JP2007211059A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition excellent also in flexibility in addition to barrier property to gases, organic liquids, etc., which is an advantage of an ethylene-vinyl alcohol-based copolymer and scarcely causing contamination by metal components. <P>SOLUTION: The thermoplastic elastomer composition is obtained by carrying out dynamic crosslinking treatment of (A) 10-90 pts.mass ethylene-vinyl alcohol-based copolymer, (B) 10-90 pts.mass elastomer and (C) 0.01-20 pts.mass organic peroxide or a phenol resin-based crosslinking agent, wherein total of components A and B is 100 pts.mass, under melted conditions. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, an elastomer such as an ethylene-vinyl alcohol copolymer, an isobutylene-isoprene copolymer rubber (butyl rubber), or an ethylene / α-olefin / non-conjugated diene copolymer is dynamically used with a specific crosslinking agent. The present invention relates to a thermoplastic elastomer composition formed by crosslinking and a molded article comprising the thermoplastic elastomer composition.

  The ethylene-vinyl alcohol copolymer has a high barrier property against gases, organic liquids, etc., and does not generate harmful gases during incineration like vinylidene chloride resin and vinyl chloride resin. Therefore, it is used for various applications such as food packaging materials. However, since an ethylene-vinyl alcohol copolymer is inferior in flexibility, it is known to be used in the form of a composition with a soft resin such as polyolefin (see Patent Document 1) or a laminate.

  Since the ethylene-vinyl alcohol copolymer and other resins usually have low affinity and poor compatibility, in the composition formed by blending a soft resin with the ethylene-vinyl alcohol copolymer, Insufficient flexibility and barrier properties. In addition, in a laminate obtained by laminating a soft resin layer to an ethylene-vinyl alcohol copolymer layer, the flexibility is improved as compared with the ethylene-vinyl alcohol copolymer layer alone. However, it may still lack flexibility depending on the application.

Therefore, recently, a thermoplastic elastomer composition including an elastomer in an ethylene-vinyl alcohol copolymer and dynamically crosslinked in the presence of a crosslinking agent and a molded product thereof have been proposed (Patent Document 2). See). Molded articles made of this thermoplastic elastomer composition are excellent in both barrier properties and flexibility. However, depending on the type of cross-linking agent used, the amount of metal components such as sodium and potassium contained exceeds a predetermined level, and electrons There was a problem that it would be inconvenient for applications such as parts.
JP-A-4-164947 JP 2002-60500 A

  Accordingly, the present invention has been made in view of the above-described conventional problems, and the object of the present invention is to provide flexibility and shielding properties against gases, organic liquids, and the like, which are the advantages of ethylene-vinyl alcohol copolymers. It is another object of the present invention to provide a thermoplastic elastomer composition and a molded product thereof that are excellent in that the metal component is less contaminated.

  As a result of intensive studies, the present inventors have dynamically crosslinked an ethylene-vinyl alcohol copolymer, an elastomer, and a specific crosslinking agent, so that the crosslinked elastomer is homogeneous in the ethylene-vinyl alcohol copolymer. It was found that a thermoplastic elastomer composition that is non-contaminating and has both barrier properties and flexibility can be obtained, and the present invention has been completed.

  According to the present invention, (A) 10-90 parts by mass of an ethylene-vinyl alcohol copolymer, (B) 10-90 parts by mass of an elastomer, and (C) an organic peroxide or phenol resin-based crosslinking agent. There is provided a thermoplastic elastomer composition obtained by dynamically crosslinking 01 to 20 parts by mass (provided based on a total of 100 parts by mass of (A) and (B)) under melting conditions.

［一般式（１）において、Ｒ^１は、水素原子又は炭素数１〜１０の炭化水素基を示し、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立して、水素原子、炭素数１〜１０の炭化水素基又は−ＣＯＯＨを示し、Ｙ^１、Ｙ^２及びＹ^３のうち少なくとも１つは−ＣＯＯＨであり、また、Ｙ^１、Ｙ^２及びＹ^３のうち２つ以上が−ＣＯＯＨである場合は、それらは互いに連結して形成された酸無水物（−ＣＯ−Ｏ−ＣＯ−）であってもよい。ｏは０〜２の整数であり、ｐは０〜５の整数である。］ In the present invention, (B) elastomer includes isobutylene-isoprene copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, butadiene rubber, maleic anhydride-modified ethylene / α-olefin copolymer rubber. , Maleic anhydride modified ethylene / α-olefin / non-conjugated diene copolymer rubber, maleic anhydride modified isobutylene-isoprene copolymer rubber, maleic anhydride modified butadiene rubber, ethylene, α having 3 to 10 carbon atoms -Use at least one selected from olefin, a functional cyclic monomer represented by the following general formula (1), and an olefin random copolymer obtained by copolymerizing a non-conjugated diene if necessary. Is preferred.

[In the general formula (1), ^{R 1} represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon ^atoms, Y 1, ^{Y 2} and ^{Y 3} are each independently a hydrogen atom, C1-10 When at least one of Y ¹ , Y ² and Y ³ is —COOH, and two or more of Y ¹ , Y ² and Y ³ are —COOH May be acid anhydrides (—CO—O—CO—) formed by being linked to each other. o is an integer of 0 to 2, and p is an integer of 0 to 5. ]

According to the present invention, (A) 10-90 parts by mass of an ethylene-vinyl alcohol copolymer, (B) 10-90 parts by mass of an elastomer, and (C) an organic peroxide or a phenol resin-based crosslink 0.01-20 parts by weight of the agent (however, with respect to the total of 100 parts by weight of (A) and (B)) is dynamically crosslinked under melting conditions to obtain a thermoplastic elastomer composition. A method for producing a plastic elastomer composition is provided.
Furthermore, according to this invention, the molded article formed by shape | molding said thermoplastic elastomer composition is provided.
Furthermore, the sealing material or tube material formed by molding the thermoplastic elastomer composition is for a capacitor, a battery, a toner case, an ink jet printer (including an ink cartridge), a flat panel display, or a housing. It can be preferably applied for use.

The present invention is described in detail below. First, each component which comprises the thermoplastic elastomer composition which concerns on this invention is demonstrated.
(A) Ethylene-vinyl alcohol copolymer:
The ethylene-vinyl alcohol copolymer (A) in the present invention is a copolymer mainly composed of ethylene units (—CH ₂ CH ₂ —) and vinyl alcohol units (—CH ₂ —CH (OH) —). . The ethylene-vinyl alcohol copolymer used in the present invention is not particularly limited, and examples thereof include known ones used in molding applications. However, the ethylene unit content of the ethylene-vinyl alcohol copolymer is preferably 10 to 99 mol% from the viewpoint of high shielding property against gas, organic liquid and the like and good moldability. More preferably, it is 20-75 mol%, More preferably, it is 25-60 mol%, Especially preferably, it is 25-50 mol%.

  As will be described later, the ethylene-vinyl alcohol copolymer is typically an ethylene-fatty acid vinyl ester copolymer saponified product, but in the case of an ethylene-fatty acid vinyl ester copolymer saponified product, The degree of saponification of the ester unit is preferably 50 mol% or more, and preferably 90 mol% or more, from the viewpoint of the barrier property and high thermal stability of the resulting ethylene-vinyl alcohol copolymer. More preferably, it is more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The melt flow rate of the ethylene-vinyl alcohol copolymer (measured by the method described in JIS K7210 under the conditions of a temperature of 210 ° C. and a load of 2.16 kg) is 0.1 from the viewpoint of good moldability. It is preferably ˜100 g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes, and particularly preferably 1 to 20 g / 10 minutes. The intrinsic viscosity of the ethylene-vinyl alcohol copolymer is preferably 0.1 to 5 dl / g at a temperature of 30 ° C. in a mixed solvent of 85% by weight of phenol and 15% by weight of water. More preferably, it is 2-2dl / g.

  In addition to the ethylene unit and the vinyl alcohol unit, the ethylene-vinyl alcohol copolymer has other structural units in a small amount (preferably 10 mol% or less based on the total structural units). Also good. Other structural units include α-olefins such as propylene, isobutylene, 4-methylpentene-1, 1-hexene, 1-octene; vinyl acetate, vinyl propionate, vinyl vinyl versatate, vinyl pivalate, Carboxylic acid vinyl esters such as valeric acid vinyl ester, capric acid vinyl ester and benzoic acid vinyl ester; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride, or derivatives thereof (eg, salts, esters, nitriles) And units derived from vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; N-methylpyrrolidone; In addition, the ethylene-vinyl alcohol copolymer may have a functional group such as an alkylthio group at the terminal.

  The method for producing the ethylene-vinyl alcohol copolymer is not particularly limited. For example, an ethylene-fatty acid vinyl ester copolymer is produced according to a known method, and then saponified. By this, an ethylene-vinyl alcohol copolymer can be produced. The ethylene-fatty acid vinyl ester copolymer is prepared by, for example, treating a monomer mainly composed of ethylene and a fatty acid vinyl ester under pressure in an organic solvent such as methanol, t-butyl alcohol, dimethyl sulfoxide, or the like. It can be obtained by polymerization using a radical polymerization initiator such as isobutyronitrile. Examples of the fatty acid vinyl ester include vinyl acetate vinyl ester, propionic acid vinyl ester, versatic acid vinyl ester, pivalic acid vinyl ester, valeric acid vinyl ester, capric acid vinyl ester, and the like. preferable. An acid catalyst or an alkali catalyst can be used for the saponification of the ethylene-fatty acid vinyl ester copolymer.

(B) Elastomer:
The elastomer (B) used in the present invention includes ethylene-α-olefin / non-conjugated diene copolymer rubber, isobutylene-isoprene copolymer rubber (butyl rubber), butadiene rubber, acrylic rubber, acrylonitrile butadiene rubber polybutadiene, and styrene-butadiene random. Examples thereof include copolymers, styrene-isoprene random copolymers, acrylonitrile-butadiene copolymers, chloroprene rubber, acrylic rubber, and natural rubber. Of these, isobutylene-isoprene copolymer rubber (butyl), ethylene-α-olefin / non-conjugated diene copolymer rubber, and butadiene are preferable, and isobutylene-isoprene copolymer rubber (butyl), ethylene-α-olefin /- Non-conjugated diene copolymer rubber is preferred.

(Ethylene-α-olefin-nonconjugated diene copolymer rubber)
The ethylene-α-olefin-nonconjugated diene copolymer rubber is not particularly limited as long as it is a copolymer including a structural unit (a1) derived from ethylene and a structural unit (a2) derived from an α-olefin. Therefore, the ethylene-α-olefin-nonconjugated diene copolymer rubber is a structural unit derived from another monomer in addition to the binary copolymer containing the structural unit (a1) and the structural unit (a2). A terpolymer further containing (a3) may be used. Furthermore, as long as it contains the structural unit (a1) and the structural unit (a2), it may be a multi-component copolymer containing 4 or more different structural units. The ethylene-α-olefin-nonconjugated diene 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-nonconjugated diene copolymer rubber is preferably 35 mol% or more when all the structural units are 100 mol%. When the proportion of the structural unit (a1) is less than 35 mol%, the mechanical strength of the resulting thermoplastic elastomer composition 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 thermoplastic elastomer composition obtained to become inadequate. Therefore, the proportion of the structural unit (a1) contained in the ethylene-α-olefin-nonconjugated diene copolymer rubber is more preferably 40 to 90 mol% when all the structural units are 100 mol%, It is especially preferable that it is -85 mol%.

  Specific 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 -Methylbutene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene and the like can be mentioned. Of these, propylene and 1-butene are preferable. These α-olefins can be used alone or in combination of two or more.

  The proportion of the structural unit (a2) contained in the ethylene-α-olefin-nonconjugated diene copolymer rubber is preferably 5 to 65 mol% when the total structural unit is 100 mol%, and 10 to 45 mol%. Is more preferable, and it is especially preferable that it is 15-40 mol%. When the proportion of the structural unit (a2) is less than 5 mol%, the resulting thermoplastic elastomer composition 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 thermoplastic elastomer composition tends to decrease.

  When the ethylene-α-olefin-nonconjugated diene copolymer rubber contains the structural unit (a3), examples of the monomer constituting the structural unit (a3) include a nonconjugated diene compound. . Specific 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 -Branching of dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydromyrcene, etc. Chain acyclic diene compounds; 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. Of these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferable. These comparative conjugated diene compounds can be used singly or in combination of two or more.

  When the ethylene-α-olefin-nonconjugated diene copolymer rubber contains the structural unit (a3), the proportion of the structural unit (a3) contained in the ethylene-α-olefin-nonconjugated diene copolymer rubber Is preferably 10 mol% or less, more preferably 1 to 8 mol%, when the total structural unit is 100 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.

  Further, as the ethylene-α-olefin-nonconjugated diene copolymer rubber, a graft polymer obtained by polymerizing an unsaturated monomer to the ethylene-α-olefin-nonconjugated diene copolymer described so far is used. You can also. Examples of unsaturated monomers include vinyl acetate; (meth) acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, (meth) acrylamide; maleic acid; maleic anhydride, maleimide And maleic acid derivatives such as dimethyl maleate; conjugated diene compounds such as butadiene, isoprene and chloroprene.

  The crystallinity of the ethylene-α-olefin-nonconjugated diene 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-nonconjugated diene copolymer is more than 20%, the flexibility of the resulting thermoplastic elastomer composition tends to be lowered.

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

  Further, as the ethylene-α-olefin-nonconjugated diene copolymer rubber, an oil-extended rubber obtained by adding a mineral oil softener to the ethylene-propylene-nonconjugated diene copolymer rubber described so far may be used. it can. Such oil-extended rubber. It is easy to handle. Therefore, it is preferable to use an oil-extended rubber as an ethylene-α-olefin-nonconjugated diene copolymer rubber because the production of the thermoplastic elastomer composition becomes easy. In addition, the ratio of the ethylene-α-olefin-nonconjugated diene copolymer rubber and the mineral oil softener contained in the oil-extended rubber is 20 to 80 respectively when the total oil-extended rubber is 100% by mass. It is preferably mass%, more preferably 25 to 75 mass%, and particularly preferably 30 to 70 mass%.

  The intrinsic viscosity (measured in decalin solvent at 135 ° C.) of the ethylene-α-olefin-nonconjugated diene copolymer rubber is preferably 1.8 dl / g or more. When the intrinsic viscosity of the ethylene-α-olefin-nonconjugated diene copolymer is less than 1.8 dl / g, mechanical strength and rubber elasticity tend to be lowered. On the other hand, when the intrinsic viscosity of the ethylene-α-olefin-nonconjugated diene copolymer is too large, the moldability tends to be lowered. Therefore, the intrinsic viscosity of the ethylene-α-olefin-nonconjugated diene copolymer rubber is more preferably 2.0 to 7.0 dl / g, and particularly preferably 2.0 to 6.0 dl / g. preferable.

(Isobutylene-isoprene copolymer rubber)
Isobutylene-isoprene copolymer rubber (hereinafter also referred to as “butyl rubber”) is a rubbery amorphous copolymer having a low degree of unsaturation, including a structural unit derived from isobutylene and a structural unit derived from isoprene. This isobutylene-isoprene copolymer rubber is obtained, for example, by slurry-polymerizing isobutylene and a small amount of isoprene in methyl chloride at a low temperature of about -100 ° C. using anhydrous aluminum chloride as a catalyst, and then drying. Can do.

  The proportion of the structural unit derived from isoprene contained in the isobutylene-isoprene copolymer rubber is preferably 0.5 to 15 mol% when the total structural unit is 100 mol%, and 0.8 to 5.0 mol. % Is more preferable. If the proportion of the structural unit derived from isoprene is less than 0.5 mol%, the crosslinking reaction tends to be delayed, and the mechanical strength may not be sufficient. On the other hand, when the proportion of the structural unit derived from isoprene is more than 15 mol%, the crosslinking density of the thermoplastic elastomer composition is excessively increased and the mechanical properties of the sealing material tend to be decreased.

  Examples of the unsaturated carboxylic acid-modified polymer rubber include a modified product (graft-modified product) obtained by subjecting a polymer rubber to an addition reaction of an α, β-unsaturated carboxylic acid or an acid anhydride thereof. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, crotonic acid, fumaric acid, and itaconic acid.

Suitable polymer rubbers in the case of graft modified products include ethylene-propylene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-hexene-1 copolymer rubber, ethylene-4-methylpentene-1 copolymer rubber, Ethylene-octene-1 copolymer rubber, ethylene-propylene copolymer rubber, ethylene-octene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-octene-nonconjugated diene copolymer Examples thereof include rubber and ethylene-butene-nonconjugated diene copolymer rubber.
The polymer rubber modified with these unsaturated carboxylic acid compounds is not limited to one type, and two or more types may be mixed and used. The amount of the unsaturated carboxylic acid compound in the modified polymer rubber is generally about 0.1 to 20% by weight.

[Olefin random copolymer obtained by copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, a functional cyclic monomer, and, if necessary, a non-conjugated diene]
An olefin random copolymer obtained by copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, a functional cyclic monomer, and, if necessary, a non-conjugated diene used in the present invention, Ethylene is used as the monomer. The proportion of ethylene used is preferably 35 to 94.99 mol%, more preferably 40 to 89.99 mol%, particularly preferably 45 to 84.99 mol%, based on the whole monomer. When the proportion of ethylene used is less than 35 mol%, it may be difficult to copolymerize a functional cyclic compound described later. On the other hand, compatibility with elastomers in which the proportion of ethylene used exceeds 94.99 mol% tends to deteriorate.

  An olefin random copolymer obtained by copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, a functional cyclic monomer, and, if necessary, a non-conjugated diene has a carbon number as a monomer. 3 to 10 α-olefin (hereinafter sometimes referred to as “specific α-olefin”) is used. By using an α-olefin having 10 or less carbon atoms, the copolymerizability between the α-olefin and the other monomer is improved. Specific examples of the specific α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-pentene-1,1-hexene, 1-heptene, 1-octene and 1-decene. . Among these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene and 1-butene are more preferable. These compounds can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the specific α-olefin used is preferably 5 to 50 mol%, more preferably 10 to 45 mol%, and particularly preferably 15 to 40 mol% of the whole monomer. When the usage ratio of the specific α-olefin is less than 5 mol%, the rubber elasticity of the resulting thermoplastic elastomer of the present invention may be deteriorated. On the other hand, when the use ratio of the specific α-olefin exceeds 50 mol%, the resulting thermoplastic elastomer composition may have low durability.

The olefin random copolymer uses a functional cyclic compound represented by the general formula (2) as a monomer. In the general formula (2), R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. . Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a butyl group, an alicyclic hydrocarbon group such as a cyclohexyl group, and a benzyl group. An aromatic hydrocarbon group is mentioned. Among these, it is particularly preferable that all of R ^{1 to} R ³ are ethyl groups, or one is a tert-butyl group (t-butyl group) and two are methyl groups. R ⁴ is independently a hydrogen atom, a halogen atom or a monovalent organic group independently of R ^{1 to} R ³ , preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a methyl group. . Moreover, the value of the repetition number n is 0 or 1, and preferably 1.

Specific examples of functional cyclic compounds include
Trimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate triethylsilyl,
T-butyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid tri-n-butylsilyl,
N-butyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Cyclohexyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Tribenzylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Trimethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Triethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyldimethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid tri-n-butylsilyl,
N-butyldimethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Cyclohexyldimethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Tribenzylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate trimethylsilyl;
Triethylsilyl 2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyldimethylsilyl 2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid tri-n-butylsilyl,
N-butyldimethylsilyl 2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Cyclohexyldimethylsilyl 2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Triethylsilyl 2-ethylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid n-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid allyldichlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid diallylchlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate vinyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid chloromethyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid t-butylphenylchlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid tribenzylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate dimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid n-butyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid allyldichlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid diallylchlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate vinyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid chloromethyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid t-butylphenylchlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid tribenzylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate dimethylsilyl,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
4-Chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
4-Chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-methoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl and the like. These functional cyclic compounds can be used alone or in combination of two or more.

Among these, from the viewpoint of the polymerizability of the functional cyclic compound and the stability of the obtained ionomer,
Trimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate triethylsilyl,
T-butyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid tri-n-butylsilyl,
N-butyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Cyclohexyldimethylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Tribenzylsilyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid n-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid tribenzylsilyl is preferred, and particularly preferred is
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid n-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
Can be mentioned.

  The functional cyclic compound described above is a compound obtained by silylation of the carboxyl group of a cyclic compound having a carboxyl group, so that the functional group-containing olefin random copolymer can be obtained without masking and unmasking. Can be manufactured.

  The use ratio of the functional cyclic compound is preferably 0.01 to 5 mol%, more preferably 0.01 to 4 mol% of the whole monomer. When the use ratio of the functional cyclic compound exceeds the above range, the compatibility tends to deteriorate.

  In the olefin random copolymer, a non-conjugated diene can be used as an arbitrary monomer in addition to the above monomers. Specific examples of this non-conjugated diene include linear acyclic dienes such as 1,4-hexadiene, 1,6-hexadiene, 1,5-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, 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, 5-vinyl- - it can be mentioned alicyclic dienes such as norbornene and the like. These compounds can be used individually by 1 type or in combination of 2 or more types. Among the non-conjugated dienes, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and the like can be mentioned. The proportion of non-conjugated diene used is preferably 0 to 10 mol% of the total monomer components. When this conjugated diene is used in an amount exceeding 10 mol%, the resulting thermoplastic elastomer composition may have low durability.

  The olefin-based random copolymer can be obtained by subjecting the above-described ethylene, the α-olefin having 3 to 10 carbon atoms, and the functional cyclic compound represented by the general formula (2) to addition polymerization. The addition polymerization treatment is performed by supplying ethylene, an α-olefin having 3 to 10 carbon atoms, a functional cyclic compound, and a conjugated diene used as necessary in an inert atmosphere such as nitrogen or argon. It is preferable to carry out the reaction in the presence of an appropriate solvent or diluent under conditions where the temperature of the reaction system is 0 to 150 ° C. The temperature of the reaction system is more preferably 10 to 100 ° C.

  As a catalyst for performing the addition polymerization treatment, a structural unit derived from each monomer in a copolymerization reaction of a functional cyclic compound, ethylene, an α-olefin, and a non-conjugated polyene used as necessary. It is preferable to use an olefin copolymerization catalyst that can obtain a copolymer in which is relatively randomly arranged. As such an olefin copolymerization catalyst, it is preferable to use a transition metal compound, preferably a compound composed of a metal compound selected from Groups 4 and 5 of the periodic table and an organoaluminum compound. Examples of suitable catalyst systems include the following.

(1) A catalyst system comprising a vanadium compound soluble in a hydrocarbon compound and an organoaluminum compound, wherein one or both of the vanadium compound and the organoaluminum compound contains at least one chlorine atom. it can. Here, as the vanadium compound, a compound represented by the following general formula (3-1), VCl ₄ , VO (acac) ₂ , V (acac) ₃ (where “acac” represents an acetylacetonate group. And a compound represented by the following general formula (3-2) can be used.

Formula (3-1): O = VCl _k (OR ¹¹ ) _3-k
(In the formula, R ¹¹ represents a hydrocarbon group such as an ethyl group, a propyl group, a butyl group, or a hexyl group. K represents an integer of 0 to 3.)
Formula (3-2): VCl ₃ · mZ
(Wherein Z represents a Lewis base capable of forming a complex soluble in a hydrocarbon compound such as tetrahydrofuran, 2-methyl-tetrahydrofuran, 2-methoxymethyl-tetrahydrofuran, dimethylpyridine, etc. m is an integer of 2 to 3) .)

  As the organoaluminum compound, a trialkylaluminum compound represented by the following general formula (3-3), an alkylaluminum hydride represented by the following general formula (3-4) or the following general formula (3-5), Chlorinated alkylaluminum represented by general formula (3-6), general formula (3-7) or general formula (3-8) below, general formula (3-9) or general formula (3-10) below Or an aluminoxane or phenoxy-substituted organoaluminum, methylalumoxane (MAO), ethylalumoxane, butylalumoxane or the like obtained by the reaction of water with the above trialkylaluminum compound can be used.

Formula (3-3): AlR ¹² ₃ ,
Formula (3-4): HAlR ¹² ₂ ,
Formula (3-5): H ₂ AlR ¹² ,
Formula (3-6): R ¹² AlCl ₂ ,
General formula (3-7): R ¹² ₃ Al ₂ Cl ₃ ,
Formula (3-8): R ¹² ₂ AlCl,
Formula _{^{(3-9): R 12 2 Al}} (OR 13),
Formula (3-10): R ¹² Al (OR ¹³ ) ₂
(In General Formula (3-3) to General Formula (3-10), R ¹² represents a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. R ¹³ represents a methyl group. , Ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyloxysilyl group, 2,6-di-t-butylphenyl group, 4-methyl-2,6-di-t-butylphenyl group or 2,6 -A dimethylphenyl group and a 4-methyl-2,6-dimethylphenyl group are shown.)

  In this catalyst system, an oxygen-containing or nitrogen-containing electron donor such as an organic acid or inorganic acid ester, ether, amine, ketone, alkoxysilane may be added to the vanadium compound and the organoaluminum compound. it can.

(2) A catalyst system comprising a titanium halide or zirconium halide supported on a carrier made of silica or magnesium chloride and an organoaluminum compound can be mentioned. Here, as titanium halide or zirconium halide, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, or the like can be used. As the organoaluminum compound, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylalumoxane and the like can be used. In this catalyst system, dioctyl phthalate, tetraalkoxysilane, diphenyldimethoxysilane and the like can be further added to the above compound.

(3) A metal selected from titanium, zirconium, and halfnium having one or two cyclopentadienyl groups or indenyl groups having a substituent selected from hydrogen, an alkyl group, and an allyl group as a ligand And a catalyst system comprising an organoaluminum compound containing at least 50 mol% of methylalumoxane.

  Specific examples of the transition metal compound include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) methylzirconium monochloride, ethylenebis (cyclopentadienyl). Zirconium dichloride, ethylenebis (cyclopentadienyl) methylzirconium monochloride, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4-methyl-1-indenyl) Luconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (indenyl) zirconium dichloride, dimethylsilylbis (dimethylcyclopentadienyl) ) Zirconium dichloride, dimethylmethyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylsilylbis (indenyl) zirconium dichloride, dimethylsilylbis (2-methyl-4) -Phenyl-indenyl) zirconium dichloride, bis (cyclopentadienyl) dimethyltitanium, bis (cycl Pentadienyl) methyltitanium monochloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, methylenebis (cyclopentadienyl) titanium dichloride, η1: η5- { [(Tert-Butyl-amido) dimethylsilyl] (2,3,4,5-tetramethyl-1-cyclopentadienyl)} titanium dichloride.

(4) A catalyst system comprising a periodic table group 4 transition metal complex having bisalkyl-substituted or N-alkyl-substituted salicylaldoimine as a ligand and methylalumoxane (MAO).

  As the solvent or diluent for performing the addition polymerization treatment, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof can be used. Specific examples include butane, pentane, hexane, heptane, 2-butene, 2-methyl-2-butene, cyclopentane, methylcyclopentane, cyclohexane, isooctane, benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane, and the like. It is done. These solvents or diluents are preferably used in a state where the water concentration is 20 ppm or less by distillation treatment or adsorption treatment.

  In such an addition polymerization treatment, the molecular weight of the specific addition copolymer obtained is adjusted by adding a molecular weight regulator, adjusting the amount of the polymerization catalyst, controlling the polymerization temperature, adjusting the addition rate to the polymer, etc. It can be done by the method. As the molecular weight regulator, hydrogen, diethyl zinc, diisobutylaluminum hydride, or the like can be used. Moreover, the reactor for performing the addition polymerization treatment may be either a batch type or a continuous type. As the continuous reactor, a tube reactor, a column reactor, a tank reactor, or the like can be used.

  The olefin-based random copolymer, after removing the solvent by blowing water vapor into the polymerization solution after the above addition polymerization treatment, separates solids from the resulting slurry, and further, screw-type squeezers, extrusion It can be obtained by dehydration and drying using a machine or a heating roll. Alternatively, the polymerization solution can be concentrated by heating and then dried using a vented extruder. If necessary, the polymerization catalyst residue can be separated and removed from the polymerization solution. As a specific method of such separation / removal treatment, a method of passing through an adsorption column packed with silica, alumina, diatomaceous earth, etc., a method of adding a large amount of water, alcohol, etc. to the polymerization solution and washing Can be used.

  The olefin random copolymer thus obtained has a polystyrene-reduced weight average molecular weight of 1,000 to 3,000,000 as measured by gel permeation chromatography using o-dichlorobenzene as a solvent. More preferably, it is 3,000 to 1,000,000, and particularly preferably 5,000 to 700,000. Moreover, it is preferable that the glass transition temperature of an olefin type random copolymer is -90-50 degreeC, especially -70-10 degreeC, and, thereby, the ionomer which has sufficient elasticity is obtained. Here, the glass transition temperature can be measured by a scanning differential thermal analyzer (DSC).

  (B) Component elastomers include isobutylene-isoprene copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, butadiene rubber, maleic anhydride-modified ethylene / α-olefin copolymer rubber, maleic anhydride Acid-modified ethylene / α-olefin / non-conjugated diene copolymer rubber, maleic anhydride-modified isobutylene-isoprene copolymer rubber, maleic anhydride-modified butadiene rubber, ethylene, α-olefin having 3 to 10 carbon atoms, The functional cyclic monomer represented by the following general formula (1) and, if necessary, at least one selected from an olefin random copolymer obtained by copolymerizing a non-conjugated diene may be used. When (B) elastomer having no functional group is used, it is blended with the polar group-containing (B) elastomer component. Better to use are preferred. Specifically, isobutylene-isoprene copolymer rubber and maleic anhydride modified ethylene / α-olefin copolymer rubber, and isobutylene-isoprene copolymer rubber and maleic anhydride modified ethylene / α-olefin / non-conjugated diene copolymer rubber. Polymerized rubber, isobutylene-isoprene copolymer rubber and maleic anhydride modified isobutylene-isoprene copolymer rubber, isobutylene-isoprene copolymer rubber and ethylene, α-olefin having 3 to 10 carbon atoms, represented by the following general formula (1) Functional cyclic monomer, olefin random copolymer obtained by copolymerization of non-conjugated diene if necessary, ethylene / α-olefin / non-conjugated diene copolymer rubber and maleic anhydride modified ethylene・ With α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber Maleic acid-modified ethylene / α-olefin / non-conjugated diene copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber and maleic anhydride-modified isobutylene / isoprene copolymer rubber, ethylene / α-olefin / A non-conjugated diene copolymer rubber and ethylene, an α-olefin having 3 to 10 carbon atoms, a functional cyclic monomer represented by the following general formula (1), and a non-conjugated diene are copolymerized as necessary. A combination of olefinic random copolymers is preferred. The blend ratio is preferably no functional group-containing (B) component / functional group-containing (B) component = 99/1 or more. If it is less than 1 part by weight, the mechanical properties tend to decrease.

(C) Crosslinking agent:
The component (C) used for producing the thermoplastic elastomer composition of the present invention is not particularly limited, but a compound capable of crosslinking at least the elastomer by dynamic heat treatment is a preferable crosslinking agent.

  Specific examples of the component (C) include organic peroxides, phenol resin crosslinking agents, sulfur, sulfur compounds, p-quinones, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, polyol crosslinking agents. And triazine compounds. Of these, organic peroxides and phenol resin crosslinking agents are preferred. 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-trimethyl Cyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl Okishido, benzoyl peroxide, may be mentioned di (t-butylperoxy) perbenzoate, n- butyl-4,4-bis (t-butylperoxy) valerate, and t-butyl peroxy isopropyl carbonate. Among them, 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. 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. Of these, p-substituted phenolic compounds are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  In said general formula (3), X is a hydroxyl group, R is a C1-C15 saturated hydrocarbon group, and n is an integer of 0-10. The p-substituted phenol compound can be obtained by a condensation reaction between a p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst.

  Examples of the above-mentioned phenolic cross-linking agents include tackol 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), tackol 250-I (brominated alkylphenol formaldehyde resin having a bromination rate of 4%, manufactured by Taoka Chemical Industries), and tackolol. 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (manufactured by Gunei Chemical Industry Co., Ltd.), ST137X (manufactured by ROHM & Haas Co., Ltd.), Sumilite Resin PR-22193 (manufactured by Sumitomo Durez) TAMANOL 531 (manufactured by Arakawa Chemical Co., Ltd.), SP1059 (manufactured by Schenectady), SP1045 (manufactured by Schenectady), SP1055 (manufactured by Schenectady), SP1056 (manufactured by Schenectady), CRM-0803 (manufactured by Showa Union Synthesis Co., Ltd.) Mentioned Among them, tackolol 201 (alkylphenol formaldehyde resin) is preferably used.

  The blending ratio of the component (A) and the component (B) in the thermoplastic elastomer composition of the present invention is such that the ethylene-vinyl alcohol copolymer (A) is 10 to 90 parts by weight, preferably 15 to 85 parts by weight. More preferably, the range is 20 to 85 parts by mass, and the elastomer (B) is 10 to 90 parts by mass, preferably 15 to 85 parts by mass, and more preferably 20 to 85 parts by mass. (However, A + B = 100 parts by mass)

  When the ethylene-vinyl alcohol copolymer (A) is less than 10 parts by mass or the elastomer (B) is more than 90 parts by mass, the phase structure (morphology) of the resulting thermoplastic elastomer composition is a dynamically crosslinked type. A good sea-island structure (the thermoplastic resin is the sea (matrix), the crosslinked rubber particles are less likely to be islands (domains)), and the fluidity and molding processability tend to decrease. When the ethylene-vinyl alcohol copolymer (A) is more than 90 parts by mass or the elastomer (B) is less than 10 parts by mass, the flexibility and rubber elasticity of the resulting thermoplastic elastomer composition tend to decrease. .

  Moreover, the usage-amount of a crosslinking agent (C) is 0.01- 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. 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 1.0 to 10 parts by mass.

  In the case of using an organic peroxide as a crosslinking agent, the amount of the organic peroxide used is the sum of the components (A) and (B) contained 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 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 exceeds 10 parts by mass, the degree of crosslinking becomes excessively high, the moldability is lowered, and the mechanical properties of the resulting thermoplastic elastomer composition tend to be lowered. On the other hand, when the amount of the organic peroxide used is less than 0.05 parts by mass, the degree of cross-linking is insufficient and the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition tend to be lowered.

  Moreover, when using a phenol resin crosslinking agent as a crosslinking agent, the usage-amount of this phenol resin crosslinking agent is (A) component and (B) component 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, and it is still more preferable to set it as 0.5-5 mass parts. If the amount of the phenol resin crosslinking agent used exceeds 10 parts by mass, the moldability tends to be lowered. On the other hand, 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 be lowered.

  It is preferable to use a crosslinking aid and / or a crosslinking accelerator together with the crosslinking agent because the crosslinking reaction can be performed gently and uniform crosslinking can be formed. When organic peroxide is used as a crosslinking agent, sulfur, sulfur compounds (powder sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, etc.), oxime compounds are used as crosslinking aids. (P-quinone oxime, p, p′-dibenzoylquinone oxime, etc.), polyfunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene) Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N′-m-phenylenebismaleimide, N N'- toluylene bismaleimide, maleic anhydride, divinylbenzene, the use of di (meth) zinc acrylate and the like) or the like. Of these, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide, and divinylbenzene are preferable. These can be used individually by 1 type or in combination of 2 or more types. Note that N, N′-m-phenylenebismaleimide exhibits an action as a crosslinking agent, and therefore can be used alone as a crosslinking agent.

  When a phenol resin crosslinking agent is used as the crosslinking agent, zinc oxide, magnesium oxide, soot dichloride or the like may be used as the crosslinking accelerator.

  In the case of using an organic peroxide as the crosslinking agent, the amount of the crosslinking aid used is 10 parts by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B) contained in the raw material composition. It is preferable to make it 0.2 to 5 parts by mass. 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.

  Use of amine-based crosslinking agents (for example, hexamethylenetetramine, hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6-hexadiamine) and amine-based anti-aging agents because contamination occurs Is not preferred.

  The thermoplastic elastomer composition of the present invention is obtained by dynamically crosslinking each of the components (A) to (C) described above under melting conditions. In this step, the ethylene-vinyl alcohol copolymer (A) and the elastomer (B) are melt-kneaded to finely and uniformly disperse, and the elastomer (B) is cross-linked by the cross-linking agent (C). Consists of. For melt-kneading, any apparatus may be used as long as it is a melt-kneading apparatus capable of uniformly mixing each component. Examples of such a melt-kneading apparatus include a single-screw extruder, a twin-screw extruder, A kneader, a Banbury mixer, etc. can be mentioned. Among them, it is preferable to use a twin screw extruder which has a large shearing force during kneading and can be operated continuously.

  As a specific example, the thermoplastic elastomer composition of the present invention can be produced through the following processing steps. That is, an ethylene-vinyl alcohol copolymer (A) elastomer (B) is mixed and charged into a hopper of an extruder. A part of the ethylene-vinyl alcohol copolymer (A) may be added from the middle of the extruder. The crosslinking agent (C) may be added from the beginning together with the ethylene-vinyl alcohol copolymer (A) and the elastomer (B), or may be added from the middle of the extruder. Further, two or more extruders may be used and melt kneaded sequentially in a stepwise manner. The melt kneading temperature is preferably about 160 to 280 ° C, more preferably 200 to 240 ° C. The melt kneading time is preferably about 30 seconds to 5 minutes.

  The thermoplastic elastomer composition obtained as described above has a structure in which an elastomer (B) crosslinked with a crosslinking agent (C) is dispersed in a matrix of an ethylene-vinyl alcohol copolymer (A). The dispersed particle diameter of the crosslinked elastomer is preferably 0.1 μm to 50 μm, and more preferably 0.1 μm to 30 μm.

  In order to stabilize the phase structure of the component (A) and the component (B), a compatibilizing material can be added to the thermoplastic elastomer composition of the present invention as necessary. It is a component necessary for stabilizing the phase structure of the thermoplastic elastomer composition of the present invention, and is capable of stabilizing the dispersion of (B) elastomer in (A) ethylene-vinyl alcohol copolymer. If there is no particular limitation. As such a compatibilizing agent, for example, an olefin resin, a hydrogenated diene polymer in which a polar group is introduced in the main chain or in the side chain in the molecule, a polar group in the main chain or in the side chain in the molecule. Examples thereof include a hydrogenated diene polymer and a vinyl polymer graft copolymer. In general, polar groups include, for example, acid hydride, carboxyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, imide group, hydroxyl group, epoxy Groups, oxazoline groups, thiol groups, etc., but preferred polar groups of the compatibilizer used in the present invention are carboxyl groups, acid anhydrides, carboxylic acid esters, isocyanate esters, epoxy groups, oxazoline groups. Of these, a carboxyl group, an acid anhydride, a carboxylic acid ester, and an epoxy group are preferable. The compatibilizer is such that the olefin resin or vinyl polymer as the skeleton is compatible with the elastomer of the component (B), and the polar group reacts with the ethylene-vinyl alcohol copolymer of the component (A). In order to occur, it is possible to form a stable dispersion form of the component (B) in the component (A).

  The amount of the compatibilizer is 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total amount of the component (A) and the component (B). It can be a weight part. If it exceeds 20 parts by weight, the rubber elasticity of the finally obtained thermoplastic elastomer composition tends to be lowered.

(Softener and / or plasticizer)
In addition to the components (A) to (C), the thermoplastic elastomer composition of the present invention may further contain a softener and / or a plasticizer as necessary.
Examples of the softener used in the present invention include petroleum softeners such as aromatic oil, naphthenic oil, paraffin oil, white oil, petrolatum, and gilsonite, castor oil, cottonseed oil, rapeseed oil, palm oil, coconut oil, and rosin. Examples include vegetable oil-based softeners.

Examples of the plasticizer used in the present invention 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, diisooctyl azelate, diisobutyl azelate, Fatty acid esters such as dibutyl sebacate, di- (2-ethylhexyl) sebacate, diisooctyl sebacate, trimellitic acid isodecyl ester, In addition to trimellitic esters such as rimellitic acid octyl ester, trimellitic acid n-octyl ester, trimellitic acid isononyl ester, di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, Examples of the plasticizer include tristearyl phosphate, tri- (2-ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, and polyether ester. In practicing the present invention, the softener and / or plasticizer can be used alone or in combination of two or more.
The softener and / or the plasticizer may be added to the component (A) and the component (B) during the production of the thermoplastic elastomer composition, or may be added during the polymerization of the component (A).

  The blending amount of the softener and / or plasticizer can be 100 parts by weight or less, preferably 95 parts by weight or less, more preferably 100 parts by weight or less per 100 parts by weight of the total amount of the component (A) and the component (B). It can be 90 parts by weight or less. When the amount exceeds 100 parts by weight, the softening agent bleeds out from the finally obtained thermoplastic elastomer composition, and mechanical strength and rubber elasticity tend to decrease.

  In addition to the components described above, the thermoplastic elastomer composition of the present invention may contain other polymers, if necessary, within a range that does not substantially impair the effects of the present invention. Examples of other polymers that can be blended include ionomers, aminoacrylamide polymers, polyisobutylene, vinyl chloride polymers, ethylene vinyl acetate copolymers, polyethylene oxide, ethylene acrylic acid copolymers, chlorinated polypropylene, 4- Methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, acrylic resin, methacrylic resin , Vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, vinyl acetal resin, methyl methacrylate resin, fluorine resin, polyether resin, polyethylene terephthalate, polyacrylate, polyamide resin, poly Urethane, polyimide, polyurea resins, epoxy resins, phenol resins, urea resins, polybutene-1, methylpentene resins, and polyacrylonitrile.

  Furthermore, the thermoplastic elastomer composition of the present invention can contain an inorganic filler, a pigment, and the like as necessary for the purpose of reinforcement, weight increase, coloring and the like. Examples of inorganic fillers and dyes include calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, and barium sulfate. The blending amount of the inorganic filler and the dye / pigment is preferably within a range that does not impair the barrier property to the gas, organic liquid, etc. of the thermoplastic elastomer composition, and is generally an ethylene-vinyl alcohol copolymer (A). And 50 parts by mass or less with respect to 100 parts by mass in total of the elastomer (B).

  In addition to the above-described components, the thermoplastic elastomer composition of the present invention includes a lubricant, a light stabilizer, a flame retardant, an antistatic agent, silicone oil, an antiblocking agent, an ultraviolet absorber, an antioxidant, as necessary. You may contain the 1 type (s) or 2 or more types of other components, such as a mold release agent, a foaming agent, and a fragrance | flavor.

  The thermoplastic elastomer composition of the present invention can be used as a molding material in any form such as pellets and powders. Furthermore, since the elastomer composition of the present invention has thermoplasticity, it can be molded using a normal molding method or molding apparatus used for general thermoplastic polymers. As the molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calendar molding, or vacuum molding can be employed. Molded articles comprising the elastomer composition of the present invention produced by such a method include a wide variety of pipes, sheets, films, disks, rings, bags, bottles, strings, fibers, and the like. In addition, a laminated structure or a composite structure with other materials is also included. By adopting a laminated structure with other materials, it is possible to introduce the properties of other materials such as moisture resistance and mechanical properties into the molded product.

  In a molded article having a laminated structure of at least one layer made of the thermoplastic elastomer composition of the present invention and at least one layer made of another material, the other material has required characteristics, intended use, etc. Appropriate ones may be selected according to the situation. Examples of the other materials include polyolefin (eg, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, polypropylene, etc.), ionomer, ethylene-vinyl acetate copolymer. Examples thereof include thermoplastic polymers such as a polymer (EVA), an ethylene-acrylic acid ester copolymer (EEA), polystyrene (PS), a vinyl chloride resin (PVC), and a vinylidene chloride resin (PVDC).

  In the molded article having the laminated structure, an adhesive layer may be interposed between a layer made of the thermoplastic elastomer composition of the present invention and a base material layer made of another material. By interposing the adhesive layer, the layers made of the thermoplastic elastomer composition of the present invention on both sides thereof and the base material layer made of another material can be firmly joined and integrated. Examples of the adhesive used in the adhesive layer include acid anhydride-modified products of diene polymers; acid anhydride-modified products of polyolefins; polymer polyols (for example, glycol compounds such as ethylene glycol and propylene glycol, and adipic acid) Polyester polyol obtained by polycondensation of a dibasic acid, a partially saponified product of a copolymer of vinyl acetate and vinyl chloride, and a polyisocyanate compound (for example, a glycol compound such as 1,6-hexamethylene glycol) A reaction product of a molar ratio of 1 to 2 with a diisocyanate compound such as 2,4-tolylene diisocyanate; a molar ratio of a triol compound such as trimethylolpropane and a diisocyanate compound such as 2,4-tolylene diisocyanate of 1: 3 A mixture with a reaction product or the like can be used. For forming the laminated structure, a known method such as co-extrusion, co-injection, or extrusion coating can be used.

  The molded article made of the elastomer composition of the present invention has excellent barrier properties against many gases, organic liquids, etc. and excellent flexibility, and also has excellent compression set (rubber elasticity), and as a crosslinking agent. Since no amine compound is used, the thermoplastic elastomer composition can be widely used for general processed products. General processed products include, for example, automobile bumpers, exterior moldings, wind seal gaskets, door seal gaskets, trunk seal gaskets, roof side rails, emblems, interior / exterior skin materials, weather strips, etc. Sealing materials and interior / exterior skin materials, etc., civil engineering / architecture sealing materials, interior / exterior skin materials or waterproof sheet materials, general machinery / equipment sealing materials, etc., weak electrical parts, flat panel displays, liquid crystal panels, fuel cells, Examples include packings and housings for inkjet printer parts, daily miscellaneous goods, sports equipment, and the like.

  In addition, the molded article which consists of an elastomer composition of this invention also has the advantage that it can fuse | melt and can be reused in the case of disposal.

  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. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Oxygen permeability coefficient]
Using the thermoplastic elastomer composition pellets produced in the following examples and comparative examples, the pellets were compression-molded under heating by a compression molding machine to produce a sheet-like test piece having a thickness of 500 μm, and these were used. Then, the oxygen permeability coefficient was measured. The oxygen permeability coefficient was measured under the conditions of an oxygen pressure of 1 atm, a temperature of 40 ° C., and a humidity of 90% RH in accordance with A method (atmospheric pressure method) of JIS K7126.

[hardness]
Based on JIS K6253, the hardness 10 seconds after the start of measurement in the Duro D hardness was measured and used as an index of flexibility.

[Tensile test]
Based on JIS K6251, 100% modulus M ₁₀₀ (MPa), tensile strength T _B (MPa), and tensile elongation E _B (%) were measured.

[Compression set]
It was measured under conditions of 70 ° C. × 22 h in accordance with JIS K6262, and used as an index of rubber elasticity.

[Contamination]
JIS K6267 contact and migration contamination test In accordance with the heating promotion method, using a white coated plate as a non-contaminating material, the test is conducted at a temperature of 70 ° C., a heating time of 24 hours, and without secondary exposure. The degree of contamination of the material was visually evaluated. In addition, “○” indicates that there is no contamination, and “×” indicates that there is contamination.

[Ethylene-vinyl alcohol copolymer (A)]
Saponified ethylene-vinyl acetate copolymer having an ethylene unit content of 44 mol%, a temperature of 210 ° C., and a load flow of 2.16 kg measured at 12 g / 10 min: Nippon Synthetic Chemical Co., Ltd. "Soarnol A4412" manufactured by
[Elastomer (B-1)]
Isobutylene-isoprene copolymer rubber: “IIR268” manufactured by JSR Corporation.
[Elastomer (B-2)]
Ethylene / α-olefin / non-conjugated diene copolymer rubber: “EP57C” manufactured by JSR Corporation.
[Elastomer (B-3)]
Ethylene / α-olefin copolymer rubber modified with maleic anhydride: “T7761P” manufactured by JSR.
[Elastomer (B-4)]
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid 32.8 g (150 mmol), dry tetrahydrofuran 200 mL and dry pyridine 13.1 g (165 mmol) were added to the reaction system at a temperature of 0 ° C. and triethylchlorosilane 24 .9 g (165 mmol) was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 5 hours. Next, the reaction solution was filtered, and the filtrate was concentrated. Then, 100 ml of n-hexane was added and stirred for 1 hour, and then this solution was filtered. Next, the filtrate was concentrated and distilled under reduced pressure under conditions of 143 to 147 ° C. and 1.5 mmHg to give 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate triethylsilyl was obtained.

In a 2 L separable flask substituted with nitrogen, 1000 mL of hexane as a solvent and 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 1.0 mL / L hexane solution of triethylsilyl dodeca-9-ene-4-carboxylate and 3.5 mL of 5-ethylidene-2-norbornene were added, and ethylene (supplied amount) was added at 20 ° C. : 5.0 L / min.) / Propylene (feed amount: 4.5 L / min.) / Hydrogen (feed amount: 0.6 L / min.) Mixed gas was continuously fed, and a 2 L separable flask after 5 minutes. Then, 3.66 mL of a 0.32 mol / L hexane solution of VOCl ₃ was added, and 50.7 minutes later, 20.7 mL of a 0.41 mol / L hexane solution of Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ was added into a ₂ L separable flask. Was added to initiate addition polymerization of the monomer. After addition polymerization treatment at 25 ° C. for 10 minutes, 4.8 mL of acetic acid was added to the reaction system to stop the polymerization reaction.

  The obtained polymerization solution is washed with 500 mL of water, and then poured into a large amount of methanol to precipitate a copolymer, which is vacuum-dried to give a white olefin random copolymer (F) 21. 1 g was obtained.

When this olefin random copolymer was analyzed, the content ratio of structural units derived from ethylene was 73.18 mol%, the content ratio of structural units derived from propylene was 25.50 mol%, and 5-ethylidene-2- The content rate of the structural unit derived from norbornene is 0.94 mol%, 4-methyltetracyclo [6.2.1.1 ^3,6 . The content ratio of the structural unit derived from triethylsilyl 0 ^2,7 ] dodec-9-ene-4-carboxylate was 0.38 mol%. Moreover, the polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography using o-dichlorobenzene as a solvent was 25.5 × 10 ⁴ .

[Elastomer (B-5)]
Triblock copolymer composed of polystyrene-hydrogenated polybutadiene block-polystyrene block and modified with maleic anhydride: “Tuftec M1943” manufactured by Asahi Kasei Corporation.

[Crosslinking agent (C-1)]
Alkylphenol formaldehyde resin: “Tacchi Roll 201” manufactured by Taoka Chemical Co., Ltd.
[Crosslinking agent (C-2)]
Mixture of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and silica: “Perhexine 25B-40” manufactured by NOF Corporation.
[Crosslinking agent (C-3)]
1,6-hexanediamine.
[Crosslinking aid (D)]
“Divinylbenzene (concentration 81%)” manufactured by Nippon Steel Chemical Co., Ltd.

Example 1
30 parts of ethylene-vinyl alcohol copolymer (A), 50 parts of elastomer (B-1), and 20 parts of elastomer (B-3) in a pressure type kneader (capacity 10 liters, manufactured by Moriyama Co., Ltd.) heated to 160 ° C Was introduced at a rate of. A kneaded material in a molten state was obtained by kneading at 40 rpm (shear rate 200 / sec) for 15 minutes until the ethylene-vinyl alcohol copolymer (A) was melted and each component was uniformly dispersed. The obtained kneaded material in a molten state was pelletized using a feeder ruder (manufactured by Moriyama Co., Ltd.) to obtain a kneaded material. 100 parts of the pelletized kneaded material and 2 parts of the crosslinking agent (C-1) were 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.), 200 ° C., residence time 1 minute 30 seconds, 300 rpm, (shear speed 400 / sec) And extruding while carrying out dynamic heat treatment to obtain a pellet-shaped thermoplastic elastomer composition (Example 1).

The obtained thermoplastic elastomer composition is injection-molded using an injection molding machine (model number “N-100”, manufactured by Nippon Steel Works Co., Ltd.) to evaluate the physical properties of a 120 mm × 120 mm × 2 mm sheet. A test piece was prepared. The test piece prepared using the thermoplastic elastomer composition obtained in Example 1 has an oxygen permeability coefficient of 31 ml · 20 μm / m ² · day · atm, a hardness of 34, a ₁₀₀ % modulus M ₁₀₀ of 8.0 MPa, and a tensile strength. T _B is 10.5 MPa, the tensile elongation _{E B} 230% rubber elasticity (compression set) 45%, and contamination of the result of evaluation was "○".

(Examples 2-4, Comparative Examples 1-3)
Except having set it as the mixing | blending prescription shown in Table 1, it carried out similarly to the case of the above-mentioned Example 1, and obtained the pellet-shaped thermoplastic elastomer composition (Examples 2-4, Comparative Examples 1-3). The obtained thermoplastic elastomer composition was injection-molded in the same manner as in Example 1 to prepare test pieces for evaluating physical properties. Table 1 shows the measurement results of various physical properties and the evaluation results of the properties of the prepared test pieces.

(result)
From the results shown in Table 1, the following is clear.
Ethylene-vinyl alcohol copolymer (A), elastomer (B-1) or elastomer (B-2), cross-linking agent (C-1) or cross-linking agent (C-2), cross-linking agent (C-2) When using the thermoplastic elastomer composition of Examples 1 to 3 produced using the crosslinking aid (D), a non-staining material having excellent oxygen permeability, flexibility and rubber elasticity can be obtained. I understand.
On the other hand, the thermoplastic elastomer composition (Comparative Examples 1 and 2) containing the elastomer (B-5) is inferior in flexibility and rubber elasticity, and the thermoplastic elastomer composition containing the crosslinking agent (C-3) ( It can be seen that Comparative Examples 1 and 3) have a problem of contamination.

  The thermoplastic elastomer composition of the present invention has excellent barrier properties and flexibility to gases, organic liquids and the like, and also has good non-staining properties. Therefore, packaging materials for foods and beverages, containers and containers that require these properties. In addition to applications such as packing, it is effectively used especially as an electronic component.

Claims (6)

(A) 10-90 parts by mass of an ethylene-vinyl alcohol copolymer,
(B) 10 to 90 parts by mass of elastomer, and (C) 0.01 to 20 parts by mass of a crosslinking agent that is an organic peroxide or phenol resin (however, with respect to 100 parts by mass of (A) and (B) in total) )
Is a thermoplastic elastomer composition obtained by dynamically crosslinking under melting conditions. (B) The elastomer is an isobutylene-isoprene copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, butadiene rubber, maleic anhydride-modified ethylene / α-olefin copolymer rubber, or maleic anhydride-modified rubber. Ethylene / α-olefin / non-conjugated diene copolymer rubber, maleic anhydride-modified isobutylene-isoprene copolymer rubber, maleic anhydride-modified butadiene rubber, ethylene, α-olefin having 3 to 10 carbon atoms, the following general formula The functional cyclic monomer represented by (1) and at least one selected from an olefin-based random copolymer obtained by copolymerizing a non-conjugated diene if necessary. A thermoplastic elastomer composition.

[In the general formula (1), ^{R 1} represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon ^atoms, Y 1, ^{Y 2} and ^{Y 3} are each independently a hydrogen atom, C1-10 When at least one of Y ¹ , Y ² and Y ³ is —COOH, and two or more of Y ¹ , Y ² and Y ³ are —COOH May be acid anhydrides (—CO—O—CO—) formed by being linked to each other. o is an integer of 0 to 2, and p is an integer of 0 to 5. ]   (A) 10-90 parts by mass of an ethylene-vinyl alcohol copolymer, (B) 10-90 parts by mass of an elastomer, and (C) 0.01-20 parts by mass of an organic peroxide or phenol resin-based crosslinking agent. A method for producing a thermoplastic elastomer composition, wherein a thermoplastic elastomer composition is obtained by dynamically crosslinking (with respect to a total of 100 parts by mass of (A) and (B)) under melting conditions.   A molded article obtained by molding the thermoplastic elastomer composition according to claim 1.   3. A seal formed by molding a thermoplastic elastomer composition according to claim 1 or 2 for a capacitor, a battery, a toner case, an ink jet printer (including an ink cartridge), a flat panel display, or a housing. Wood.   3. A tube formed by molding the thermoplastic elastomer composition according to claim 1 or 2 for a capacitor, a battery, a toner case, an ink jet printer (including an ink cartridge), a flat panel display, or a housing. Wood.