JP2009235192A - Thermoplastic elastomer composition and sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition that scarcely causes the contamination and corrosion on an electronic device and in addition is served as a material for a sealing material having sufficient recyclability. <P>SOLUTION: The thermoplastic elastomer composition is used in an electronic device and is produced by subjecting a raw material composition comprising (A) an ethylene-α-olefin-based copolymer rubber having a chlorine content of not more than 60 ppm as measured by X-ray fluorescence spectrometry and (B) at least one kind of thermoplastic resin selected from the group consisting of an α-olefin-based crystalline thermoplastic resin, an α-olefin-based amorphous thermoplastic resin and a cycloolefin-based thermoplastic resin, to a dynamic heat treatment, (C) in the presence of a crosslinking agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic elastomer composition and a sealing material. More specifically, the present invention relates to a thermoplastic elastomer composition and a sealing material that are materials of a sealing material that is sufficiently recyclable in addition to being difficult to contaminate and corrode electronic equipment.

  For example, in various electronic devices such as hard disks, various sealing materials are used as members for partitioning at least a part thereof. Examples of the various sealing materials include those used for electrolytic capacitors (hereinafter sometimes referred to as “capacitors”). That is, the capacitor accommodates an outer case made of a metal material or the like having an opening at one end, and a capacitor element impregnated with an electrolyte in the outer case, and the sealing material covers the opening of the outer case. Used for sealing.

  As such a sealing material, for example, one formed by a composition containing ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) is known. This composition is a sealing material having excellent sealing properties because the EPDM contained therein contains a large amount of diene.

  Specifically, a thermoplastic elastomer composition obtained by using polypropylene and EPDM containing a structural unit derived from 5-ethylidene-2-norbornene, 1,4-hexadiene, and 5-vinyl-2-ylbornene A part (seal material) formed by an object has been reported (for example, Patent Document 1).

JP 2001-316383 A

  However, the sealing material described in Patent Document 1 may contaminate an electronic device and corrode the electronic device, and is not sufficiently recyclable. Further, when the electronic device is contaminated or corroded, the electronic device may malfunction. In addition, from the viewpoint of environmental protection in recent years, the importance of being recyclable is also increasing for materials constituting electronic devices, and therefore a recyclable sealing material is required. From these viewpoints, development of a thermoplastic elastomer composition and a sealing material, which are materials of a sealing material having sufficient recyclability, in addition to being difficult to contaminate or corrode electronic equipment, is desired.

  The present invention has been made to solve the above-mentioned problems of the prior art, and is a thermoplastic elastomer that is a material for a sealing material that has sufficient recyclability in addition to being difficult to contaminate or corrode electronic equipment. A composition and a sealing material are provided.

  As a result of intensive studies to solve the above problems, the present inventors have found the following points. That is, (1) When an electronic device generates heat due to its use, a sealing material provided in the electronic device is exposed to a high temperature and generates a high-concentration gas. The gas generated from the sealing material, for example, clouded the disk surface of the hard disk disposed in the precision instrument product together with the electronic device, and contaminated the hard disk. This contamination was one of the causes of hard disk malfunction. (2) If chlorine is present in a high concentration in the gas generated from the sealing material, the electronic device may be contaminated or corroded by the chlorine. In view of the above, the inventors have found that the above problem can be solved by setting the chlorine content in the predetermined copolymer rubber to be contained in the raw material composition to a predetermined amount or less, and complete the present invention. It came to.

  Specifically, the present invention provides the following thermoplastic elastomer composition and sealing material.

[1] A thermoplastic elastomer composition used for electronic equipment, (A) an ethylene / α-olefin copolymer rubber having a chlorine content of 60 ppm or less by fluorescent X-ray analysis, and (B) an α-olefin. A raw material composition comprising: a crystalline thermoplastic resin, an α-olefin amorphous thermoplastic resin, and at least one thermoplastic resin selected from the group consisting of cyclic olefin thermoplastic resins, (C) A thermoplastic elastomer composition obtained by dynamically heat-treating in the presence of a crosslinking agent.

[2] The thermoplastic elastomer composition according to [1], which does not substantially contain a plasticizer and a softener.

[3] 0.5 g in a sealed container with a head space of 20 ml when 0.5 g is added, sealed under atmospheric pressure and heated in an atmosphere at 150 ° C. for 20 minutes. The thermoplastic elastomer composition according to the above [1] or [2], wherein the concentration of the gas component in the head space is 100 ppm or less.

[4] A sealing material obtained by molding the thermoplastic elastomer composition according to any one of [1] to [3].

[5] The sealing material according to [4], which is for household appliances or a housing of an AV device.

  The thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition used for electronic equipment, and (A) an ethylene / α-olefin copolymer rubber having a chlorine content of 60 ppm or less by fluorescent X-ray analysis; And (B) at least one thermoplastic resin selected from the group consisting of an α-olefin-based crystalline thermoplastic resin, an α-olefin-based amorphous thermoplastic resin, and a cyclic olefin-based thermoplastic resin. Since the composition is obtained by dynamically heat-treating in the presence of (C) a crosslinking agent, it is difficult to generate a high-concentration gas even when exposed to high temperatures, and it is difficult to contaminate electronic equipment. There is an effect. Moreover, since the chlorine content in the generated gas is low, the electronic device is hardly corroded. Furthermore, since it has recycle characteristics, it has an effect that a sealing material having sufficient recyclability can be formed.

  Since the sealing material of the present invention is formed from the thermoplastic elastomer composition of the present invention, it has the effect of being sufficiently recyclable in addition to being difficult to contaminate or corrode electronic equipment.

  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Thermoplastic elastomer composition:
One embodiment of the thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition used for electronic equipment, and (A) an ethylene / α-olefin system having a chlorine content of 60 ppm or less by fluorescent X-ray analysis Copolymer rubber (hereinafter sometimes referred to as “component (A)”), (B) α-olefin crystalline thermoplastic resin, α-olefin amorphous thermoplastic resin, and cyclic olefin thermoplastic A raw material composition comprising at least one thermoplastic resin selected from the group consisting of resins (hereinafter sometimes referred to as “component (B)”), in the presence of (C) a crosslinking agent, It is obtained by heat treatment.

  The thermoplastic elastomer composition of the present embodiment thus obtained does not easily generate a high-concentration gas even when exposed to a high temperature, so that it is difficult to contaminate an electronic device, and the chlorine content in the generated gas. Because it is low, it is difficult to corrode electronic equipment. Furthermore, since it has recycling characteristics, it is possible to form a sealing material having sufficient recyclability. Therefore, the thermoplastic elastomer composition of the present embodiment is, for example, a material used for an electronic device such as a hard disk, that is, a material for a member used for the electronic device. Components used in electronic equipment are used in environments adjacent to the base of electronic equipment such as hard disks and, specifically, shock absorbing materials, vibration absorbing materials, noise reducing materials, cable protection materials. , Clamps, spacers and the like.

[1-1] Ethylene / α-olefin copolymer rubber:
The ethylene / α-olefin copolymer rubber contained in the raw material composition for obtaining the thermoplastic elastomer composition of the present embodiment has a chlorine content by fluorescent X-ray analysis of 60 ppm or less, and 0 to 50 ppm. Is preferable, and it is still more preferable that it is 0-40 ppm. If the chlorine content exceeds 60 ppm, the electronic equipment may be contaminated or corroded. Thus, by making the chlorine content in the component (A) to be contained in the raw material composition 60 ppm or less, it is difficult to generate a high-concentration gas even when exposed to high temperatures, and the chlorine content in the generated gas There is an advantage that a thermoplastic elastomer composition having a low amount can be obtained. The “chlorine content by fluorescent X-ray analysis” in the present specification can be measured using, for example, “Magix PRO” manufactured by Spectris.

  This ethylene / α-olefin copolymer rubber imparts elastic properties derived from a rubber-like component to a thermoplastic elastomer composition. In addition, since ethylene / α-olefin copolymer rubber is also a main component constituting the thermoplastic elastomer composition, the chlorine content in the ethylene / α-olefin copolymer rubber (component (A)) used is reduced. By reducing, that is, by setting the chlorine content in the component (A) to be contained in the raw material composition to 60 ppm or less, the chlorine content of the obtained thermoplastic elastomer composition can also be reduced.

  In the ethylene / α-olefin copolymer rubber, since the catalyst component usually used in the production process contains chlorine, free chlorine is generated during the polymerization process. Therefore, the ethylene / α-olefin copolymer rubber usually contains chlorine. The content thereof is about 100 to 200 ppm in the produced ethylene / α-olefin copolymer rubber. Even when the chlorine content is in such a range (about 100 to 200 ppm), if it is used as a material for automobiles such as weather strips, roofing, and other industrial products such as hoses and gaskets, a high concentration Even if chlorine is present in the gas at a high concentration, there is no particular problem, but when it is used as a material for electronic devices such as hard disks, the generated high concentration There was a risk that the electronic equipment was contaminated or corroded by the gas.

  On the other hand, the thermoplastic elastomer composition of the present invention is thermoplastic by adjusting the chlorine content of the ethylene / α-olefin copolymer rubber contained in the raw material composition for obtaining the thermoplastic elastomer composition to 60 ppm or less. In addition to being able to reduce the concentration of chlorine gas generated from the sealing material formed by the elastomer composition, it is possible to reduce the concentration of the mixed gas containing chlorine gas. Therefore, when used as a material for an electronic device such as a hard disk, there is an advantage that the electronic device is hardly contaminated or corroded by the generated chlorine or mixed gas.

  As the ethylene / α-olefin copolymer rubber, a conventionally known ethylene / α-olefin copolymer rubber having a chlorine content of 60 ppm or less can be appropriately selected and used. Such an ethylene / α-olefin copolymer rubber can be produced, for example, by polymerizing ethylene and α-olefin in the presence of a catalyst component and an alkyl ester compound and then washing. . Thus, by carrying out the polymerization in the presence of an alkyl ester compound, free chlorine derived from the catalyst component generated during the polymerization process can be trapped. Thereafter, by removing the alkyl ester compounds capturing free chlorine by washing, an ethylene / α-olefin copolymer rubber having a reduced chlorine content can be obtained.

  Examples of commercially available ethylene / α-olefin copolymer rubbers include (trade name) “EP331” (chlorine content 22 ppm) manufactured by JSR Corporation.

  The ethylene / α-olefin copolymer rubber is not particularly limited as long as it is a copolymer rubber containing a structural unit (a1) derived from ethylene and a structural unit (a2) derived from an α-olefin. Therefore, in the ethylene / α-olefin copolymer rubber, in addition to the binary copolymer containing the structural unit (a1) and the structural unit (a2), the structural unit (a3) derived from another monomer is used. Furthermore, a ternary copolymer may be included. Furthermore, as long as the structural unit (a1) and the structural unit (a2) are included, a multi-component copolymer including four or more different structural units may be used. The ethylene / α-olefin copolymer rubber can be used alone or in combination of two or more.

  The proportion of the structural unit (a1) contained in the ethylene / α-olefin copolymer rubber is preferably 35 mol% or more when the total structural unit is 100 mol%. When the proportion of the structural unit (a1) is less than 35 mol%, the mechanical strength of the obtained sealing material tends to be insufficient. In addition, when there are too many ratios of a structural unit (a1), it exists in the tendency for the softness | flexibility of the sealing material obtained to become inadequate. Therefore, the proportion of the structural unit (a1) contained in the ethylene / α-olefin copolymer rubber is more preferably 40 to 90 mol%, when the total structural unit is 100 mol%, and is preferably 45 to 85 mol%. It is particularly preferred.

  Examples of the α-olefin constituting the structural unit (a2) include propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3- Examples thereof include methylbutene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene and 1-undecene. Among these, propylene and 1-butene are preferable. In addition, these alpha olefins can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the structural unit (a2) contained in the ethylene / α-olefin copolymer rubber is preferably 5 to 65 mol%, and preferably 10 to 45 mol%, when all the structural units are 100 mol%. More preferably, it is 15-40 mol%, and it is especially preferable. When the proportion of the structural unit (a2) is less than 5 mol%, the resulting sealing material tends to hardly exhibit desired rubber elasticity. On the other hand, when the proportion of the structural unit (a2) is more than 65 mol%, the durability of the resulting sealing material tends to be lowered.

  As a monomer which comprises a structural unit (a3), a nonconjugated diene compound can be mentioned, for example. Examples of the non-conjugated diene compound include linear acyclic diene compounds such as 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene; 5-methyl-1,4-hexadiene, 3,7- Branched chain such as dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydromyrcene Acyclic diene compounds of: tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene , It can be mentioned alicyclic diene compounds such as 5-vinyl-2-norbornene. Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferable. In addition, these nonconjugated diene compounds can be used individually by 1 type or in combination of 2 or more types.

  When the ethylene / α-olefin copolymer rubber contains the structural unit (a3), the proportion of the structural unit (a3) contained in the ethylene / α-olefin copolymer rubber is 100 mol% of all the structural units. When it is, it is preferable that it is 10 mol% or less, and it is still more preferable that it is 1-8 mol%. When the proportion of the structural unit (a3) is more than 10 mol%, the durability of the resulting thermoplastic elastomer composition tends to be lowered.

  The ethylene / α-olefin copolymer rubber can also be used as a graft polymer by further polymerizing an unsaturated monomer. Examples of the unsaturated monomer include vinyl acetate; (meth) acrylic acid; (meth) acrylic acid derivatives such as methyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylamide; maleic acid; maleic anhydride And maleic acid derivatives such as maleimide and dimethyl maleate; conjugated diene compounds such as butadiene, isoprene and chloroprene.

  The crystallinity of the ethylene / α-olefin copolymer rubber by X-ray diffraction measurement is preferably 20% or less, and more preferably 15% or less. When the crystallinity of the ethylene / α-olefin copolymer rubber exceeds 20%, the flexibility of the obtained sealing material tends to be lowered.

  The iodine value of the ethylene / α-olefin copolymer rubber is preferably 5 to 30, and more preferably 7 to 20. When the iodine value of the ethylene / α-olefin copolymer rubber is less than 5, the crosslinking density is lowered, and the mechanical properties of the thermoplastic elastomer composition tend to be lowered. On the other hand, when the iodine value of the ethylene / α-olefin copolymer rubber is more than 30, the crosslinking density is excessively increased and the mechanical properties of the thermoplastic elastomer composition tend to be decreased.

  In addition, so-called oil-extended rubber, in which a mineral oil softener is added to ethylene / α-olefin copolymer rubber, generates a high-concentration gas from the sealing material formed due to the mineral oil softener. Such a sealing material is not particularly preferred for use in electronic equipment. However, a small amount can be used as long as the effect of the present invention is not impaired.

  The intrinsic viscosity of the ethylene / α-olefin copolymer rubber is preferably 1.8 dl / g or more. When the intrinsic viscosity of the ethylene / α-olefin copolymer rubber is less than 1.8 dl / g, mechanical strength and rubber elasticity tend to be lowered. On the other hand, if the intrinsic viscosity of the ethylene / α-olefin copolymer rubber is too large, the moldability tends to decrease. Therefore, the intrinsic viscosity of the ethylene / α-olefin copolymer rubber is more preferably 2.0 to 7.0 dl / g, and particularly preferably 2.0 to 6.0 dl / g. The intrinsic viscosity of the ethylene / α-olefin copolymer rubber is a value measured at 135 ° C. after dissolving the thermoplastic elastomer composition in a decalin solvent using an Ubbelohde viscometer.

[1-2] α-Olefin-based crystalline thermoplastic resin:
The α-olefin-based crystalline thermoplastic resin contained in the raw material composition for obtaining the thermoplastic elastomer composition of the present embodiment imparts thermoplastic properties to the composition and is processed near the plastic deformation temperature. Thereby, the fluid moldability and recyclability of the composition can be obtained. Further, by cooling and solidifying, it acts on the mechanical strength of the composition and the shape retention of the molded product.

  The α-olefin-based crystalline thermoplastic resin is a crystalline polymer containing a structural unit (b1) derived from an α-olefin.

  The α-olefin-based crystalline thermoplastic resin of the present embodiment has a crystallinity by X-ray diffraction of 50% or more, preferably 53% or more, and more preferably 55% or more. When the crystallinity is less than 50%, the heat resistance, mechanical strength, etc. of the resulting thermoplastic elastomer composition tend to be lowered.

Α- olefin crystalline thermoplastic resin of the present embodiment, the density is preferably at 0.89 g / cm ³ or more, further preferably 0.90~0.94g / cm ^3. When the density is less than 0.89 g / cm ³ , the heat resistance and mechanical strength of the resulting thermoplastic elastomer composition tend to be lowered.

The crystallinity and density have a correlation. Specifically, when the α-olefin-based crystalline thermoplastic resin is polypropylene, α-type crystals (monoclinic crystal, crystallinity of 100 %) Of polypropylene has a density of 0.936 g / cm ³ , and Smetica type microcrystalline (pseudo hexagonal crystal form, 43% crystallinity) polypropylene has a density of 0.886 g / cm ³ , Crystalline (atactic, crystallinity 0%) polypropylene has a relationship that its density is 0.850 g / cm ³ . From such a relationship, the α-olefin-based crystalline thermoplastic resin of the present embodiment can have a crystallinity of 50% or more by setting its density to 0.89 g / cm ³ or more.

  The α-olefin constituting the structural unit (b1) preferably has 2 to 12 carbon atoms. Among these, propylene and 1-butene are more preferable. The proportion of the structural unit (b1) contained in the α-olefin-based crystalline thermoplastic resin is preferably 80 mol% or more, more preferably 90 to 100 mol% when all the structural units are 100 mol%. preferable. If it is less than 80 mol%, the mechanical strength may not be sufficient.

  The α-olefin-based crystalline thermoplastic resin may be a copolymer containing a structural unit (b2) other than the structural unit (b1). In the case of a copolymer, the α-olefin-based crystalline thermoplastic resin is a random copolymer and a block copolymer. Any polymer may be used, and the polymer can be produced using a Ziegler-Natta catalyst or a metallocene catalyst.

  However, when the α-olefin-based crystalline thermoplastic resin is a block copolymer, the proportion of the structural unit (b2) is based on 100 mol% of all structural units from the viewpoint of setting the crystallinity to 50% or more. It is preferably 40 mol% or less, and more preferably 20 mol% or less.

  When the α-olefin-based crystalline thermoplastic resin is a random copolymer, the proportion of the structural unit (b2) is based on 100 mol% of all structural units from the viewpoint of setting the crystallinity to 50% or more. It is preferably 15 mol% or less, and more preferably 10 mol% or less.

  The random copolymer can be obtained, for example, by polymerizing an α-olefin in the presence of a catalyst component including a Ziegler-Natta catalyst, a soluble vanadium compound, an organoaluminum compound, and a solvent. Examples of the polymerization method include a medium / low pressure method. It can also be produced by a gas phase method (fluidized bed or stirred bed), a liquid phase method (slurry method or solution method) and the like. During polymerization, a molecular weight regulator such as hydrogen gas may be used as necessary.

As the soluble vanadium compound contained in the catalyst component, it is preferable to use, for example, a product produced by a reaction between an alcohol selected from the group consisting of VOCl _3, VCl ₄ , and a mixture thereof. As alcohol used for the said reaction, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol Etc. Among these, C3-C8 alcohol is preferable.

  Examples of the organoaluminum compound contained in the catalyst component include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethyl. Examples thereof include aluminum dichloride, butyl aluminum dichloride, methylaluminoxane which is a reaction product of trimethylaluminum and water, and a mixture thereof. Among these, ethylaluminum sesquichloride, butylaluminum sesquichloride, a mixture of ethylaluminum sesquichloride and triisobutylaluminum, and a mixture of triisobutylaluminum and butylaluminum sesquichloride are preferable.

  As the solvent contained in the catalyst component, for example, a hydrocarbon is preferable. Among the hydrocarbons, n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane are more preferable. In addition, these can be used individually by 1 type or in combination of 2 or more types.

  The maximum peak temperature (melting point) measured by the differential scanning calorimetry of the α-olefin-based crystalline thermoplastic resin is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and 140 to 170. It is particularly preferable that the temperature is C. When the melting point of the α-olefin-based crystalline thermoplastic resin is less than 100 ° C., the resulting thermoplastic elastomer composition tends to have insufficient heat resistance and mechanical strength.

  The melt flow rate (MFR) of the α-olefin-based crystalline thermoplastic resin is preferably 0.1 to 1000 g / 10 minutes, more preferably 0.5 to 500 g / 10 minutes. It is particularly preferred that it is ˜100 g / 10 min. When the MFR of the α-olefin-based crystalline thermoplastic resin is less than 0.1 g / 10 minutes, the kneadability and extrusion processability of the raw material composition tend to be insufficient. On the other hand, when it exceeds 1000 g / 10 minutes, the mechanical strength of the resulting thermoplastic elastomer composition tends to be lowered. Here, in this specification, “melt flow rate” refers to a value measured under conditions of a temperature of 230 ° C. and a load of 21 N in accordance with JIS K7210.

  As the α-olefin-based crystalline thermoplastic resin, polypropylene, a copolymer of ethylene and propylene (ethylene-propylene copolymer), and a mixture of polypropylene and ethylene-propylene copolymer are preferable. Examples thereof include a polypropylene polymer, an ethylene-propylene random polymer, an ethylene-propylene block polymer and the like sold by Prime Polymer, Sun Allomer, and Nippon Polypro. More specifically, the product name “NOVATEC” (manufactured by Nippon Polypro), the product name “Wintech” (manufactured by Nippon Polypro), the product name “New Former” (manufactured by Nippon Polypro), "(Manufactured by Nippon Polypro Co., Ltd.), trade name" Newcon "(manufactured by Nippon Polypro Co., Ltd.) In addition, these (alpha) -olefin type | system | group crystalline thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

[1-3] α-olefin-based amorphous thermoplastic resin:
The α-olefin-based amorphous thermoplastic resin, like the α-olefin-based crystalline thermoplastic resin described above, imparts thermoplastic properties to the composition, and is processed near the plastic deformation temperature. The fluid moldability and recyclability of the composition can be obtained. Further, by cooling and solidifying, it acts on the mechanical strength of the composition and the shape retention of the molded product.

  The α-olefin-based amorphous thermoplastic resin is an amorphous polymer containing a structural unit (b3) derived from an α-olefin.

  The α-olefin-based amorphous thermoplastic resin has a crystallinity by X-ray diffraction of less than 50%, preferably 30% or less, and more preferably 20% or less. When the degree of crystallinity is 50% or more, the resulting thermoplastic elastomer composition tends to have high hardness and tends to be unsuitable for uses requiring low hardness.

  The α-olefin constituting the structural unit (b3) preferably has 3 or more carbon atoms, more preferably 3 to 12 carbon atoms. The proportion of the structural unit (b3) contained in the α-olefin-based amorphous thermoplastic resin is preferably 60 mol% or more when the total structural unit is 100 mol%. If it is less than 60 mol%, the mechanical strength may not be sufficient.

  Homopolymers such as atactic polypropylene and atactic poly 1-butene; propylene and, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene A copolymer obtained by copolymerizing an α-olefin such as propylene (the proportion of structural units derived from propylene is more than 50 mol% based on the total structural units); 1-butene and, for example, ethylene, propylene, Copolymer obtained by copolymerizing with α-olefin such as 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene (ratio of structural units derived from 1-butene) However, it is more than 50 mol% with respect to all the structural units).

  Among these, atactic polypropylene; a copolymer obtained by copolymerizing propylene, 1-butene, and ethylene (the proportion of structural units derived from propylene is more than 50 mol% with respect to all structural units) A copolymer obtained by copolymerizing 1-butene, propylene, and ethylene (the proportion of the structural unit derived from 1-butene is more than 50 mol% based on the total structural units);

  Atactic polypropylene and atactic poly-1-butene can be produced by a polymerization method using a zirconocene compound-methylaluminoxane catalyst. In addition, atactic polypropylene can also be obtained as a by-product of the polypropylene exemplified as the α-olefin crystalline thermoplastic resin.

  When the α-olefin-based amorphous thermoplastic resin is a copolymer, the copolymer may be either a block copolymer or a random copolymer.

  However, when the α-olefin-based amorphous thermoplastic resin is a block copolymer, the proportion of the structural unit (b3) is preferably 60 to 100 mol% when all the structural units are 100 mol%. . When the ratio is less than 60 mol%, the mechanical strength may not be sufficient.

  The number average molecular weight (hereinafter sometimes referred to as “Mn”) of the α-olefin-based amorphous thermoplastic resin is preferably 1,000 to 20,000, and preferably 1,500 to 15,000. More preferably. When the Mn of the α-olefin-based amorphous thermoplastic resin is less than 1,000, physical properties tend to be inferior. On the other hand, when Mn exceeds 20,000, kneadability and extrusion processability of the raw material composition tend to be insufficient. Here, “number average molecular weight” in the present specification means the number average molecular weight in terms of polystyrene measured by gel permeation chromatography.

  Examples of commercially available products of the α-olefin-based amorphous thermoplastic resin include a trade name “Best Plast” (manufactured by Degussa), a trade name “APAO” (manufactured by Huntsman), and the like. In addition, these (alpha) -olefin type | system | group amorphous thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

[1-4] Cyclic olefin-based thermoplastic resin:
The cyclic olefin thermoplastic resin imparts thermoplastic properties to the composition in the same manner as the α-olefin crystalline thermoplastic resin and the α-olefin amorphous thermoplastic resin described above, and is plastic. By processing in the vicinity of the deformation temperature, the fluid moldability and recyclability of the composition can be obtained. Further, by cooling and solidifying, it acts on the mechanical strength of the composition and the shape retention of the molded product.

  As a cyclic olefin type thermoplastic resin, the (co) polymer formed with the cyclic olefin represented by following General formula (1) can be mentioned, for example.

In the general formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and R ¹ and R ² , and R ³ and R ⁴ are either May be integrated to form a divalent organic group. R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other to form a monocyclic structure or a polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer.

  More specifically, as the cyclic olefin-based thermoplastic resin, (i) a ring-opened polymer of a cyclic olefin represented by the general formula (1), and (ii) a cyclic represented by the general formula (1). A ring-opening copolymer of an olefin and a copolymerizable monomer, (iii) a hydrogenated (co) polymer of the ring-opening (co) polymer of (i) or (ii), (iv) the (i) ) Or (ii) a ring-opened (co) polymer cyclized by Friedel-Craft reaction and then hydrogenated to obtain a (co) polymer, (v) represented by the general formula (1) A saturated copolymer of a cyclic olefin and an unsaturated double bond-containing compound, (vi) a cyclic olefin represented by the general formula (1), a vinyl cyclic hydrocarbon monomer and / or a cyclopentadiene Addition type (co) polymers with monomers, as well as hydrogenated (co) polymers thereof, ( A cycloolefin represented by ii) the general formula (1), and the like alternating copolymer of acrylate.

[1-4-1] Cyclic olefin:
The monovalent organic group in the general formula (1) may be referred to as a C1-C30 hydrocarbon group or a monovalent polar group other than a hydrocarbon group (hereinafter referred to as “monovalent polar group”). ). Examples of the monovalent polar group include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups may be bonded via a linking group such as a methylene group. Further, the polar group may be a hydrocarbon group or the like bonded through a linking group composed of a divalent organic group having polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group.

  Of these polar groups, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and an allyloxycarbonyl group are particularly preferable. In addition, a cyclic olefin can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the cyclic olefin represented by the general formula (1) include bicyclo [2.2.1] hept-2-ene and tricyclo [4.3.0.1 ^2,5 ] -8-. Decene, tricyclo [4.4.0.1 ^2,5 ] -3-undecene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene ,

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5-phenylbicyclo [2.2.1] hept-2-ene, 8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

  5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept- 2-ene, 5-pentafluoroethylbicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene, 5,6-difluorobicyclo [2 2.1] hept-2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2 .1] Hept-2-ene, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hept- 2-ene, 5,5,6-tris (fluoro Til) bicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrakis ( Trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

  5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2. 2.1] Hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-fluoro-5-pentafluoroethyl-6 6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] Hept-2-ene, 5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [ 2.2.1] Hept 2-ene, 5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2. 2.1] hept-2-ene,

8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . And a compound such as 1 ^7,10 ] -3-dodecene. The cyclic olefin is not limited to these compounds.

In the general formula (1), R ¹ and R ³ are preferably each independently a hydrogen atom or a hydrocarbon group. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and particularly preferably 1 or 2. R ¹ and R ³ are particularly preferably an alkyl group, and most preferably a methyl group.

In the general formula (1), R ² and R ⁴ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ is a hydrogen atom, Or it is preferable that it is the monovalent polar group illustrated as a monovalent organic group in General formula (1).

  In the general formula (1), m is preferably an integer of 0 to 3, and p is preferably an integer of 0 to 3. In addition, it is preferable that the value of m + p is 0-4, and it is still more preferable that it is 0-2. Particularly preferably, m = 1 and p = 0. Use of a cyclic olefin where m = 1 and p = 0 is preferable because a cyclic olefin-based thermoplastic resin having a high glass transition temperature and excellent mechanical strength can be obtained.

Furthermore, at least one of R ² and R ⁴ is preferably a cyclic olefin having a polar group represented by the following general formula (2). In this case, a high glass transition temperature and low hygroscopicity, And the cyclic olefin type thermoplastic resin which has the outstanding adhesiveness with various materials can be obtained.
^{_{- (CH 2) n COOR 5}} (2)

In the general formula (2), R ⁵ is a hydrocarbon group. The hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2. R ⁵ is preferably an alkyl group among the hydrocarbon groups. Moreover, in said general formula (2), n is an integer of 0-5. If the value of n is small, a cyclic olefin-based thermoplastic resin having a high glass transition temperature can be obtained. Further, when the “n” of the polar group represented by the general formula (2) in the cyclic olefin is “0”, it is particularly preferable because the cyclic olefin can be easily synthesized.

In addition, R ¹ and R ³ in the general formula (1) are alkyl groups, and the polar group represented by the general formula (2) is bonded to the carbon atom to which R ¹ or R ³ is bonded. Thus, a cyclic olefin-based thermoplastic resin having low hygroscopicity can be obtained.

  In addition, the ring-opening polymer of the cyclic olefin represented by (i) general formula (1) can be obtained by ring-opening polymerization of a cyclic olefin in the presence of a metathesis catalyst. Moreover, (ii) the ring-opening copolymer of the cyclic olefin represented by the general formula (1) and the copolymerizable monomer is obtained by ring-opening copolymerization of the cyclic olefin and the copolymerizable monomer. Obtainable.

  (Ii) Examples of the copolymerizable monomer used for obtaining the ring-opening copolymer include cycloolefin. The cycloolefin has preferably 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms. More specifically, cyclobutene, cyclopentene, cycloheptene, cyclooctene, dicyclopentadiene and the like can be mentioned. These cycloolefins can be used alone or in combination of two or more.

  Commercially available products of cyclic olefin-based thermoplastic resins include, for example, trade name “ARTON” (manufactured by JSR), trade name “TOPAS” (manufactured by Ticona (Germany)), trade name “Apel” (manufactured by Mitsui Chemicals). Trade name “ZEONEX” (manufactured by Nippon Zeon Co., Ltd.), trade name “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.), and the like.

[1-5] Ratio of copolymer rubber and thermoplastic resin:
The content ratio of the component (A) in the thermoplastic elastomer composition of the present embodiment is 10 to 90% by mass when the total amount of the component (A) and the component (B) is 100% by mass. Is preferable, it is still more preferable that it is 15-85 mass%, and it is especially preferable that it is 20-85 mass%. When the content ratio of the component (A) is less than 10% by mass, the flexibility and rubber elasticity of the resulting thermoplastic elastomer composition tend to decrease. On the other hand, when the content ratio of the component (A) is more than 90% by mass, the resulting thermoplastic elastomer composition has a favorable phase structure (morphology) and a good sea-island structure (thermoplastic resin is the sea (matrix), copolymer rubber) Particles are difficult to form islands (domains), and fluidity and molding processability tend to decrease.

[1-6] (C) Crosslinking agent:
The type of (C) crosslinking agent used for producing the thermoplastic elastomer composition of the present embodiment is not particularly limited, but at least (A) is obtained by dynamic heat treatment at a temperature equal to or higher than the melting point of component (B). It is preferably a compound capable of crosslinking the component.

  (C) Examples of the crosslinking agent include organic peroxides, phenol resin crosslinking agents, sulfur, sulfur compounds, p-quinones, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, amino resins, Examples include polyol cross-linking agents, polyamines, triazine compounds, and metal soaps. Among these, an organic peroxide and a phenol resin crosslinking agent are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy)- p-isopropylbenzene, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide, p-menthane peroxide,

  1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butylperoxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chloro Examples include benzoyl peroxide, benzoyl peroxide, di (t-butylperoxy) perbenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxyisopropyl carbonate, and the like. .

  Among these, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide and di-t-butyl peroxide are preferred. In addition, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the phenol resin crosslinking agent include p-substituted phenol compounds represented by the following general formula (3), o-substituted phenol / aldehyde condensate, m-substituted phenol / aldehyde condensate, brominated alkylphenol / aldehyde condensate. And the like. Among these, p-substituted phenol compounds represented by the following general formula (3) are preferable. In addition, these can be used individually by 1 type or in combination of 2 or more types.

In the general formula (3), ^{R 6} is a saturated hydrocarbon group having 1 to 15 carbon atoms, k is an integer of 0. The p-substituted phenol compound represented by the general formula (3) can be obtained, for example, by a condensation reaction between a p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst. The saturated hydrocarbon groups for R ⁶ may be the same or different.

  Commercially available phenolic crosslinking agents include, for example, trade name “Tactrol 201” (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), trade name “Tactrol 250-I” (brominated alkylphenol formaldehyde resin having a bromination rate of 4%). , Manufactured by Taoka Chemical Industry Co., Ltd.), trade name “Tactrol 250-III” (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industries), trade name “PR-4507” (produced by Gunei Chemical Industry Co., Ltd.), trade name “ST137X” (Rohm and Haas), trade name “Sumilite Resin PR-22193” (Sumitomo Durez), trade name “Tamanor 531” (Arakawa Chemical Co., Ltd.), trade name “SP1059”, trade name “ SP1045 ", product name" SP1055 ", product name" SP1056 " Tadi Co., Ltd.), trade name "CRM-0803" (Showa Union Gosei Co.), and the like. Among these, the trade name “Tackyroll 201” manufactured by Taoka Chemical Industry Co., Ltd. can be suitably used.

  (C) The usage-amount of a crosslinking agent is 0.01-20 with respect to a total of 100 mass parts of (A) component and (B) component contained in the raw material composition for manufacturing a thermoplastic elastomer composition. It is preferable to set it as a mass part, It is more preferable to set it as 0.1-15 mass parts, It is still more preferable to set it as 1-10 mass parts.

  (C) When using an organic peroxide as a crosslinking agent, the amount of the organic peroxide used is the components (A) and (B) included in the raw material composition for producing the thermoplastic elastomer composition. It is preferable to set it as 0.05-10 mass parts with respect to a total of 100 mass parts, and it is still more preferable to set it as 0.1-5 mass parts. When the amount of the organic peroxide used is less than 0.05 parts by mass, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition tend to be reduced. On the other hand, when the amount of the organic peroxide used is more than 10 parts by mass, the degree of crosslinking becomes excessively high, the molding processability is lowered, and the mechanical properties of the resulting thermoplastic elastomer composition tend to be lowered. is there.

  Moreover, when using a phenol resin crosslinking agent as (C) crosslinking agent, the usage-amount of a phenol resin crosslinking agent is (A) component and (B) contained in the raw material composition for manufacturing a thermoplastic elastomer composition. It is preferable to set it as 0.2-10 mass parts with respect to a total of 100 mass parts with a component, and it is still more preferable to set it as 0.5-5 mass parts. When the amount of the phenol resin crosslinking agent used is less than 0.2 parts by mass, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition tend to decrease. On the other hand, when the amount of the phenol resin crosslinking agent used exceeds 10 parts by mass, the moldability tends to be lowered.

  When the thermoplastic elastomer composition of the present embodiment uses (C) a crosslinking agent, a crosslinking aid, a crosslinking accelerator, or a combination thereof, the crosslinking reaction can be performed gently, and uniform crosslinking is achieved. Can be formed.

  (C) When an organic peroxide is used as the crosslinking agent, it is preferable to use sulfur, a sulfur compound, an oxime compound, polyfunctional monomers, or the like as a crosslinking aid.

  Examples of the sulfur compound include powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, and the like. Examples of the oxime compound include p-quinone oxime and p, p′-dibenzoylquinone oxime. Examples of multifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N′-m-phenylene bismaleimide, N, N′-toluylene bismaleimide, maleic anhydride, divinylbenzene And zinc di (meth) acrylate.

  Among these, p, p'-dibenzoylquinone oxime, N, N'-m-phenylene bismaleimide, and divinylbenzene are preferable. In addition, these can be used individually by 1 type or in combination of 2 or more types. Since N, N′-m-phenylenebismaleimide also exhibits an action as a crosslinking agent, it can also be used alone as the (C) crosslinking agent.

  (C) When using an organic peroxide as a crosslinking agent, the amount of crosslinking aid used is 10 masses per 100 parts by mass in total of the (A) component and the (B) component contained in the raw material composition. Part or less, and more preferably 0.2 to 5 parts by weight. When the amount of the crosslinking aid used is more than 10 parts by mass, the degree of crosslinking becomes excessively high, the molding processability is lowered, and the mechanical properties of the resulting thermoplastic elastomer composition tend to be lowered.

  The thermoplastic elastomer composition for sealing materials of this embodiment can also contain a hydrogenated diene polymer. Specific examples of hydrogenated diene polymers include hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene-isoprene block copolymers, and hydrogenated butadiene blocks. A copolymer etc. can be mentioned. Among these, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-butadiene-isoprene block copolymer, and a hydrogenated butadiene block polymer are preferable.

  Commercially available hydrogenated diene polymers include, for example, the trade name “Septon” (manufactured by Kuraray Co., Ltd.), the trade name “Hiblar” (manufactured by Kuraray Co., Ltd.), the trade name “Tough Tech” (manufactured by Asahi Kasei Co., Ltd.), and the trade name “ Dynalon ”(manufactured by JSR), trade name“ Clayton ”(manufactured by Kraton Polymers), and the like.

[1-7] Other polymer components:
The raw material composition for obtaining the thermoplastic elastomer composition of the present embodiment includes (A) component, (B) component, and other polymers in addition to the hydrogenated diene polymer used as necessary. Ingredients may be contained. The type of “other polymer component” is not particularly limited as long as it does not impair the mechanical strength, flexibility and the like of the thermoplastic elastomer composition obtained.

  Other polymer components include, for example, ionomer resins, aminoacrylamide polymers, polyethylene and its maleic anhydride graft polymers, polyisobutylene, ethylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymers, polyethylene oxide, Ethylene / acrylic acid copolymer, polypropylene and its maleic anhydride graft polymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene,

  4-methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, polyamide resin, polycarbonate, vinyl alcohol resin, vinyl acetal resin, polyether resin , Polyethylene terephthalate, ethylene / α-olefin / non-conjugated diene copolymer rubber, nitrile rubber and its hydrogenated product, acrylic rubber, silicone rubber, butyl rubber, natural rubber, syndiotactic 1,2-polybutadiene,

  Simple blend type olefin thermoplastic elastomer, implant type olefin thermoplastic elastomer, dynamically crosslinked olefin thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, fluorine thermoplastic elastomer Can be mentioned. These “other polymer components” can be used singly or in combination of two or more.

[1-8] Additives and fillers:
The thermoplastic elastomer composition of the present embodiment can contain various additives and fillers as long as the effects of the present invention are not impaired. Examples of additives include anti-aging agents, antioxidants, ultraviolet absorbers, antistatic agents, weathering agents, non-halogen flame retardants, fillers, antibacterial / antifungal agents, blocking agents, sealability improvers, Stabilizers such as heat stabilizers, light stabilizers, copper damage inhibitors, metal deactivators, crystal nucleating agents, tackifiers, foaming aids, colorants (dyes, pigments, etc.) and the like can be mentioned.

  Further, in order to improve the sliding characteristics such as the wearability of the final product, a lubricant component can be added within a range not impairing the effects of the present invention. Examples of the lubricant component include metal soap, olefin resin wax, fatty acid, fatty acid amide, fatty alcohol, fatty acid ester and the like. In addition, the lubricant component is preferably a solid component or a compound exhibiting high viscosity characteristics under the normal use temperature of the final product. In the case of a liquid or low-viscosity characteristic, problems such as thinning due to elution from the thermoplastic elastomer composition are likely to occur, and the sealability may not be maintained over a long period of time.

  Fillers include metal powders such as ferrite, inorganic fibers such as glass fibers and metal fibers, organic fibers such as carbon fibers and aramid fibers, composite fibers, inorganic whiskers such as potassium titanate whiskers, glass beads, and glass balloons. , Glass flakes, mica, calcium carbonate, talc, wet silica, dry silica, alumina, alumina silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton flock, cork powder, sulfuric acid Examples thereof include barium, fluororesin, polymer beads, carbon black, cellulose powder, rubber powder, and wood powder.

  However, it is preferable that the thermoplastic elastomer composition of the present embodiment contains substantially no plasticizer and softener. By substantially not containing a plasticizer, defects such as thinning due to volatilization of the plasticizer hardly occur, and excellent sealing properties are exhibited over a long period of time. Moreover, since the sealing characteristics can be maintained over a long period of time by not containing the softening agent, it is possible to reduce the permeation loss of the encapsulated substance.

  Here, in the present specification, the phrase “substantially does not contain a plasticizer and a softener” means that the total content of the plasticizer and the softener is 5.0 with respect to the entire thermoplastic elastomer composition. It means less than mass%. The total content of the plasticizer and the softener is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.1% by mass or less (that is, completely contained). Most preferably).

  As described above, the thermoplastic elastomer composition of the present embodiment preferably contains substantially no plasticizer, but contains a small amount of plasticizer as long as the effects of the present invention are not impaired. It can also be made.

  Examples of the plasticizer that can be contained include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate. Acid esters; dimethyl adipate, diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di- (2-ethylhexyl) azelate,

  Fatty acid esters such as diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octyl ester, trimellitic acid In addition to trimellitic esters such as n-octyl ester and trimellitic isononyl ester, di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, tristearyl phosphate, tri- (2-ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, polyether ester and the like can be mentioned.

  On the other hand, examples of plasticizers and softeners that are not preferable to use include petroleum-based softeners such as aromatic oil, naphthenic oil, paraffin oil, white oil, petrolatum, and gilsonite; castor oil, cottonseed oil, rapeseed oil, palm oil, There may be mentioned vegetable oil softeners such as coconut oil and rosin.

  The thermoplastic elastomer composition of this embodiment preferably has a melt flow rate (MFR) of 0.1 g / 10 min or more, more preferably 1.0 g / 10 min or more, and 2.0 g. / 10 minutes or more is particularly preferable, and 3.0 g / 10 minutes or more is most preferable. If the MFR is less than 0.1 g / 10 min, the processability by various molding methods tends to be insufficient.

  The thermoplastic elastomer composition of the present embodiment controls the morphology of the component (A) and the component (B) and constitutes a complete sea-island structure, and therefore has excellent fluidity. Therefore, even when various molded products are produced using a mold, mold contamination is unlikely to occur and the mold can be used for a long period of time. Moreover, since the thermoplastic elastomer composition of this embodiment is recyclable, the material can be used without waste.

[2] Method for producing thermoplastic elastomer composition:
The thermoplastic elastomer composition of the present embodiment is obtained by dynamically heat-treating a raw material composition containing a component (A) and a component (B) in the presence of (C) a crosslinking agent.

  Here, “dynamically heat-treating” refers to both applying a shearing force and heating. And the thermoplastic elastomer composition of this embodiment obtained by heat-treating dynamically in this way, specifically, the component (B) is the sea phase, and in this sea phase, the component (A) It forms a so-called sea-island structure in which particles are dispersed as island phases.

  When preparing the raw material composition, the component (A) and the component (B) may be used as they are, or those prepared as compositions containing the same or different additives may be used. The shape of the component (A) may be any of a veil shape, a crumb shape, a pellet shape, and a powder shape (including a crushed product of a veil rubber or a crumb rubber). Moreover, you may use combining several (A) component from which a shape differs.

  As a device used for “dynamic heat treatment”, a melt kneading device or the like can be cited as a suitable example. The treatment by the melt kneader may be either a continuous type or a batch type. Examples of the melt-kneading apparatus include an open type mixing roll, a non-open type Banbury mixer, a single screw extruder, a twin screw extruder, a continuous kneader, and a pressure kneader.

  Among these, it is preferable to use a continuous melt kneading apparatus such as a single-screw extruder, a twin-screw extruder, or a continuous kneader from the viewpoints of economy, processing efficiency, and the like. Further, two or more continuous melt kneaders having the same or different types may be used in combination.

  The L / D ratio (ratio between the screw effective length L and the outer diameter D) of the twin-screw extruder is preferably 30 or more, and more preferably 36-80. In addition, as the twin screw extruder, for example, an arbitrary twin screw extruder such as one in which two screws mesh or not mesh can be used, but the rotation direction of the two screws is the same direction. Are more preferable. As such a twin screw extruder, for example, a trade name “PCM” (manufactured by Ikegai Co., Ltd.), a trade name “KTX” (manufactured by Kobe Steel), a trade name “TEX” (manufactured by Nippon Steel Works), a product The name “TEM” (manufactured by Toshiba Machine Co., Ltd.), the product name “ZSK” (manufactured by Warner), and the like can be mentioned.

  The L / D ratio (ratio between the screw effective length L and the outer diameter D) of the continuous kneader is preferably 5 or more, and more preferably 10 or more. Examples of such a continuous kneader include a trade name “Mixtron KTX / LCM / NCM” (manufactured by Kobe Steel), a trade name “CIM / CMP” (manufactured by Nippon Steel).

  The heat treatment temperature during “dynamic heat treatment” is preferably 120 to 350 ° C., and more preferably 150 to 290 ° C. The treatment time is preferably 20 seconds to 320 minutes, more preferably 30 seconds to 25 minutes. Further, the shearing force to be applied is preferably 10 to 20,000 / second, more preferably 100 to 10,000 / second in terms of shear rate.

  The thermoplastic elastomer composition of the present embodiment is prepared by sealing 0.5 g in a sealed container in which the head space is 20 ml when 0.5 g of the thermoplastic elastomer composition is placed, and is sealed at 150 ° C. under atmospheric pressure. The concentration of the gas component in the head space of the container after heating in an atmosphere for 20 minutes is preferably 100 ppm or less, more preferably 80 ppm or less, and particularly preferably 60 ppm or less. If the concentration of the gas component is more than 100 ppm, the gas component may contaminate the electronic device. Here, the density | concentration of a gas component means the density | concentration (ppm) of n-hexane conversion using the head space method.

  A thermoplastic elastomer composition satisfying such conditions is less likely to contaminate an electronic device, less likely to corrode an electronic device, and has good recyclability.

[3] Sealing material:
One embodiment of the sealing material of the present invention is obtained by molding the thermoplastic elastomer composition of the present invention. Therefore, the sealing material of this embodiment has sufficient recyclability in addition to being difficult to contaminate or corrode electronic equipment. The sealing material of this embodiment is preferably a sealing material for household appliances and a housing for AV equipment. In particular, it is preferably for at least one selected from the group consisting of a hard disk, a battery, a fuel cell, a wire connector, an inkjet printer including an ink cartridge, and a flat panel display.

  The molded member of this embodiment can be manufactured by various molding methods, such as injection molding, press molding, and extrusion molding, for example.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Various measurements in Examples and Comparative Examples were performed by the following methods.

[Chlorine content]:
(A) The chlorine content (ppm) in the copolymer rubber is measured using a spectroscopic X-ray fluorescence apparatus “Magix PRO”.

[Tensile test]:
First, a thermoplastic elastomer composition is injection-molded using an injection molding machine (model number “N-100”, manufactured by Nippon Steel Works), and is a sheet-like molded product having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm. Is made. From this molded product, a test piece for a tensile test is collected by punching out using a test piece-shaped blade according to JIS K6251. The test method in conformity with JIS K6251, measuring the tensile strength _T B (MPa), and tensile elongation _E B (%).

The tensile stress _{M 100} is described above for JIS K6251 test piece was punched into the shape conforming to, using "Autograph AG2000G" of Shimadzu Corporation, at 100 elongation at test according to JIS K6251 stress ( M ₁₀₀₎ to measure.

[Compression set (%)]:
Measurement is performed in accordance with JIS K6262. Specifically, the thermoplastic elastomer composition was injection molded using an injection molding machine (model number “N-100”, manufactured by Nippon Steel Works), and a test piece having a diameter of 29 mm and a thickness of 12.5 mm was obtained. Make it. The test piece is measured at a temperature of 105 ° C. for 72 hours. The measurement result of compression set (%) can be used as an evaluation index of seal characteristics.

[Outgas concentration]:
It was measured by a head space gas chromatography method (HS / GC method). Specifically, 0.5 g of the thermoplastic elastomer composition is placed in a sealed container in which the head space is 20 ml when 0.5 g of the thermoplastic elastomer composition is placed, and is sealed under atmospheric pressure at 150 ° C., 20 Heated for minutes. Thereafter, it was cooled to room temperature, 1 ml of gas in the head space was collected, and the gas components in the head space were analyzed by gas chromatography. After the analysis, the total amount of gas components in the head space was converted using n-hexane as a standard sample, and the obtained value was defined as the outgas concentration (ppm).

[Recycling characteristics]:
A pellet-shaped thermoplastic elastomer composition is obtained using an injection molding machine (model number “N-100”, manufactured by Nippon Steel Co., Ltd.), and the obtained thermoplastic elastomer composition is obtained at 180 to 250 ° C. (thermoplastic elastomer composition). Plastic deformation characteristics after heating to the range of the temperature used when recycling the product (that is, processing temperature) and then press molding using a press machine (manufactured by Kansai Roll Co., Ltd.) and a mold mold The presence or absence of was observed and evaluated. The evaluation criteria are “◯” as good recycling characteristics when plastic deformation characteristics are recognized, that is, when fluid molding is performed in the shape of the mold, and mold molding characteristics when plastic deformation characteristics are not recognized. When it was not fluidly molded into the shape of, “×” was evaluated as a poor recycling characteristic.

Example 1
A pressure type kneader (capacity: 10 liters, manufactured by Moriyama Co., Ltd.) heated to 150 ° C., ethylene propylene rubber (trade name “EP331”, manufactured by JSR, chlorine content 22 ppm, Table 1) 75 parts (shown as “ethylene propylene rubber (1)”), (B) 12.5 parts of polypropylene (trade name “B241”, manufactured by Ube Industries) as α-olefin crystalline thermoplastic resin, and (B ) 12.5 parts of trade name “RT2780” manufactured by Ube Industries, Ltd. was added as an α-olefin-based amorphous thermoplastic resin.

  Thereafter, the thermoplastic resin (polypropylene and α-olefin-based amorphous thermoplastic resin) is melted and the components added to the kneader are uniformly dispersed at 40 rpm (shearing speed 200 / sec) at 15 until the components are uniformly dispersed. It knead | mixed for minutes and the kneaded material (raw material composition) of the molten state was obtained. The obtained kneaded material in a molten state was pelletized using a feeder ruder (manufactured by Moriyama).

  100 parts of pelletized kneaded product, (C) 1.5 parts of crosslinking agent (trade name “Perhexine 25B-40”, manufactured by NOF Corporation), and divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., table) 1 part (shown as “co-crosslinking agent” in 1 and 2) was put into a Henschel mixer and mixed for 30 seconds. Then, using a twin-screw extruder (same direction complete meshing screw, L / D = 33.5, manufactured by Ikegai Co., Ltd.), 220 ° C., residence time 1 minute 30 seconds, 400 rpm (shear rate 400 / second) Then, a dynamic heat treatment was performed to obtain a pellet-shaped thermoplastic elastomer composition.

Each evaluation of the thermoplastic elastomer composition of the present embodiment is a tensile stress 2.5 MPa, tensile strength _{T B} is 7.4 MPa, a tensile elongation _{E B} is the 410%, compression set It was 35%, the outgas concentration was 13 ppm, and the evaluation result of the recycling characteristics was “◯”.

(Examples 2 and 3, Comparative Example 1)
Except having set it as the mixing | blending prescription shown in Table 1, it carried out similarly to Example 1, and obtained the pellet-shaped thermoplastic elastomer composition (Example 2, 3, comparative example 1). Each said evaluation was performed about the obtained thermoplastic elastomer composition. The evaluation results are shown in Table 1. In Table 1, “ethylene propylene rubber (2)” indicates ethylene propylene rubber (trade name “EP342”, chlorine content 80 ppm) manufactured by JSR.

(Comparative Example 2)
To a Banbury mixer heated to 100 ° C. (capacity 1.7 liters, manufactured by Kobe Steel), ethylene propylene rubber (trade name “EP21”, manufactured by JSR, chlorine content 105 ppm as ethylene / α-olefin copolymer rubber) , 100 parts shown in Table 1 as “ethylene propylene rubber (3)”, 10 parts softener (trade name “PW-380”, manufactured by Idemitsu Kosan Co., Ltd.), carbon black (trade name “SEAST S”, Tokai Carbon Co., Ltd.) 55 parts), zinc oxide (trade name “Zinc Hana 2”, manufactured by Hakusui Chemical Co., Ltd.) 5 parts, stearic acid (trade name “Lunac S-30”, manufactured by Kao Corporation) 0.5 part, The compounded rubber composition was obtained by kneading at 60 rpm for about 10 minutes until the components were uniformly dispersed. With respect to 170.5 parts of the obtained compounded rubber composition, 0.5 parts of a crosslinking aid (trade name “powder sulfur”, manufactured by Tsurumi Chemical Co., Ltd., shown as “vulcanizing agent” in Tables 1 and 2) Sulfur accelerator (trade name “Noxeller DM”, manufactured by Ouchi Shinsei Chemical Co., Ltd., indicated as “vulcanization accelerator (1)” in Table 1), vulcanization accelerator (trade name “Noxeller M”, Ouchi) 0.5 parts by Shinsei Chemical Co., Ltd., indicated as “vulcanization accelerator (2)” in Table 1, vulcanization accelerator (trade name “Noxeller TT”, manufactured by Ouchi Shinsei Chemical Co., Ltd., “vulcanization” in Table 1 0.75 parts of accelerating agent (3) ”, vulcanization accelerator (trade name“ Noxeller TRA ”, manufactured by Ouchi Shinsei Chemical Co., Ltd., shown as“ vulcanization accelerator (4) ”in Table 1) 5 parts and a 6 inch roll (manufactured by Kansai Roll Co., Ltd.) were added to obtain a compounded rubber composition containing a crosslinking agent (Comparative Example 2).

  The obtained compounded rubber composition containing a crosslinking agent is press-molded at 160 ° C. for 20 minutes using a press machine (manufactured by Kansai Roll Co., Ltd.) and a sheet having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm. A test piece for evaluating physical properties was prepared. Table 1 shows the evaluation results of the above evaluations of the prepared test pieces. The trade names and manufacturers of the various components and additives used are shown in Table 2.

  As is apparent from Table 1, the sheet material formed from the thermoplastic elastomer compositions of Examples 1 to 3 is the sheet formed from the thermoplastic elastomer composition of Comparative Example 1 and the vulcanized rubber composition of Comparative Example 2. Compared to the material, it was difficult to generate gas even when exposed to high temperatures, and the chlorine content in the generated gas was low, and it was confirmed that it had recycling characteristics.

  The thermoplastic elastomer composition of the present invention can be suitably used as a material for a sealing material used in an electronic device such as a hard disk.

  The sealing material of this invention can be used suitably as a sealing material used for electronic devices, such as a hard disk, for example.

Claims (5)

A thermoplastic elastomer composition used in electronic equipment,
(A) an ethylene / α-olefin copolymer rubber having a chlorine content by fluorescent X-ray analysis of 60 ppm or less;
(B) at least one thermoplastic resin selected from the group consisting of an α-olefin-based crystalline thermoplastic resin, an α-olefin-based amorphous thermoplastic resin, and a cyclic olefin-based thermoplastic resin;
A raw material composition containing
(C) A thermoplastic elastomer composition obtained by dynamically heat-treating in the presence of a crosslinking agent.   The thermoplastic elastomer composition according to claim 1, which is substantially free of a plasticizer and a softener.   In the head space of the container after 0.5 g was put in a sealed container with a head space of 20 ml when sealed with 0.5 g and sealed under atmospheric pressure and heated at 150 ° C. for 20 minutes. The thermoplastic elastomer composition according to claim 1, wherein the concentration of the gas component is 100 ppm or less.   The sealing material obtained by shape | molding the thermoplastic elastomer composition as described in any one of Claims 1-3.   The sealing material according to claim 4, wherein the sealing material is for household appliances or a housing for AV equipment.