JP6837853B2 - Thermoplastic elastomer composition - Google Patents

Description

The present invention is useful for various molded products such as automobiles, electronic materials, home appliances, electrical equipment, medical tools, packaging materials, stationery and miscellaneous goods, and further, grips, tubes, packings, gaskets, cushions, films, sheets. The present invention relates to a thermoplastic elastomer composition used for various members such as, and a molded product obtained by using the composition.

Conventionally, as a polymer material having elasticity, rubbers obtained by blending rubbers such as natural rubber or synthetic rubber with a cross-linking agent or a reinforcing agent and cross-linking under high temperature and high pressure have been widely used. However, such rubbers require a process of cross-linking and molding for a long time under high temperature and high pressure, and are inferior in processability. Further, since the crosslinked rubber does not exhibit thermoplasticity, it is generally impossible to recycle molding like a thermoplastic resin. Therefore, in recent years, various thermoplastic elastomers have been developed that can easily manufacture molded products by using general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding in the same manner as ordinary thermoplastic resins. There is.

Conventionally, a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from isoprene or a mixture of isoprene and butadiene are contained, and 3,4-bonding units and 1,2-bonding units are contained. A thermoplastic elastomer composition containing a hydrogenated block copolymer having a polymer block (B) having a total unit content of 45% or more and a softening agent or a polyolefin resin is used as a medical sealant. It is known that it exhibits liquid leakage resistance and oxygen barrier property (see Patent Document 1).

On the other hand, Patent Document 2 is selected from a composition in which an isobutylene-based polymer having an alkenyl group at the terminal is crosslinked with a hydrosilyl group-containing polysiloxane, polybutene oil, a polyolefin resin, and an aromatic vinyl-based block copolymer. A thermoplastic elastomer composition having improved compressive permanent strain characteristics and gas barrier properties by using at least one of the components is disclosed.

Patent Document 3 discloses a thermoplastic resin composition containing a styrene-based block copolymer, an olefin-based resin, and a softening agent with a silicone compound as a slidability improver, thereby improving slipperiness. Is disclosed.

International Publication No. 2011/40586 Japanese Unexamined Patent Publication No. 2005-68224 Japanese Unexamined Patent Publication No. 2006-316804

However, the thermoplastic elastomer composition described in Patent Document 1 does not have sufficient compression-resistant permanent strain resistance, and when used for packing of a connection portion, the return of compression deformation is poor, a gap is formed in the connection portion, and a nipple is formed. The tube inserted into the tube may bend and block or fall out.

Further, the thermoplastic elastomer composition described in Patent Document 2 has poor melt fluidity and tends to have a rough surface when molded, and polybutene oil tends to bleed out, which may cause the surface of the molded product to become sticky. There is. Furthermore, although there is a description that the gas barrier property was measured with air by the JIS K 7126A method in the examples, there is no problem of the invention regarding the permeability of water vapor, and what kind of material exhibits the effect of moisture permeation resistance? Is not known about.

The thermoplastic resin composition described in Patent Document 3 is intended for use as a gasket for a plunger of a syringe, and its gas barrier property and water vapor barrier property have not been studied.

Generally, it is known that the smaller the gas molecule is, the easier it is to permeate the non-polar gas with respect to a single polymer material. However, in the case of an elastomer composition, the constituent components contained therein and how they are mixed. , Morphology and the like affect the permeability of the gas, so it is difficult to predict the permeability. In the case of a polar gas such as water vapor that permeates, the influence of the chemical composition becomes even greater, and the measurement conditions of 40 ° C and 90% relative humidity, which are conventionally specified by JIS K 7129, are common technical knowledge. There are no known issues or means of reducing the permeability of water vapor at higher temperatures.

On the other hand, not to mention automobile applications, even in home appliances, elastic parts are exposed to higher temperatures as home appliances become smaller and denser. Therefore, even in higher temperature environments, these are used. There is a demand for products that demonstrate the performance of. When the temperature rises, the saturated water vapor pressure rises exponentially, so for example, the saturated water vapor pressure at 70 ° C is about four times that at 40 ° C, which is sufficient performance in the conventional moisture permeation resistance test at 40 ° C. What was thought to be, can become unusable in hotter environments. That is, a thermoplastic elastomer composition and a molded product that exhibit high water vapor barrier properties even at high temperatures in addition to properties such as moldability, flexibility, and compression resistance to permanent strain are required.

The subject of the present invention is excellent moldability and flexibility, and has high compression constant strain resistance, gas barrier property, water vapor barrier property, and bleed resistance even at high temperatures, and further, in tube applications, slidability. An object of the present invention is to provide a thermoplastic elastomer composition having excellent wear resistance and kink resistance, and a molded product obtained by using the composition.

The present invention
[1] Component A: Contains a structural unit derived from an aromatic vinyl polymer block and a mixture of isoprene or isoprene and butadiene, and the total content of 1,2-bonding units and 3,4-bonding units is A hydrogenated block copolymer having an isoprene-based polymer block of 45 mol% or more, and a hydrogenated block copolymer having a weight average molecular weight of 150,000 to 500,000.
Ingredient B: Polybutene oil with kinematic viscosity of 3,000 to 20,000 mm ² / s at 40 ° C.
Ingredient C: Polyolefin,
Component D: Crosslinked isobutylene polymer D1, and / or triblock copolymer D2 composed of an aromatic vinyl polymer block and isobutylene polymer block, and component E: a slidability improver. And then
With respect to 100 parts by mass of the component A, the content of the component B is 10 to 200 parts by mass, the content of the component C is 1 to 200 parts by mass, the content of the component D is 50 to 1200 parts by mass, and the content of the component E is contained. A molded product comprising a thermoplastic elastomer composition having an amount of 1 to 150 parts by mass, and [2] the thermoplastic elastomer composition according to the above [1].
Regarding.

The thermoplastic elastomer composition of the present invention has the effects of being excellent in moldability and flexibility, and having high compression set resistance, gas barrier property, water vapor barrier property, and bleed resistance even at high temperatures. Furthermore, it has excellent slidability, wear resistance, and kink resistance, and is particularly excellent for tube applications.

The thermoplastic elastomer composition of the present invention (hereinafter, also referred to as the composition of the present invention) is
Component A: Contains structural units derived from aromatic vinyl polymer blocks and isoprene, or a mixture of isoprene and butadiene, with a total content of 1,2-bonding units and 3,4-bonding units of 45 mol%. A hydrogenated block copolymer having the above-mentioned isoprene-based polymer block, and a hydrogenated block copolymer having a weight average molecular weight of 150,000 to 500,000.
Ingredient B: Polybutene oil with kinematic viscosity of 3,000 to 20,000 mm ² / s at 40 ° C.
Ingredient C: Polyolefin,
Component D: Crosslinked isobutylene polymer D1, and / or triblock copolymer D2 composed of an aromatic vinyl polymer block and isobutylene polymer block, and component E: a slidability improver. It is something to do.

The hydrogenated block copolymer of component A is a hydrogenated block copolymer having an aromatic vinyl polymer block and an isoprene-based polymer block.

The aromatic vinyl polymer block contains a structural unit derived from the aromatic vinyl compound (hereinafter, also referred to as an aromatic vinyl compound unit). Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like, and two or more of these are used. It may be used together. Of these, styrene, which is easily available, is preferable.

The aromatic vinyl polymer block may contain a structural unit derived from a monomer other than the aromatic vinyl compound as long as the effects of the present invention are not impaired. Examples of other monomers include copolymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether, which can be ion-polymerized. The content of the aromatic vinyl compound unit in the total structural units constituting the aromatic vinyl polymer block is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more.

The isoprene-based polymer block contains a structural unit derived from isoprene or a mixture of isoprene and butadiene, and contains a high content of 1,2-bonding unit and 3,4-bonding unit. Structural units derived from isoprene (hereinafter, also referred to as isoprene units) include 1,2-bonding units, 3,4-bonding units, and 1,2, depending on the difference in carbon that binds to the structural units on both sides, as described below. 4-There is a binding unit. Of these, the 1,2-bonding unit and the 3,4-bonding unit are bulkier than the 1,4-bonding unit in the side chain due to hydrogenation because the carbon chain of the side chain contains a double bond. It will have an alkyl group. Similarly, structural units derived from butadiene (hereinafter, also referred to as butadiene units) also have 1,2-bonding units, 3,4-bonding units, and 1,4-bonding units, but 1,2-. The binding unit and the 3,4-bonding unit are regarded as substantially the same structural unit. In the present invention, the gas barrier property of the thermoplastic elastomer composition is improved by containing a large amount of 1,2-bonding units and 3,4-bonding units whose side chains become bulky due to hydrogenation.

The total content of the 1,2-bonding unit and the 3,4-bonding unit is 45 mol% or more, preferably 47 mol, in the total structural units constituting the isoprene-based polymer block from the viewpoint of gas barrier property. % Or more, more preferably 50 mol% or more, still more preferably 53 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, still more preferably 70 mol%. It is as follows. From these viewpoints, the total content of the 1,2-bonding unit and the 3,4-bonding unit is 45 mol% or more, preferably 47 to 95, based on the total structural units constituting the isoprene-based polymer block. It is mol%, more preferably 50 to 90 mol%, still more preferably 50 to 80 mol%, still more preferably 50 to 70 mol%, still more preferably 53 to 70 mol%.

When the isoprene-based polymer block contains both isoprene units and butadiene units, the molar ratio (isoprene units / butadiene units) is preferably 50/50 to 95/5, more preferably 60/40 to 90/10. , More preferably 70/30 to 85/15.

The bond form between the isoprene unit and the butadiene unit may be random, block, or tapered.

The isoprene-based polymer block may contain a structural unit derived from a monomer other than the isoprene unit and the butadiene unit as long as the effect of the present invention is not impaired. Other monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, 4-propylstyrene, Examples thereof include anion-polymerizable copolymerizable monomers such as aromatic vinyl compounds such as 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and 4- (phenylbutyl) styrene. From the viewpoint of gas barrier property, the total content of the isoprene unit or the content of the isoprene unit and the butadiene unit in all the structural units constituting the isoprene-based polymer block is preferably 80% by mass or more, more preferably 90% by mass. % Or more, more preferably 95% by mass or more.

In the present invention, the block copolymer having an aromatic polymer block and an isoprene-based polymer block is hydrogenated (sometimes abbreviated as "hydrogenation"), and is substantially an isoprene-based weight. Part or all of the unsaturated double bond (carbon-carbon double bond) in the coalesced block is hydrogenated. The hydrogenation rate of the isoprene-based polymer block is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, still more preferably 80% or more. The hydrogenation rate may be described as "hydrogenation rate of hydrogenated block copolymer".

The hydrogenated block copolymer may have a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group at the molecular chain and / or at the end of the molecule as long as the effect of the present invention is not impaired. It may have one kind or two or more kinds of.

The hydrogenated block copolymer is a hydrogenated additive of a block copolymer containing at least one aromatic vinyl polymer block and one isoprene-based polymer block, preferably two or more aromatic vinyl polymer blocks. It is a hydrogenated additive of a block copolymer containing at least one block of isoprene-based polymer. The bonding form of the aromatic vinyl polymer block and the isoprene-based polymer block is not particularly limited, and may be linear, branched, radial, or a bonding form in which two or more of them are combined. , The linearly bonded form is preferable, and when the aromatic vinyl polymer block is represented by "A" and the isoprene-based polymer block is represented by "B", ( _{AB) l} , A- (BA). _{It is preferable that the bond form is m} , B- (AB) _n (in the formula, l, m and n each independently represent an integer of 1 or more), and rubber elasticity, mechanical properties, handleability, etc. From the viewpoint of, _{it is more preferable that the bonded form is represented by (AB) l} and A- (BA) _m , and the diblock structure represented by AB or represented by ABA. It is more preferable that the triblock structure is bonded.

When the hydrogenated block copolymer has two or more aromatic vinyl polymer blocks or two or more isoprene-based polymer blocks, the aromatic vinyl polymer blocks and the isoprene-based polymer blocks are mutually exclusive. The blocks may have the same configuration or blocks having different configurations. For example, in the two aromatic vinyl polymer blocks in the triblock structure represented by [ABA], the types of aromatic vinyl compounds constituting them may be the same or different. Good.

The content of the aromatic vinyl polymer block in the hydrogenated block copolymer of component A is preferably 5 to 70% by mass or more, more preferably 15 to 50% by mass or more, from the viewpoint of flexibility and compression set. More preferably, it is 15 to 35% by mass or more.

In the hydrogenated block copolymer of component A, the mass ratio of the aromatic vinyl polymer block to the isoprene-based polymer block (aromatic vinyl polymer block / isoprene-based polymer block) is determined from the viewpoint of flexibility and gas barrier property. , Preferably 5/95 to 70/30, more preferably 15/85 to 50/50, and even more preferably 15/85 to 35/65.

The weight average molecular weight of the hydrogenated block copolymer of component A is 150,000 or more from the viewpoint of improving compression set resistance and bleed resistance, and 500,000 or less from the viewpoint of fluidity and moldability. From these viewpoints, the weight average molecular weight of the hydrogenated block copolymer of component A is 150,000 to 500,000, preferably 160,000 to 400,000, and more preferably 170,000 to 350,000.

The content of the component A in the composition of the present invention is preferably 5% by mass or more from the viewpoint of bleed resistance, and preferably 80% by mass or less from the viewpoint of water vapor barrier property. From these viewpoints, the content of the component A is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, still more preferably 7 to 65% by mass, still more preferably 10 to 10 to 80% by mass in the composition of the present invention. It is 50% by mass.

Ingredient B is polybutene oil. Polybutene oil is effective in improving the flexibility of the composition, has good compatibility with the composition and is easy to mix, and has a higher gas barrier property than other softeners such as paraffin oil. Further, by using an polybutene oil having a high kinematic viscosity, the bleeding resistance is improved and the stickiness of the surface of the molded product due to the oil bleeding is suppressed.

^{The kinematic viscosity of polybutene oil at 40 ° C is 3,000 mm 2} / s or more from the viewpoint of improving long-term heat resistance and bleed resistance, and ^{20,000 mm 2} / s from the viewpoint of slidability, moldability and gas barrier properties. It is less than or equal to s. From these viewpoints, the kinematic viscosity of polybutene oil at 40 ° C. is 3,000 to 20,000 mm ² / s, preferably 4,000 to 17,500 mm ² / s, and more preferably 5,000 to 15,000 mm ² / s.

The content of component B is 10 parts by mass or more with respect to 100 parts by mass of component A from the viewpoint of flexibility and dispersibility during melt-kneading, and has moldability, bleed resistance, abrasion resistance, and slidability. And, from the viewpoint of gas barrier property, it is 200 parts by mass or less. From these viewpoints, the content of the component B is 10 to 200 parts by mass, preferably 15 to 100 parts by mass, and more preferably 20 to 75 parts by mass with respect to 100 parts by mass of the component A. When the crosslinked isobutylene polymer D1 described later is used as a melt-mixed mixture with the component B in advance, the component B contained in the crosslinked isobutylene polymer D1 is the crosslinked isobutylene polymer D1. It is considered to be blended as a part and is not included in the content of component B in the composition of the present invention.

The content of the component B is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass in the composition of the present invention.

Component C is a polyolefin.

Examples of the polyolefin include polyethylene, polypropylene, and an ethylene-propylene copolymer. Among these, polypropylene is preferable from the viewpoint of abrasion resistance, slidability, and kink resistance.

The melting point of the polyolefin is preferably 140 ° C. or higher from the viewpoint of long-term heat resistance, and preferably 200 ° C. or lower from the viewpoint of moldability. From these viewpoints, the melting point of the polyolefin is preferably 140 to 190 ° C, more preferably 145 to 185 ° C, still more preferably 150 to 180 ° C.

The melt mass flow rate of the polyolefin at 230 ° C. and 21 N is preferably 0.1 g / 10 min or more from the viewpoint of moldability, and preferably 100 g / 10 min or less from the viewpoint of heat resistance. From these viewpoints, the melt mass flow rate of the polyolefin at 230 ° C. and 21 N is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 80 g / 10 min, and further preferably 1.0 to 50 g / 10 min.

The flexural modulus of polyolefin is preferably 30 MPa or more from the viewpoint of gas barrier properties, and preferably 2500 MPa or less from the viewpoint of flexibility. From these viewpoints, the flexural modulus of polyolefin is preferably 30 to 2000 MPa, more preferably 100 to 1850 MPa, and even more preferably 200 to 1700 MPa.

The content of component C is 1 part by mass or more from the viewpoint of dispersibility during melt-kneading with respect to 100 parts by mass of component A, and 200 parts by mass or less from the viewpoint of flexibility and compression set resistance. is there. From these viewpoints, the content of component C is 1 to 200 parts by mass, preferably 5 to 175 parts by mass, more preferably 10 to 150 parts by mass, and further preferably 15 parts by mass with respect to 100 parts by mass of component A. It is ~ 100 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 20 to 50 parts by mass. When the crosslinked isobutylene polymer D1 described later is used as a melt-mixed mixture with the component C in advance, the component C contained in the crosslinked isobutylene polymer D1 is the crosslinked isobutylene polymer D1. It is considered to be blended as a part and is not included in the content of component C in the composition of the present invention.

The content of the component C is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass in the composition of the present invention.

The component D is a crosslinked isobutylene polymer D1 and / or a triblock copolymer D2 composed of an aromatic vinyl polymer block and an isobutylene polymer block.

The isobutylene polymer contains a structural unit derived from isobutylene (hereinafter, also referred to as an isobutylene unit).

The isobutylene-based polymer may contain a structural unit derived from a monomer other than isobutylene as long as the effects of the present invention are not impaired. Examples of other monomers include aliphatic olefins, alicyclic olefins, aromatic vinyls, dienes, vinyl ethers, silanes, vinylcarbazoles, β-pinenes, acenaftylene and the like. The content of the isobutylene unit in all the structural units constituting the isobutylene polymer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass from the viewpoint of water vapor barrier property at high temperature. % Or more.

From the viewpoint of hygiene and compression resistance, the crosslinked isobutylene polymer D1 is preferably a hydrosilylated crosslinked isobutylene polymer having an allyl group.

The isobutylene-based polymer having an allyl group can be obtained by introducing an allyl group into the isobutylene-based polymer by the following method or the like. As a method of introducing an unsaturated group into a polymer having a functional group such as a hydroxyl group, a method of reacting a polymer having a functional group such as a hydroxyl group with a compound having an unsaturated group to introduce an unsaturated group into the polymer. And so on. Further, as a method for introducing an unsaturated group into a polymer having a halogen atom, there are various methods such as a Friedel-Crafts reaction with an alkenylphenyl ether and a substitution reaction with an allyltrimethylsilane or the like in the presence of Lewis acid. Examples thereof include a method of carrying out a Friedel-Crafts reaction with the phenols of the above to introduce a hydroxyl group and then further carrying out the above-mentioned alkenyl group introduction reaction.

The amount of allyl groups in the isobutylene-based polymer can be arbitrarily selected depending on the required properties, but from the viewpoint of the properties after cross-linking, the isobutylene-based polymer having an allyl group has at least 0.2 allyls per molecule. A polymer having a group at the end is preferable, a polymer having 1.0 or more allyl groups per molecule at the end is more preferable, and a polymer having 1.5 or more allyl groups per molecule at the end is preferable. Is more preferable. The amount of allyl groups in the isobutylene polymer ^{can be measured by 1} H-NMR spectral analysis.

The hydrosilylation cross-linking of the isobutylene polymer can be carried out, for example, by melt-kneading with an extruder using a cross-linking agent having a plurality of hydrosilyl groups in the molecule and a platinum-based catalyst.

The cross-linking reaction improves the compression-resistant permanent strain resistance and heat resistance of the polymer, but at the same time, the hardness and melt viscosity also increase. Therefore, when the component D is used as the composition of the elastomer composition, the molecular weight after cross-linking is adjusted. It is preferable to use it as an index of selection from the viewpoint of blending without disturbing the physical property balance of the entire composition.

The weight average molecular weight of the crosslinked isobutylene polymer D1 is preferably 50,000 or more from the viewpoint of suppressing compression set, and preferably 500,000 or less from the viewpoint of moldability. From these viewpoints, the weight average molecular weight of the crosslinked isobutylene polymer D1 is preferably 50,000 to 500,000, more preferably 55,000 to 450,000, still more preferably 75,000 to 425,000, still more preferably 100,000 to 400,000.

The triblock copolymer D2 having an aromatic vinyl polymer block and an isobutylene polymer block is preferably composed of two aromatic vinyl polymer blocks and one isobutylene polymer block. It is more preferable that the isobutylene-based polymer block is provided with aromatic vinyl polymer blocks on both sides.

The aromatic vinyl polymer block contains an aromatic vinyl compound unit. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like, and two or more of these are used. It may be used together. Of these, styrene, which is easily available, is preferable.

The aromatic vinyl polymer block may contain a structural unit derived from a monomer other than the aromatic vinyl compound as long as the effects of the present invention are not impaired. Examples of other monomers include copolymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether, which can be ion-polymerized. The content of the aromatic vinyl compound unit in the total structural units constituting the aromatic vinyl polymer block is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more.

The isobutylene polymer block contains isobutylene units.

The isobutylene-based polymer block may contain a structural unit derived from a monomer other than isobutylene as long as the effects of the present invention are not impaired. Examples of other monomers include aliphatic olefins, alicyclic olefins, aromatic vinyls, dienes, vinyl ethers, silanes, vinylcarbazoles, β-pinenes, acenaftylene and the like. The content of the isobutylene unit in all the structural units constituting the isobutylene-based polymer block is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70 from the viewpoint of water vapor barrier property at high temperature. It is by mass% or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more.

The content of the isobutylene polymer block contained in the triblock copolymer D2 is preferably 50% by mass or more from the viewpoint of water vapor barrier property at high temperature, and 90% by mass or less from the viewpoint of bleed resistance. .. From these viewpoints, the content of the isobutylene polymer block contained in the triblock copolymer D2 is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, and further preferably 60 to 80% by mass. is there.

The mass ratio of the isobutylene-based polymer block to the aromatic vinyl polymer block (isobutylene-based polymer block / aromatic vinyl polymer block) in the triblock copolymer D2 is determined from the viewpoint of water vapor barrier property at high temperature. It is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and even more preferably 60/40 to 80/20.

The weight average molecular weight of the triblock copolymer D2 is preferably 50,000 or more from the viewpoint of suppressing compression set, and preferably 500,000 or less from the viewpoint of moldability. From these viewpoints, the weight average molecular weight of the triblock copolymer D2 is preferably 50,000 to 500,000, more preferably 60,000 to 400,000, and even more preferably 70,000 to 300,000.

The content of the component D is 50 to 1200 parts by mass with respect to 100 parts by mass of the component A, and when both are used in combination, the total amount thereof shall be in the above range.
When the crosslinked isobutylene polymer D1 is contained alone, the content thereof is 50 parts by mass or more with respect to 100 parts by mass of the component A from the viewpoint of water vapor barrier property at high temperature, and molding is performed. From the viewpoint of smoothing the surface of the body and improving the appearance, it is 1200 parts by mass or less. From these viewpoints, the content of the crosslinked isobutylene polymer D1 is 50 to 1200 parts by mass, preferably 100 to 1100 parts by mass, and more preferably 200 to 1000 parts by mass with respect to 100 parts by mass of the component A. It is a department.
When the triblock copolymer D2 is contained alone, the content thereof is 50 parts by mass or more with respect to 100 parts by mass of the component A from the viewpoint of water vapor barrier property at high temperature, and the compression resistance is permanent. From the viewpoint of strainability, it is 1200 parts by mass or less. From these viewpoints, the content of the triblock copolymer D2 is 50 to 1200 parts by mass, preferably 100 to 1100 parts by mass, and more preferably 200 to 1000 parts by mass with respect to 100 parts by mass of the component A. is there.

The content of the component D is preferably 5 to 90% by mass, more preferably 10 to 85% by mass in the composition of the present invention.

Component E is a slidability improver. Examples of the slidability improving agent include higher alcohols, fatty acids, fatty acid amides, metal soaps, polyolefin waxes, organopolysiloxanes, polytetrafluoroethylenes, polyalkylene glycols, etc. Among these, from the viewpoint of heat resistance, At least one selected from the group consisting of metal soap, fatty acid amide, and organopolysiloxane is preferable, and organopolysiloxane is more preferable.

Examples of the higher alcohol include stearyl alcohol, and alcohols having 8 to 22 carbon atoms are preferable.

Examples of the fatty acid include stearic acid and 1,2-hydroxystearic acid, and fatty acids having 9 to 23 carbon atoms are preferable.

Examples of the fatty acid amide include oleic acid amide, stearic acid amide, erucic acid amide, methylene bisstearic acid amide, and ethylene bisstearic acid amide.

Examples of the metal soap include magnesium stearate, calcium stearate, zinc stearate, lead stearate, aluminum stearate, barium stearate, barium stearate / zinc complex, zinc stearate / calcium stearate complex and the like.

Examples of the organopolysiloxane include so-called silicone oil (E-1) having a polysiloxane bond as a main chain and an organic group in a side chain. Examples of the organic group include a methyl group, a vinyl group, an ethyl group, a propyl group, a phenyl group, a fluoroalkyl group and the like, and the polysiloxane bond may have a branch.

Specific examples of the silicone oil include dimethyl silicone, methyl phenyl silicone, methyl hydrogen silicone and the like, and among these, dimethyl silicone is preferable.

The silicone oil (E-1) in the present invention has a weight average molecular weight of about 10,000 to 1,000,000, more preferably an ultrahigh molecular weight of 100,000 to 800,000, among the silicone oils, from the viewpoint of bleed resistance. Is preferable. Such ultra-high molecular weight silicone oils are sometimes called silicone gums because they are viscous to be called silicone oils and have high fluidity to be called silicone rubbers at room temperature (25 ° C.). CF-9150 "(manufactured by Toray Dow Corning Silicone Co., Ltd., weight average molecular weight of 100,000 or more, kinematic viscosity at 25 ° C 1 million mm ² / s) and" X21-3043 "(manufactured by Shinetsu Silicone Co., Ltd., Weight average molecular weight 100,000 or more, kinematic viscosity at 25 ° C 1 million mm ² / s), "TSF-451-10M" (manufactured by Momentive Performance Materials Co., Ltd., number average molecular weight 100,000, kinematic viscosity at 25 ° C 100,000 mm ² / s) etc. are known. These commercially available ultra-high molecular weight silicones are linear polymers of dimethyl silicone, and it is known that the molecular weight and the kinematic viscosity show an almost linear interphase relationship. Therefore, specify the kinematic viscosity instead of the molecular weight. You can also. In terms of kinematic viscosity, the kinematic viscosity is preferably 50 to 5 million mm ² / s at 25 ° C, more preferably 10,000 to 2 million mm ² / s.

Silicone oil has a smaller change in kinematic viscosity with respect to temperature changes than petroleum-based oil, and even if the temperature is raised, the viscosity does not decrease and it may be difficult to disperse in other materials. From the viewpoint of uniform dispersion, it is preferable to use a master batch that has been mixed with a thermoplastic resin, inorganic oxide particles, or the like in advance. Master batches include "BY27-001" (manufactured by Toray Dow Corning Silicone Co., Ltd., 50/50 composition of dimethyl silicone (mass average molecular weight 420,000) and polypropylene) and "GENIO PLAST Pellet S" (Asahi Kasei Wacker Silicone (Asahi Kasei Wacker Silicone). A 70/30 (dimethylsilicone / fumed silica) composition of dimethylsilicone having a kinematic viscosity of 100,000 mm ^{2 / s or more at 25 ° C and fumed silica manufactured by Co., Ltd.) is known, and the present invention} In the above, it is preferably used because it can be quickly dispersed when the composition is produced. Among such master batches, a composite of silicone oil and inorganic oxide particles is preferable, and as the inorganic oxide particles, SiO ₂ is preferable from the viewpoint of compatibility with silicone oil, and the dispersibility is high. From the viewpoint, fine particle fumed silica having a particle size of about 1 to 100 nm is more preferable, and hydrophobic fumed silica whose surface is treated with organic silane, silazane or the like to improve dispersibility is further preferable. The content of the inorganic oxide particles in such a masterbatch is 10 to 50% by mass, more preferably 20 to 40% by mass in the entire complex with the silicone oil.

Further, as a preferable organopolysiloxane other than silicone oil, there is a copolymer (E-2) of a polyorganosiloxane structure and another organic monomer, and a polyorganosiloxane and an alkyl (meth) acrylate are used. Examples thereof include copolymers. Commercially available copolymers of polyorganosiloxane and alkyl (meth) acrylate include "Metabrene S2001", "SRK200A", "SX-005" (manufactured by Mitsubishi Rayon Co., Ltd.), and "Charine R-". Examples include "180S", "Charine R-170", and "Charine R-170S" (manufactured by Nissin Chemical Industry Co., Ltd.).

That is, among the organopolysiloxanes, silicone oil (E-1) and a copolymer (E-2) of a polyorganosiloxane structure and another organic monomer can be mentioned (E). Among -1), the preferred one is ultrahigh molecular weight silicone and its master batch, and among (E-2), the preferred one is a copolymer of polyorganosiloxane and alkyl (meth) acrylate.

The content of component E is 1 part by mass or more from the viewpoint of slidability, wear resistance and moldability with respect to 100 parts by mass of component A, and 150 parts by mass from the viewpoint of gas barrier property, kink resistance and the like. It is less than a part. From these viewpoints, the content of component C is 1 to 150 parts by mass, preferably 5 to 130 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 20 parts by mass with respect to 100 parts by mass of component A. ~ 60 parts by mass.

The content of the component E is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass in the composition of the present invention.

The composition of the present invention preferably contains component F: polyphenylene ether from the viewpoint of surface smoothness of the molded product.

The reduced viscosity of polyphenylene ether shall be the viscosity of a solution dissolved in chloroform at a concentration of 0.5 g / dL at 30 ° C. by a method conforming to JIS K 7367. From the viewpoint of compatibility, 0.1 or more is preferable, and from the viewpoint of dispersibility and surface property of the molded product, less than 0.45 is preferable. From these viewpoints, the reducing viscosity of the polyphenylene ether is preferably 0.1 to 0.45, more preferably 0.15 to 0.45, and even more preferably 0.2 to 0.45.

The glass transition temperature of the polyphenylene ether is preferably 170 ° C. or higher from the viewpoint of heat resistance, and preferably 260 ° C. or lower from the viewpoint of moldability. From these viewpoints, the glass transition temperature of the polyphenylene ether is preferably 170 to 260 ° C, more preferably 180 to 250 ° C, and even more preferably 190 to 240 ° C.

The volume median particle diameter of the polyphenylene ether is preferably 0.1 μm or more from the viewpoint of dispersibility, and is preferably 1000 μm or less from the viewpoint of productivity (classification). From these viewpoints, the volume median particle size of the polyphenylene ether is preferably 0.1 to 1000 μm, more preferably 10 to 800 μm, and even more preferably 50 to 500 μm.

The content of the component F is preferably 1 part by mass or more from the viewpoint of surface smoothness of the molded product, and preferably 100 parts by mass or less from the viewpoint of compression set with respect to 100 parts by mass of the component A. From these viewpoints, the content of the component F is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and further preferably 10 to 70 parts by mass with respect to 100 parts by mass of the component A.

The content of the component F is preferably 0.1 to 30% by mass, more preferably 1.0 to 15% by mass in the composition of the present invention.

From the viewpoint of water vapor barrier property, the composition of the present invention preferably contains component G: an inorganic filler.

Inorganic fillers include talc, mica, calcium carbonate, clay, titanium oxide, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium oxide, iron oxide, Zinc oxide, alumina, silica, diatomaceous soil, dolomite, gypsum, calcined clay, asbestos, calcium silicate, bentonite, white carbon, carbon black, iron powder, aluminum powder, stone powder, blast furnace slag, fly ash, cement, zirconia powder, etc. Among these, talc is preferable from the viewpoint of water vapor barrier property and dispersibility.

Various shapes such as granular, plate-shaped, rod-shaped, fibrous, and whisker-shaped are known as the inorganic filler, but in the present invention, the plate-shaped one is preferable from the viewpoint of water vapor barrier property and gas barrier property. .. The plate shape means a shape in which the ratio of major axis to thickness (major axis / thickness) is 5 or more, preferably 10 to 500.

The volume median particle diameter of the plate-shaped inorganic filler is preferably 1.5 μm or more from the viewpoint of dispersibility, and is preferably 150 μm or less from the viewpoint of flexibility. From these viewpoints, the volume median particle diameter of the plate-shaped inorganic filler is preferably 1.5 to 150 μm, more preferably 1.75 to 120 μm, and further preferably 2.0 to 15 μm.

The content of the component G is preferably 1 part by mass or more from the viewpoint of water vapor barrier property, and preferably 500 parts by mass or less from the viewpoint of the surface property of the molded product with respect to 100 parts by mass of the component A. From these viewpoints, the content of the component G is preferably 1 to 500 parts by mass, more preferably 20 to 400 parts by mass, and further preferably 50 to 350 parts by mass with respect to 100 parts by mass of the component A. When the inorganic filler is plate-shaped, it is preferably 250 parts by mass or less, more preferably 200 parts by mass or less, from the viewpoint of water vapor barrier property and tube smoothness.

The content of the component G is preferably 1 to 50% by mass, more preferably 5 to 35% by mass in the composition of the present invention.

The composition of the present invention is, if necessary, a reinforcing agent such as carbon black, silica, carbon fiber, glass fiber, etc., as long as the effect of the present invention is not impaired; an insulating heat conductive filler, a pigment, a flame retardant, and a charge. It may contain various additives such as an inhibitor, a mold release agent, a tackifier, a cross-linking agent, a cross-linking aid, a foaming agent, and a fragrance.

The composition of the present invention may contain other thermoplastic resins or thermoplastic elastomers as long as the effects of the present invention are not impaired.

Further, the composition of the present invention may contain a polar elastomer for the purpose of modifying the polar resin. The polar elastomer is not particularly limited, and examples thereof include NBR (nitrile rubber), polyurethane rubber, epichlorohydrin rubber, polyurethane-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer.

The composition of the present invention is preferably obtained by a method of heating and kneading a raw material mixture containing components A to E, and if necessary, component F, component G, and the like with an extruder or a kneader.

The term "mixing" as used in the present invention is not particularly limited as long as it is a method in which various components are mixed well, and various components may be dissolved in a soluble organic solvent and mixed, or the raw material may be heated. Then, it may be mixed by melt-kneading.

In the present invention, when the component D contains the crosslinked isobutylene polymer D1, the isobutylene polymer is crosslinked by being melt-mixed with at least a part of the polybutene oil of the component B and / or the polyolefin of the component C. Is preferable. Flexibility is improved by melting and mixing the isobutylene polymer with the component B in advance. Further, by melt-mixing the isobutylene polymer with the component C, the long-term heat resistance is improved. However, the amounts of the components B and C are treated as the total amount of the crosslinked isobutylene polymer D1 including these. Therefore, the amounts of the components B and C here are not added to the amounts of the components B and C used alone.

The amount of the component B previously melt-mixed with the crosslinked isobutylene polymer D1 is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the crosslinked isobutylene polymer D1. It is a department. The amount of the component C previously melt-mixed with the crosslinked isobutylene polymer D1 is preferably 1 to 20 parts by mass, more preferably 3 to 3 to 100 parts by mass with respect to 100 parts by mass of the crosslinked isobutylene polymer D1. 15 parts by mass.

"SIBSTAR P1140B" (manufactured by Kaneka Corporation) or the like can also be used as a commercially available product in which such an isobutylene polymer D1 is previously melt-mixed with the component B and the component C.

Examples of the extruder include a single-screw extruder, a parallel screw twin-screw extruder, a conical screw twin-screw extruder and the like. In the present invention, a twin-screw extruder is preferable, and a co-rotating twin-screw extruder is more preferable, from the viewpoint of excellent mixing ability (the obtained mixture has good dispersibility).

Any die can be selected as the die attached to the discharge portion of the extruder. For example, a strand die suitable for pellet production, a T die suitable for sheet or film production, a pipe die, a deformed extrusion die, etc. are used. Can be mentioned.

Further, the extruder may be provided with a vent for venting a gas connected to an air opening portion or a decompression device, or may be provided with a plurality of raw material inlets.

The kneader means a batch type mixer capable of temperature control, and examples thereof include a Banbury mixer, a lavender plast graph, and a lab plast mill.

Each component may be charged into the extruder or kneader all at once, separately, or separately.

The composition of the present invention can be in the form of pellets, powders, sheets, etc., depending on the intended use. For example, it is melt-kneaded by an extruder and extruded into a strand, and while being cooled in cold water, it is cut into pellets such as cylinders and rice granules by a cutter. The obtained pellets are usually made into a predetermined sheet-shaped molded product or mold-molded product by injection molding or extrusion molding. Further, the melt-kneaded product can be pelletized with a ruder or the like and used as a raw material for molding. It may be an intermediate product in which a mount or the like is attached to a sheet-shaped thermoplastic elastomer composition.

The composition of the present invention is not particularly limited, and can be used in fields in which general styrene-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, polyester-based elastomers, and the like are used. ..

From the viewpoint of flexibility, the A hardness of the composition of the present invention is preferably 10 to 95, more preferably 20 to 90, and even more preferably 40 to 90.

A molded product can be obtained by appropriately heat-molding the composition of the present invention according to a conventional method.

The temperature at the time of heat molding is preferably 150 to 250 ° C., more preferably 170 to 230 ° C. from the viewpoint of the appearance of the molded product.

As the apparatus used for producing a molded product using the composition of the present invention, any molding machine capable of melting the molding material can be used. For example, a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, a mixing roll and the like can be mentioned.

Specific examples of the shape of the molded product using the composition of the present invention include a tubular molded product, a sealing molded product, a sheet-shaped molded product, and the like. The tubular molded body includes a tube for an inkjet recording device, a catheter, a tube for infusion, a tube for peritoneal dialysis, a tube for blood transfusion, a medical tube such as a blood circuit tube used for artificial cardiopulmonary and hemodialysis, gas, liquid, and semi-solid. And can be used as various industrial tubes and the like used for transferring a mixture of these. Further, the sealing molded body can be used as various packings, seals, gaskets, sealing materials for solar cells, liner materials for foods, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Various physical properties of the raw materials used in Examples and Comparative Examples were measured by the following methods.

<Component A and Component A'>
[Content of aromatic vinyl compound unit in aromatic vinyl polymer block]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Total content of 1,2-bonding unit and 3,4-bonding unit in isoprene-based polymer block]
The block copolymer before hydrogenation was dissolved in _{CDCl 3} ^{and 1} H-NMR spectrum was measured [Equipment: JNM-Lambda 500 (manufactured by Nippon Denshi Co., Ltd.), measurement temperature: 50 ° C], and isoprene, butadiene, or Total peak area of structural units derived from a mixture of isoprene and butadiene, 1,2-bonding units and 3,4-bonding units in isoprene units, 1,2-bonding units in butadiene units, and in the case of a mixture of isoprene and butadiene The total content of 3,4-bonding unit and 1,2-bonding unit is calculated from the ratio of the peak areas corresponding to each of the binding units.
[Hydrogenation rate of hydrogenated block copolymer]
The iodine value of the block copolymer before and after hydrogenation is measured, and the hydrogenation rate (%) of the hydrogenated block copolymer is calculated from the following formula.

[Content of isoprene unit and / or butadiene unit in isoprene-based polymer block]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Contents of aromatic vinyl polymer block and isoprene polymer block in block copolymer]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Weight average molecular weight of block copolymer (Mw)]
Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by a gel permeation chromatograph to determine the weight average molecular weight.
Measuring device / pump: JASCO (JASCO Corporation), PU-980
・ Column oven: Showa Denko KK, AO-50
・ Detector: Hitachi, RI (Differential Refractometer) Detector L-3300
-Column type: Showa Denko Corporation "K-805L (8.0 x 300 mm)" and "K-804 L (8.0 x 300 mm)" are used in series.-Column temperature: 40 ° C
・ Guard column: KG (4.6 x 10 mm)
・ Eluent: Chloroform ・ Eluent flow rate: 1.0 ml / min
・ Sample concentration: Approximately 1 mg / ml
・ Sample solution filtration: Polytetrafluoroethylene 0.45 μm pore size disposable filter ・ Standard sample for calibration curve: Polystyrene manufactured by Showa Denko KK

<Component B and component B'>
[Kinematic viscosity]
Measure at a temperature of 40 ° C according to JIS Z 8803.

<Component C>
[Melting point]
The melting point is defined as the temperature of the melting peak obtained by raising the temperature at 10 ° C / min in accordance with the method specified in JIS K 7121 using a differential scanning calorimetry (DSC) device. When multiple melting peaks appear, the melting peak that appears at a lower temperature is taken as the melting point.
[Melt Mass Flow Rate (MFR)]
Measure at 230 ° C by a method according to ASTM D 1238.
[Flexural modulus]
Measure according to JIS K7171.

<Component D and Component D'>
[Content of isobutylene unit in crosslinked isobutylene polymer D1]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Weight average molecular weight (Mw) of crosslinked isobutylene polymer D1]
It is measured in polystyrene conversion by gel permeation chromatography (GPC) measurement using chloroform as an eluent.
[Content of aromatic vinyl compound unit in aromatic vinyl polymer block of triblock copolymer D2]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Content of isobutylene unit in isobutylene-based polymer block of triblock copolymer D2]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Contents of aromatic vinyl polymer block and isobutylene polymer block contained in triblock copolymer D2]
Measurement is performed using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER, Germany).
[Weight average molecular weight (Mw) of triblock copolymer D2]
It is measured in polystyrene conversion by gel permeation chromatography (GPC) measurement using chloroform as an eluent.

<Component E>
[Kinematic viscosity]
Measure at 25 ° C with a B-type viscometer according to JIS Z8803. The silicone oil masterbatch is a measured value of the silicone oil alone before the masterbatch.

<Component F>
[Reduced viscosity]
The viscosity of a solution dissolved in chloroform at a concentration of 0.5 g / dL at 30 ° C. is measured by a method conforming to JIS K 7367.
[Glass transition temperature (Tg)]
Measure by DSC method according to JIS K 7121.
[Medium volume particle size]
_{The cumulative 50% particle size D 50} based on the volume is measured by the laser diffraction method by a method conforming to JIS Z 8825.

<Component G>
[Medium volume particle size]
_{The cumulative 50% particle size D 50} based on the volume is measured by the laser diffraction method by a method conforming to JIS Z 8825.

Examples 1-27 and Comparative Examples 1-14 (Examples 22 and 26 are reference examples)
(1) Preparation of Thermoplastic Elastomer Composition (Pellet) The raw material components were put into a mixer at the composition ratios (mass ratios) shown in Tables 8 to 13 and premixed. Then, the obtained mixture was melt-kneaded by a twin-screw extruder (continuous kneader) under the following conditions to produce pellets of a thermoplastic elastomer composition.
・ Extruder: KZW32TW-60MG-NH (manufactured by Technobel Co., Ltd.)
・ Cylinder temperature: 180-240 ℃
・ Screw rotation speed: 300r / min

Details of the raw material components used in Examples and Comparative Examples are shown in Tables 1 to 7.

(2) Preparation of molded product
(2-1) Injection-molded pellets were injection-molded under the following conditions to prepare a plate having a width of 125 mm, a length of 125 mm, and a thickness of 2 mm.
[Injection molding conditions]
Injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.)
Injection molding temperature: 200 ° C
Injection pressure: 30%
Injection time: 10 sec
Mold temperature: 40 ℃

(2-2) Press-molded pellets were press-molded under the following conditions to prepare a sheet having a width of 90 cm, a length of 90 cm, and a thickness of 0.5 mm.
[Press molding conditions]
Press machine: 40ton electro-hydraulic molding machine Heating temperature: Upper mold 240 ℃, lower mold 240 ℃
Heating time: 5min
Press pressure: 5MPa
Cooling time: 2min

(2-3) Tube molded body Pellets were tube-molded under the following conditions to prepare tubes with an outer diameter of φ6.0 mm and an inner diameter of φ2.5 mm.
[Tube molding conditions]
Tube molding machine: Single shaft extruder Cylinder temperature: 220 ° C

Using the obtained molded product, the compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 8 to 13.

(1) Flexibility An injection molded product was used.
A hardness (value 1 second after the start of the test) with a measurement time of 1 second was measured in accordance with JIS K 6253 for a stack of 3 molded samples with a thickness of 2 mm (total 6 mm). The measurement was carried out after adjusting the condition for one day in a room with a temperature of 23 ° C and a humidity of 50%. The A hardness is preferably less than 95.

(2) Gas barrier property A press-molded product was used.
The oxygen permeability coefficient was measured by a method conforming to JIS K 7126. The oxygen permeability coefficient is ^{preferably less than 1 × 10 -15} mol · m / m ² · s · Pa.

(3) A water vapor barrier press-molded product was used.
Moisture permeability was measured in a 40 ° C environment and a 70 ° C environment. Moisture permeability is less than 40 ° C. At 3.5g / m ² · 24hr is 70 less than 20g / m ² · 24hr at ° C. are preferred.
Under 40 ℃ environment: Measured according to JIS K 0208 (cup method), Conditions: 40 ℃ x 90% RH, Sheet thickness: 0.5mm
Under 70 ℃ environment: Measuring according to JIS K 7126-1 (differential pressure method) Measuring machine: GTR-20XAGS (GTR Tech)
Test conditions: 70 ± 0.1 ° C x 90 ± 2% RH
Measurement area: 15.2 cm ²
Sample shape: 90 mm x 90 mm x t = 0.5 ± 0.1 mm

(4) A compression-resistant permanent strain injection molded product was used.
The compression distortion factor (CS) was measured in a 70 ° C., 24-hour environment and 100 ° C., 24-hour environment by a method conforming to JIS K 6262. The compression distortion factor is preferably less than 60% at 70 ° C. and less than 80% at 100 ° C.

(5) Abrasion resistance (Taber wear test)
Using an injection molded product, the amount of wear loss (mg) was measured at 23 ° C., wear wheel; H-22, rotation speed: 72r / min, number of rotations: 1000 times, load: 1000 g, in accordance with JIS K 7204. The amount of wear loss is preferably less than 800 mg.

(6) Sliding property The coefficient of dynamic friction was measured under the following conditions. The coefficient of kinetic friction is preferably less than 2.0.
<Measurement conditions>
Jig used; metal plaid (load: 200 g, 63 x 63 mm, sample ground plane; felt)
Testing machine; Friction testing machine (manufactured by Toyo Seiki Seisakusho)
Test environment; 23 ° C x 50% RH
Test piece: Injection molded product cut into a size of 50 mm x 40 mm Test method: Attach the test piece to the tester with double-sided tape, and place a metal plate in the center of the test piece. Attach the wire connected to the load cell to the metal plate and start the measurement.

(7) Bleed resistance The surface condition 3 months after the production of the injection molded product was visually observed, and the bleed resistance was evaluated according to the following evaluation criteria.
<Evaluation criteria>
⊚: The surface gloss is not different from that immediately after molding.
◯: Compared to immediately after molding, some of the surface is cloudy to the extent that it is not noticeable.
Δ: Compared to immediately after molding, cloudiness that can be seen is observed in some places.
X: A clear bloom appears on the surface, which spoils the aesthetic appearance.

(8) Tube moldability A tube molded product was used.
(8-1) Surface The surface of the tube was visually and tactilely observed and evaluated according to the following evaluation criteria. The evaluation is preferably 3 or more.
<Evaluation criteria>
1: The unevenness is extremely rough and the smoothness is extremely low.
2: Roughness is noticeable and smoothness is low.
3: Slightly rough, but smoothness is not a problem.
4: Has sufficient smoothness.
5: Very high smoothness.

(8-2) Stickiness The 10 mm length of the tip of the tube was crushed until the inner wall of the tube was completely in close contact, held for 5 seconds, and then the pressure was released and the time (sec) until the inner walls of the tube were separated was measured. The time required for the inner walls of the tubes to separate from each other is preferably less than 5 seconds.

(9) Kink-resistant tube molded product was used.
The tube was cut to a length of 300 mm, both ends of the tube were aligned, and the tube was clipped. From both ends of the sandwiched tube, gently press and trace with your finger toward the center of the tube so that the two are in contact and parallel, and stop your finger at the place where the center of the tube buckles while tracing, and stop the finger at the center of the tube. The distance from the part was measured. The distance from the center of the tube is preferably less than 70 mm.

From the above results, the thermoplastic elastomer compositions of Examples 1 to 27 are superior in moldability and flexibility as compared with Comparative Examples 1 to 14, and have high compression set resistance and gas barrier property even at high temperatures. It can be seen that it has water vapor barrier property and bleed resistance, and is also excellent in sliding property, abrasion resistance, and kink resistance.

The thermoplastic elastomer composition of the present invention is useful for various molded products such as automobiles, electronic materials, home appliances, electric devices, medical tools, packaging materials, stationery and miscellaneous goods, and further, grips, tubes, packings, gaskets, etc. It is used for various members such as cushion bodies, films, and seats.

Claims (12)

Component A: Contains structural units derived from aromatic vinyl polymer blocks and isoprene, or a mixture of isoprene and butadiene, with a total content of 1,2-bonding units and 3,4-bonding units of 45 mol%. A hydrogenated block copolymer having the above-mentioned isoprene-based polymer block, and a hydrogenated block copolymer having a weight average molecular weight of 150,000 to 500,000.
Ingredient B: Polybutene oil with kinematic viscosity of 3,000 to 20,000 mm ² / s at 40 ° C.
Ingredient C: Polyolefin,
Component D: Crosslinked isobutylene polymer D1, and / or triblock copolymer D2 composed of an aromatic vinyl polymer block and an isobutylene polymer block, and component E: 5,000 at a kinematic viscosity of 25 ° C. It ^{contains silicone oil of mm 2} / s or more and / or a slidability improver which is a copolymer of polyorganosiloxane and alkyl (meth) acrylate.
With respect to 100 parts by mass of the component A, the content of the component B is 10 to 200 parts by mass, the content of the component C is 1 to 200 parts by mass, the content of the component D is 50 to 1200 parts by mass, and the content of the component E is contained. A thermoplastic elastomer composition in an amount of 1 to 150 parts by mass. The thermoplastic elastomer composition according to claim 1, wherein the polyolefin of component C has a melting point of 140 ° C. or higher. The thermoplastic elastomer composition according to claim 1 or 2, wherein the isobutylene polymer D1 of the component D is an isobutylene polymer having an allyl group crosslinked by hydrosilylation. Claimed that, among the components D, the triblock copolymer D2 has a weight average molecular weight of 50,000 to 500,000, and the content of the isobutylene-based polymer block contained in the triblock copolymer D2 is 50 to 90% by mass. Item 3. The thermoplastic elastomer composition according to any one of Items 1 to 3. The thermoplastic elastomer composition according to any one of claims 1 to 4, further comprising component F: polyphenylene ether. The thermoplastic elastomer composition according to claim 5, wherein the polyphenylene ether of component F has a reducing viscosity of less than 0.45. The thermoplastic elastomer composition according to any one of claims 1 to 6, further comprising component G: an inorganic filler in an amount of 1 to 500 parts by mass with respect to 100 parts by mass of component A. The thermoplastic elastomer composition according to claim 7, wherein the inorganic filler of the component G is talc. The thermoplastic elastomer according to any one of claims 1 to 8, wherein the crosslinked isobutylene polymer D1 is crosslinked by melt-mixing with at least a part of the polybutene oil of the component B and / or the polyolefin of the component C. Composition. A molded product comprising the thermoplastic elastomer composition according to any one of claims 1 to 9. The molded product according to claim 10, which is a tubular molded product. The molded product according to claim 10, which is a molded product for sealing.