficient P and P _TPE ” described later. As described, it means the oxygen permeation coefficient measured by forming a styrene-based elastomer composition and (a) a styrene-based elastomer into a film.

P < _0.5 XP _TPE X (1-OF) / (1 + F / 2) (1)

 (Where F is the weight fraction of only the inorganic component of the layered inorganic compound)

When the relational expression (1) is satisfied, the improvement of the gaseous property of the styrenic elastomer composition of the present invention is at a sufficient level. In particular, such styrene of the present invention The system-based elastomer composition can be put to practical use as a material for a gas barrier property article, that is, a material for a gas-pararia article.

 In the present invention, (a) the oxygen permeability coefficient P of the styrene-based elastomer and the oxygen permeability coefficient P of the styrene-based elastomer composition can be specifically determined by the following method.

How to measure oxygen permeability coefficient P, P _TPE :

Using a 0.1 mm thick film made from a styrene-based elastomer composition, using a gas permeability tester [Yanagimoto Gas Chromatograph G2800T (Yanagimoto Co., Ltd.)] Measure the amount of oxygen permeation according to the method described in JISK 712 (isobaric method) at 35 ° C and 50% RH, and calculate the oxygen permeation coefficient こ の from this value. (A) Using a film having a thickness of 0.1 mm made of a styrene-based elastomer, calculate the oxygen permeability coefficient P _TPE in the same manner.

And the oxygen permeability coefficient P of the styrene elastomer first composition, (a) a composition the above relation (1) is not satisfied between the oxygen permeability of the styrene Elastica Tomah one P _TO is expressed Gasuparia of obtaining Therefore, it is necessary to add a large amount of the layered inorganic compound (b), and as a result, it is not preferable because problems such as a decrease in flexibility of the styrenic elastomer composition and poor moldability occur.

 The styrenic elastomer composition obtained by the present invention is used for gas-barrier articles [for example, various food packaging containers, agricultural packaging materials, medical packaging materials, gasoline tanks, iridescent cosmetic containers, drug containers, pharmaceutical packaging materials] , Inner tubes for tires, laminated products, films and sheets for various containers, sealing materials (for example, O-rings, packing, gaskets, lids, caps, cap liners, etc.), hoses, tubes, It can be used for various articles such as car parts and air cushions for shoes.

Above all, the styrenic elastomer composition obtained by the present invention can be used for sealing materials [for example, O-rings, packings, gaskets (for example, gaskets for syringes, etc.), lid materials, etc.] (For example, a medical stopper), a cap (for example, a cap for a vacuum blood collection tube), a cap liner, etc.]. Example

 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

 In the examples and comparative examples, the measurement of the oxygen permeability coefficient and the measurement of the interlayer distance of the layered inorganic conjugate in the styrene-based elastomer composition were performed by the above-described methods.

Example 1

Dimethyl O Kuta decyl ammonium Niu Mui on synthetic mica treated [layered mineralized compounds; Co.-OP Chemical, trade name: MAE; inorganic content: 68 wt _^0/0] 10 _g of ethylene Z acrylate 23 g of a copolymer resin [resin-based compatibilizer; manufactured by Nippon Polychem Co., Ltd., trade name: Novatec EAA A210K] is melt-kneaded using a Labo Plastomill [manufactured by Toyo Seiki Seisaku-sho, Ltd.]. Polystyrene-polyisoprene-hydrogenated polystyrene-triploc copolymer [styrene-based elastomer; Kuraray Co., Ltd., trade name: Septon 2002] 67 g, further melt-kneaded, then cooled to room temperature and cooled to styrene An elastomer composition was obtained.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 15, 100 CC << 20 m / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was 33.2 Å.

Control Example 1

Uses hydrogenated polystyrene-polyisoprene-polystyrene triplep copolymer [styrene-based elastomer; manufactured by Kuraray Co., Ltd., trade name: Septon 2002] and Laboplastomill [produced by Toyo Seiki Seisakusho] After melting and cooling to room temperature, press molding was performed to produce a film. When the oxygen permeability coefficient P _TPE of the obtained film was measured by the above-mentioned method, it was found to be 72,400 cc-20 / zm / m ² · day · atm.

Comparative Example 1 (1)

Untreated synthetic mica [Layered inorganic compound; manufactured by Corp Chemical Co., Ltd., trade name: ME 1 00] Hydrogenated product of 10 g and polystyrene-polyisoprene-polystyrene-triploc copolymer [styrene-based elastomer; manufactured by Kuraray Co., Ltd., trade name: Septon 2002] 67 g of Labo Plastomill Co., Ltd. And then cooled to room temperature to obtain a styrene-based elastomer composition. Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 55,700 cc-20 μm / m ² · day · atm. The interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was found to be 12.1 angstroms.

Comparative Example 1 (2)

 Hydrogenation of synthetic mica treated with dimethyldiotadecylammonium ion [Layered inorganic compound; manufactured by Corp Chemical Co., Ltd., trade name: MAE] 10 g and polystyrene-polysoprene-polystyrene triploc copolymer Product [Styrene-based elastomer; Kuraray Co., Ltd., trade name: Septon 2002] 67 g, Laboplus Tomil! : Manufactured by Toyo Seiki Seisaku-sho, Ltd.), and then cooled to room temperature to obtain a styrene-based elastomer composition.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, the value was 31,600 cc-20 m / m ² · day · atm. The interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was 32.4 Å.

Comparative Example 1 (3)

 Synthetic mica treated with dimethyldioctadecyl ammonium ion [Layered inorganic mica compound; manufactured by Corp Chemical Co., Ltd., trade name: MAE; inorganic content: 68% by weight] Untreated synthetic mica instead of 10 g [Layered inorganic compound; manufactured by Corp Chemical Co., Ltd., trade name: ME 100] A styrene-based elastomer composition was obtained in the same manner as in Example 1 except that 10 g was used.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. Oxygen permeability coefficient of the obtained film P (cc · 2 O / zm / m 2 · day · atm) was measured by the method described above, and it was found to be 41,700 cc '20 m / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was found to be 12.1 angstroms.

Example 2

 Same as Example 1 except that 23 g of ethylene-glycidinolemethacrylate copolymer (EGM A) [manufactured by Sumitomo Chemical Co., Ltd., trade name: Bond First E] was used as the resin compatibilizer. A styrenic elastomer composition was obtained.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 28,400 cc-20 μm / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and it was 32.5 Å.

Example 3

 A resin-based compatibilizer was prepared in the same manner as in Example 1 except that 23 g of an ethylene Z-ethyl acrylate copolymer (trade name: NUC Copolymer NUC-6221 manufactured by Nippon Yuka Ichi) was used. A styrenic elastomer composition was obtained.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 25,600 cc−20 ^ m / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and it was 32.6 Å.

Example 4

 The same procedure as in Example 1 was carried out except that 23 g of ethylene Z zinc methacrylate copolymer ionomer [Mitsui's Du Pont Polychemicals, trade name: Himilan 1706 Zn] was used as the resin compatibilizer. Thus, a styrene-based elastomer composition was obtained.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. The oxygen permeability coefficient P of the obtained film was measured by the method described above. However, it was 22,200 cc · 20 μττί / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and it was 32.8 angstroms.

Example 5

 Styrene-based elastomer composition in the same manner as in Example 1 except that 23 g of maleic anhydride-modified polypropylene [manufactured by Sanyo Chemical Industries, Ltd., trade name: Umex 1001] was used as the resin-based compatibilizer. I got

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 19,400 cc · 20 / zm / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was 33.4 Å.

Example 6

 As a resin compatibilizer, a polypropylene-poly (atalinoleic acid_ethy ^^ acrylate) type dibutanol copolymer synthesized according to the method described in Reference Example 7 of JP-A No. 10-306 196 [ Number average molecular weight of polypropylene block: 10,000, Number average molecular weight of poly (atacrylic acid / ethyl acrylate) block: 40,000, Structural unit derived from acrylic acid with respect to repeating unit of block copolymer Content: 8.1 mol%] A styrene-based elastomer composition was obtained in the same manner as in Example 1 except that 23 g was used.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 29,400 cc · 20 μηι / τη ² · day · atm. Further, the interlayer distance of the layered inorganic conjugate in the styrene-based elastomer composition was measured by the method described above, and was 32.6 Å.

Example 7

Polypropylene-poly (Z-ethyl acrylate acrylate) type dibutac copolymer synthesized as a resin compatibilizer according to the method described in Reference Example 7 of JP-A-10-306196. [Polypropylene block number average molecular weight: 10,000, Number average molecular weight of poly (Z-ethyl acrylate) block: 10,00

0, content of the structural unit derived from acrylic acid to the total repeating units of the block copolymer: 7 mole _^0/0] except for using 23 g in the same manner as in Example 1 styrene emissions elastomers first composition I got

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 16, OOO cc-20 μm / m ² · day · atm. Further, the interlayer distance of the layered inorganic conjugate in the styrene-based elastomer composition was measured by the method described above, and was 37.1 Å.

Example 8

As a resin-compatible agent, a polypropylene-poly (Z-ethyl acrylate) type jib mouth was synthesized according to the method described in Reference Example 7 of JP-A-10-306196. Block copolymer [Number-average molecular weight of polypropylene block: 4,000, Number-average molecular weight of poly (atalylic acid / ethyl acrylate) block: 4, 000, to acrylic acid for repeating unit of block copolymer derived structural unit containing Yuryou: 1 1 mole _^0/0] except for using 2 3 g was obtained a manner styrenic elastomer first composition as in example 1.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was found to be 12, OOO cc-20 μm / m ² · day · atm. The interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured to be 37.8 angstroms.

Example 9

 Synthetic mica treated with di (2-hydroxyethynole) methyldodecylammonium ion as a layered inorganic compound [: manufactured by Corp Chemical Co., Ltd., trade name: MEE; inorganic content: 70% by weight] 10 Example except that g was used and a hydrogenated product of polystyrene-polyisoprene-polystyrene-triploc copolymer [manufactured by Kuraray Co., Ltd., trade name: Septon 2007] was used as the styrene-based elastomer.

In the same manner as in 5, a styrene-based elastomer composition was obtained. Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, 9, 600 CC - a ^{20 M m / m 2 · day} · atm, as apparent from comparison with the pair Terurei 2 to be described later, Significant improvement in gasparability was observed. When the interlayer distance of the layered inorganic compound in the styrenic elastomer composition was measured by the method described above, the peak derived from synthetic mica completely disappeared in the X-ray diffraction pattern, and each layer of the layered inorganic compound was observed. Was completely peeled off. The interlayer distance is more than 44 angstroms.

Control 2

Using a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer [styrene-based elastomer; manufactured by Kuraray Co., Ltd., trade name: Septon 2007] using Labo Plastomill [manufactured by Toyo Seiki Seisakusho] After melting, the mixture was cooled to room temperature and then press-formed to produce a film. The oxygen permeability coefficient of the obtained film was measured by the method described above, 76, 400 cc - was ^{20 / m / m 2 · day} · atm.

Comparative Example 2 (1)

Unprocessed synthetic mica [Layered inorganic compound; hydrogenated product of 10 g of polystyrene-polyisoprene-polystyrene triblock copolymer [styrene-elastomer; Co., Ltd.] 67 g of Kuraray, trade name: SEBUTON 2007) was melt-kneaded using Labo Plastominore [manufactured by Toyo Seiki Seisakusho], and then cooled to room temperature to obtain a styrene-based elastomer composition. . Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 58,700 cc-20 / im / m ² · day · atm. The interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was found to be 12.1 angstroms.

Comparative Example 2 (2)

Synthetic mica treated with di (2-hydroxyethyl) methyldodecyl ammonium ion [manufactured by Corp Chemical Co., Ltd., trade name: MEE] 10 g and polystyrene-polypropylene Using a hydrogenated product of lysoprene-polystyrene triplep copolymer [styrene-based elastomer; Kuraray Co., Ltd., trade name: Septon 200 7] 67 g, using a lab blast mill [Toyo Seiki Seisakusho] The mixture was melted and kneaded, and then cooled to room temperature to obtain a styrene-based elastomer composition.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 48, OOO cc-20 μm / m ² · day · atm. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was 26.1 Å.

Comparative Example 2 (3)

 Synthetic mica treated with di (2-hydroxyethyl) methyldodecylammonium ion [manufactured by Corp Chemical Co., Ltd., trade name: MEE] Untreated synthetic mica instead of 10 g [layered inorganic compound; A styrene-based elastomer composition was obtained in the same manner as in Example 9 except that 10 g of a product manufactured by Corp Chemical, trade name: ME100) was used.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient of the obtained film P (cc · 2 Ο ιη / m 2 · day · atm) was measured by the method described above, 3 5, 500 cc - 20 / im / m 2 · day · atm met Was. The layer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was found to be 12.1 angstroms.

 For comparison, the X-ray diffraction pattern of a film (thickness: 0.1 mm) obtained from the styrene-based elastomer composition obtained in Example 9 and Comparative Example 2 (2) is shown in FIG. Shown in

Example 10

Styrene was prepared in the same manner as in Example 9 except that a hydrogenated product of polystyrene-polyisoprene-polystyrene block copolymer (manufactured by Kuraray Co., Ltd., trade name: Hibler 7 125) was used as the styrene-based elastomer. An elastomer composition was obtained. Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When obtained was measured with an oxygen permeability coefficient P was the method of film, 5, 300 cc - a ^{20 μ m / m 2 · day} · atm, as apparent from comparison with the pair Terurei 3 below, Significant improvement in gasparability was observed. When the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, the peak derived from synthetic mica completely disappeared in the X-ray diffraction pattern. It was confirmed that each layer of the product was completely peeled off. The interlayer distance is more than 44 angstroms.

Control 3

Using hydrogenated polystyrene-polyisoprene-polystyrene triblock copolymer [styrene-based elastomer; manufactured by Kuraray Co., Ltd., trade name: Hibler 71 25] using Labo Plast Mill [manufactured by Toyo Seiki Seisakusho] After melting, the mixture was cooled to room temperature and then press-formed to produce a film. The oxygen permeability coefficient of the obtained film was measured by the method described above, 54, 600 cc - dark 7 this in ^{20 / m / m 2 · day} · a tm.

Comparative Example 3 (1)

 Unprocessed synthetic mica [Layered inorganic compound; hydrogenated product of 10 g of polystyrene-polyisoprene-polystyrene block copolymer with trade name: ME100, manufactured by Corp Chemical Co., Ltd .; manufactured by Kuraray Co., Ltd. : Hybler 7 125] 67 g was melt-kneaded using a Labo Plastmill [: manufactured by Toyo Seiki Seisaku-sho, Ltd.], and then cooled to room temperature to obtain a styrene-based elastomer composition.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 32,700 cc <20 im / m ² · day · atm. Further, the interlayer distance of the layered inorganic conjugate in the styrene-based elastomer composition was measured by the method described above, and was 12.0 angstroms.

Comparative Example 3 (2)

Di (2-hydroxy E chill) methyl dodecyl ammonium Niu-ion treated with synthetic mica [Corporation OP Chemical Ltd., trade name: MEE; inorganic content: 70 wt _^0/0] Laboplus Tominore: 10 g and hydrogenated polystyrene-polyisoprene-polystyrene block copolymer [Kuraray Co., Ltd., trade name: Hybler 7 125] 67 g : Manufactured by Toyo Seiki Seisaku-sho, Ltd.), and then cooled to room temperature to obtain a styrene-based elastomer composition.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. In ^{20 / zm / m 2 · day} · a tm - oxygen permeability coefficient of the obtained film P (cc · 2 O / zm / m 2 · day · atm) was measured by the method described above, 26, 000 cc there were. Further, the interlayer distance of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was 24.9 angstroms.

Comparative Example 3 (3)

 Synthetic mica treated with di (2-hydroxyethyl) methyldodecylammonium ion [manufactured by Corp Chemical Co., Ltd., trade name: MEE] Untreated synthetic mica instead of 10 g [layered inorganic compound; A styrene-based elastomer composition was obtained in the same manner as in Example 10 except that 10 g of a product manufactured by Corp Chemical, trade name: ME100) was used.

Using the obtained styrene-based elastomer composition, press molding was performed to prepare a film. When the oxygen permeability coefficient P of the obtained film was measured by the method described above, it was 28, 100 cc '20 / ζm / m ² · day · atm. The distance between the eyebrows of the layered inorganic compound in the styrene-based elastomer composition was measured by the method described above, and was found to be 12.1 angstroms.

 For comparison, the X-ray diffraction patterns of the films (thickness: 0.1 mm) obtained from the styrene-based elastomer compositions obtained in Example 10 and Comparative Example 3 (2) are shown in FIG. (Figure 2).

 Further, the following observations were made in order to confirm the dispersion state of the styrene-based elastomer composition of the comparative example of the present invention.

A sheet (thickness: 1 mm) obtained from the styrene-based elastomer composition obtained in Example 10 and Comparative Example 3 (2) was freeze-thinned using an ultramicrotome (trade name, manufactured by Leica). After sectioning, stained with osmium and osmium Observation was performed using a microscope (TEM; H-800 NA type, manufactured by Hitachi, Ltd .; measurement conditions: acceleration voltage 100 KV). Cross-sectional photographs are shown in FIGS. 3 and 4, respectively.

 In FIG. 3, it can be understood that the layered inorganic compound completely peeled off between the eyebrows and was sufficiently dispersed in the styrene-based elastomer composition of Example 10. On the other hand, in FIG. 4, it is clear that the layered inorganic compound is not delaminated in the styrene-based elastomer composition of Comparative Example 3 (2).

 Industrial applicability

 According to the present invention, there is provided a styrene-based elastomer composition having improved gasparia properties and good mechanical properties.

This application is based on a priority application based on Japanese Patent Application No. 2002-147535 filed in Japan, the contents of which are incorporated in full herein. Further, the documents including patents and patent applications cited in this specification are incorporated in this specification to the same extent as if they were all disclosed by using Bow I.

Claims

The scope of the claims

1. (a) Styrenic elastomer,

 (b) a layered inorganic compound that has been organically delineated by an organic cation, and

 (c) a styrene-based elastomer composition comprising (a) a polar polymer having a polar functional group in a molecule and having compatibility with the styrene-based elastomer, wherein the ( b) A styrene-based elastomer composition, characterized in that the interlayer distance of the layered inorganic layered product obtained by the organic layering is not less than 15 angstroms.

2. The composition according to claim 1, wherein in the wide-angle X-ray diffraction measurement pattern, the peak (b) derived from the layered inorganic compound has completely disappeared.

3. said (a) a styrene-based elastomer and foremost, a polar functional group is E Rasutoma one of a proportion of less than 0.05 mole _^0/0 relative to the total molar amount of the repeating units constituting the elastomeric one The composition according to claim 1, wherein the composition is:

4. The composition according to any one of claims 1 to 3, wherein (b) the layered inorganic compound is organically formed by an organic cation containing a polar functional group in a molecule.

5. The organic cation is an organic cation having at least one polar functional group selected from a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, and an acid anhydride group in the molecule. 5. The composition according to claim 4, wherein the composition comprises

6. The polar polymer (c) is a polymer containing a polar functional group in an amount of 0.05 mol% or more based on the total molar amount of the repeating units constituting the polar polymer. The composition according to any one of claims 1 to 5.

7. The weight ratio of component (a), component (b) and component (c) is

Ingredient (b) / Ingredient (a) = 0.011 100 ~ 200/100, and

Component (c) Z component (a) = 0.011 100 ~ 500 OZ 100

The composition according to any one of claims 1 to 6, wherein

8. the oxygen permeability coefficient P of the styrene elastomer first composition, wherein (a) and styrene emissions elastomers one oxygen permeability coefficient p _E, the weight fraction wherein (b) a layered inorganic compound occupies in the polymer sets Narubutsu The composition according to any one of claims 1 to 7, wherein the following relational expression (1) is satisfied with the ratio F.

P x 0.5xP _TPE x (l-OF) / (1 + OF / 2) (1)

9. (a) Styrene-based elastomer,

 (b) a layered inorganic compound that has been organically delineated by an organic cation, and

 (c) a polar polymer having a polar functional group in a molecule, which is compatible with the (a) styrene-based elastomer,

Compounding by melt-kneading

The method for producing a composition according to claim 1, comprising:

10. (b) melt kneading the organically layered inorganic compound and (c) a polar polymer to prepare a composition, and

Melt kneading the composition with (a) a styrene-based elastomer;

The method for producing a composition according to claim 1, comprising:

1 1. An article comprising the styrenic elastomer composition according to any one of claims 1 to 8.

12. A gas barrier 'article comprising the styrenic elastomer composition according to any one of claims 1 to 8.

1 3. O-ring, no, The gas barrier article according to claim 12, which is a sealing material selected from a packing, a gasket, a lid material, a cap, and a cap liner.

14. The gas-parried article according to claim 13, wherein the sealing material is selected from a cap liner, a cap for a vacuum blood collection tube, a stopper, and a gasket for a syringe.