JP2000290446A - Thermoplastic elastmer composition and formed material consisting of the same compostion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition having excellent oil resistance, mechanical characteristics and formability and a formed material obtained from the above composition. SOLUTION: This thermoplastic elastomer composition consists of (A) a functional group-containing ethylenic copolymer obtained from ethylene with a >=6C α-olefin, having 878-893 kg/m3 density and modified by a vinyl monomer having at least one functional group selected from acid anhydride, epoxy, carboxyl and carboxyl ester groups and (B) a polyamide resin, and contains 98-55 wt.% (A) the functional group-containing ethylenic copolymer and 2-45 wt.% (B) the polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition and a molded article obtained from the composition.
More specifically, it comprises a functional group-containing ethylene copolymer and a polyamide resin, and has excellent oil resistance, mechanical properties,
The present invention relates to a thermoplastic elastomer composition having moldability and a molded article obtained from the composition.

[0002]

Technical background of the invention Olefinic copolymers such as ethylene / propylene random copolymers are excellent in that they have low specific gravity, are excellent in moldability, hydrolytic resistance and economical efficiency, and show almost no water absorption. There are many. However, olefin copolymers have a drawback that oil resistance, mechanical strength, and the like are insufficient.

As a method for solving such a drawback, for example, Japanese Patent Application Laid-Open No. 63-41554 discloses a method of blending an ethylene / propylene / ethylidene norbornene copolymer with a polyamide and an acid-modified ethylene / butene copolymer. And a method of co-crosslinking with a crosslinking agent. Although this composition has improved oil resistance and mechanical strength, it has a drawback that the moldability is deteriorated due to a marked decrease in fluidity.

Japanese Patent Application Laid-Open No. Hei 9-87475 discloses that
Polyamide resin, ethylene and α having 6 to 20 carbon atoms
A polyamide resin composition comprising a graft-modified ethylene / α-olefin random copolymer obtained by graft-modifying an ethylene / α-olefin random copolymer obtained from -olefin is described.
It is mainly composed of a polyamide resin and is intended to improve flexibility, low-temperature impact resistance, water absorption resistance, salt water resistance and moldability of the polyamide resin composition.

In view of such prior art, the present inventors have conducted intensive studies to obtain a thermoplastic elastomer composition having excellent oil resistance, mechanical properties, and moldability. As a result, ethylene and carbon having at least 6 carbon atoms have been obtained. The composition comprising an α-olefin-modified copolymer with a vinyl monomer and a functional group-containing ethylene-based copolymer having a density within a specific range, and a polyamide resin satisfy the above requirements. The inventors have found that the present invention is satisfied, and have completed the present invention.

[0006]

That is, an object of the present invention is to provide a low specific gravity,
An object of the present invention is to provide a thermoplastic elastomer composition having excellent oil resistance, mechanical properties, and moldability, and a molded article obtained from the composition.

[0007]

SUMMARY OF THE INVENTION The thermoplastic elastomer composition according to the present invention is characterized in that (A) a copolymer of ethylene and an α-olefin having 6 or more carbon atoms comprises an acid anhydride group, an epoxy group, a carboxyl group and a carboxylic acid. A functional group-containing ethylene-based copolymer modified with a vinyl monomer containing at least one functional group selected from esters and having a density in the range of 878 to 893 kg / m ³ ; Resin, the functional group-containing ethylene copolymer (A) is contained at a ratio of 98 to 55% by weight, and the polyamide resin (B) is contained at a ratio of 2 to 45% by weight. I have.

The thermoplastic elastomer composition according to the present invention is suitable for molded articles.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the thermoplastic elastomer composition according to the present invention and a molded article comprising the composition will be described in detail.

The thermoplastic elastomer composition according to the present invention contains (A) a functional group-containing ethylene copolymer and (B) a polyamide resin. First, each component forming the thermoplastic elastomer composition according to the present invention will be described.

Functional Group-Containing Ethylene Copolymer (A) The functional group-containing ethylene copolymer (A) used in the present invention is an ethylene-based copolymer obtained from ethylene and an α-olefin having 6 or more carbon atoms. The copolymer is an ethylene copolymer modified with a functional group-containing vinyl monomer.

The functional group-containing ethylene copolymer (A) comprises (i) an ethylene copolymer and (ii) a functional group-containing vinyl monomer, and (iii) an organic peroxide or the like. Is melt-kneaded in the presence of a polymerization initiator, or (iii) an organic peroxide is dissolved in a solution of (i) an ethylene-based copolymer and (ii) a functional group-containing vinyl monomer in an organic solvent. It is obtained by kneading in the presence of a polymerization initiator such as a product.

The ethylene copolymer (i) is a polymer obtained by copolymerizing ethylene and an α-olefin having 6 or more carbon atoms, and has a repeating unit derived from ethylene of 85 to 94 mol%. And preferably 87 to 93 mol%, and 6 to 15 mol%, preferably 7 to 15 mol% of repeating units derived from an α-olefin having 6 or more carbon atoms.
Desirably, the ratio is about 13 mol%. When the ratio of the repeating unit derived from ethylene and the repeating unit derived from an α-olefin having 6 or more carbon atoms is within the above range, a thermoplastic elastomer composition having excellent flexibility can be obtained.

Here, the α-olefin having 6 or more carbon atoms includes, for example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12- Α-olefins having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as ethyl-1-tetradecene.

When the α-olefin is an α-olefin having 6 or more carbon atoms, a thermoplastic elastomer composition having excellent oil resistance can be obtained. Ethylene copolymer (i)
Has a density of 878 to 893 kg / m ³ , preferably 88
0 to 891 kg / m ³ , more preferably 882 to 889
It is desirably within the range of kg / m ³ . When the density is within the above range, a thermoplastic elastomer composition having excellent oil resistance and rubber elasticity can be obtained. In addition, the ethylene copolymer (i) is an ASTM D12
It is desirable that the melt flow rate measured at 250 ° C. under a load of 2.16 kg according to No. 38 is in the range of 0.05 to 200 g / 10 min, preferably 0.1 to 150 g / 10 min. When the melt flow rate is within the above range, a functional group-containing ethylene copolymer having good blending properties with the polyamide resin (B) can be obtained, and a thermoplastic elastomer composition having excellent moldability can be obtained.

The ethylene copolymer (i) has a crystallinity of at least 5%, preferably 10 to 30, as measured by X-ray diffraction. Examples of the olefin polymerization catalyst used for producing such an ethylene copolymer (i) include a titanium catalyst comprising a solid titanium catalyst component and an organic aluminum compound, and a soluble vanadium compound and an organic aluminum compound. And a metallocene catalyst comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table and an organoaluminum oxy compound and / or an ionized ionic compound. Of these, metallocene catalysts are particularly preferred. Catalysts are preferred.

As the functional group-containing vinyl monomer (ii), a vinyl monomer containing at least one functional group selected from polar groups such as an acid anhydride group, an epoxy group, a carboxyl group and a carboxylic acid ester. And specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic acid Unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate anhydride, dimethyl bicyclo (2,2 , 1) esters of unsaturated carboxylic acids such as dimethyl hept-2-ene-5,6-dicarboxylate;
Glycidyl acrylate, glycidyl methacrylate,
Glycidyl esters of unsaturated monocarboxylic acids such as glycidyl p-styrylcarboxylate; maleic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, endo-cis-bicyclo (2,2,1) hept-5-ene-2, 3-dicarboxylic acid, endo-cis-bicyclo (2,2,1) hept-5-ene-2-
Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acid such as methyl-2,3-dicarboxylic acid; allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether of m-allylphenol And unsaturated glycidyl ethers such as glycidyl ether of p-allylphenol, glycidyl ether of isopropenylphenol, glycidyl ether of o-vinylphenol, glycidyl ether of m-vinylphenol, and glycidyl ether of p-vinylphenol.

Of these, maleic acid, bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof are preferred. Examples of the organic peroxide (iii) include organic peroxides and organic peresters, and specific examples thereof include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and dicumyl peroxide.
-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3,1,4-bis (tert
-Butylperoxyisopropyl) benzene, lauroyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl -2,5-di (t
organic peroxides such as ert-butyl peroxy) hexane; tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-
Organic peresters such as butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethyl acetate and the like can be mentioned.

Among these, in the present invention, organic peroxides are preferable, and in particular, dicumyl peroxide, di-ter
t-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t
ert-butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,4-bis (te
(rt-butylperoxyisopropyl) benzene is preferably used.

The functional group-containing ethylene copolymer (A) is
Ethylene copolymer (i) and functional group-containing vinyl monomer (ii) are melt-kneaded in the presence of a polymerization initiator such as organic peroxide (iii), or ethylene copolymer This is obtained by kneading in a solution in which (i) and the functional group-containing vinyl monomer (ii) are dissolved in an organic solvent in the presence of a polymerization initiator such as an organic peroxide (iii). In the case, the weight ratio of the ethylene polymer (i), the functional group-containing vinyl monomer (ii) and the organic peroxide (iii) is usually
The organic peroxide is used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, of the functional group-containing vinyl monomer (ii) based on 100 parts by weight of the ethylene polymer (i). (Ii
i) is 0.001 to 2 parts by weight, preferably 0.005 to
Desirably, the amount is 1 part by weight.

When melt-kneading, the reaction temperature is 100 to
It is preferably 280 ° C, preferably 180 to 260 ° C. When kneading in a solution, the reaction temperature is 60-2.
The temperature is preferably 00 ° C, preferably 80 to 180 ° C, and examples of the solvent used include xylene, toluene, and dichlorobenzene.

The amount (modification amount) of the functional group in the functional group-containing ethylene copolymer thus obtained is from 0.01 to 0.01.
It is desirably 10% by weight, preferably 0.1 to 5% by weight. When the ratio of the functional group is within the above range,
A functional group-containing ethylene copolymer having excellent thermal stability and excellent blendability with the polyamide resin (B) can be obtained, and a thermoplastic elastomer composition having excellent mechanical strength can be obtained.

Polyamide Resin (B) The polyamide resin (B) used in the present invention is prepared by starting from a polymerizable aminocarboxylic acid or its lactam or dicarboxylic acid or diamine, and subjecting it to ring-opening polymerization or polycondensation. It is obtained.

Specific examples of aminocarboxylic acids include 6-
Examples include aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. In addition, these amino acids can be used in a mixture of two or more.

The lactams include valerolactam, caprolactam, enantholactam, caprylactam,
Examples include laurolactam and the like. Of these, use of caprolactam and laurolactam is preferred, and use of ε-caprolactam is most preferred. In addition, these lactams can also be used in a mixture of two or more.

Examples of the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, and tetradecandioic acid. Aliphatic dicarboxylic acids such as pentadecandioic acid and octadecandioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. In addition, these dicarboxylic acids are 2
Mixtures of more than one species can also be used.

The diamines include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
Methyl-1,5-diaminopentane (MDP), 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane,
1,12-diaminododecane, 1,13-diaminotridecane, 1,
14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, etc. Aliphatic diamines; cycloaliphatic diamines such as cyclohexanediamine and bis- (4-aminohexyl) methane; and aromatic diamines such as xylylenediamine. These diamines can also be used in a mixture of two or more.

The polyamide used in the present invention can be used alone or as a mixture. Nylon 6, nylon 66, nylon 6/6 among polyamide resins
6 type copolymer, nylon 66 / 6T type copolymer (T: terephthalic acid), nylon 6T / 6I type copolymer (I: isophthalic acid), nylon 6T / M5T type copolymer (M
5: 2-methylpentamethylenediamine, T: terephthalic acid), or a mixture thereof, particularly nylon 6 alone or a polyamide mixture containing nylon 6 as a main component.

The molecular weight of the polyamide resin used in the present invention is not particularly limited.
The relative viscosity measured at a concentration of 100 ml is 2.0 to 4.0.
Is preferred, more preferably 2.1 to 3.8, particularly preferably 2.2 to 3.6. If the relative viscosity is less than 2.0, the mechanical properties may be reduced, On the other hand, if it exceeds 4.0, the fluidity during molding tends to decrease.

The polyamide resin used in the present invention may be one whose terminal is blocked by a carboxylic acid compound or an amine compound, if necessary. When the terminal is blocked by a monocarboxylic acid and / or a monoamine, the concentration of the terminal amino group and the terminal carboxyl group of the obtained polyamide resin (hereinafter simply referred to as “terminal group concentration”) is lower than that before the terminal blocking. descend. On the other hand, when the terminal is blocked with a dicarboxylic acid or a diamine, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration changes while the terminal group concentration does not change.

Specific examples of the carboxylic acid compound used for terminal blocking of the polyamide resin include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, and tridecanoic acid. Aliphatic monocarboxylic acids such as myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and arachinic acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; benzoic acid; Aromatic monocarboxylic acids such as toluic acid, ethylbenzoic acid and phenylacetic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecane diacid Acid, tridecandioic acid, tetradecandioic acid, pendade Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; down diacids, aliphatic dicarboxylic acids such as octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.

Specific examples of the amine compound used for blocking the terminal of the polyamide resin include butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecyl. Amines, tetradecylamine, pentadecylamine,
Aliphatic monoamines such as hexadecylamine, octadecylamine, nonadecylamine and icosylamine; alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine and β-phenylethylamine; 1,4-diaminobutane; 1,5-diaminopentane, 1,6-diaminohexane, 1,
7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14 -Diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, etc. Aliphatic diamines; cycloaliphatic diamines such as cyclohexanediamine and bis- (4-aminohexyl) methane; and aromatic diamines such as xylylenediamine.

Thermoplastic Elastomer Composition The thermoplastic elastomer composition according to the present invention is prepared by blending the functional group-containing ethylene polymer (A) and the polyamide resin (B) by a method such as melt kneading. can do.

The composition ratio of such a thermoplastic elastomer composition is such that the functional group-containing ethylene copolymer (A) is 98%.
55% by weight, 2 to 45% by weight of the polyamide resin (B), preferably 9% by weight of the functional group-containing ethylene polymer (A).
5 to 60% by weight, 5 to 40% by weight of the polyamide resin (B), more preferably 95 to 70% by weight of the functional group-containing ethylene polymer (A), and 5 to 5% by weight of the polyamide resin (B).
It is desirably about 30% by weight.

In preparing the thermoplastic elastomer composition of the present invention, if necessary, a mineral oil or a compounding agent known per se is compounded within a range that does not impair the strength, moldability and rubber properties of the obtained composition. be able to.

Mineral oil-based softeners are high-boiling petroleum fractions usually used for the purpose of increasing flexibility and rubber elasticity, and are classified into paraffinic, naphthenic, aromatic and the like. In the present invention, a paraffin-based process oil is particularly effectively used. Such mineral oil softeners can be used in amounts up to 200 parts by weight per 100 parts by weight of the thermoplastic elastomer composition. If the amount is more than this range, the strength of the obtained thermoplastic elastomer composition is lowered, or the softening agent exudes to cause inconvenience such as impairing the appearance.

Examples of the compounding agent include a filler, a coloring agent, an antioxidant, an antistatic agent, a light-fast or light-fast stabilizer,
Processing aids, antistatic agents, and other physical property improvers can be used as appropriate.

For example, fillers include carbon black, zinc oxide, clay, talc, heavy calcium carbonate,
Kaolin, diatomaceous earth, silica, alumina, asbestos, graphite, glass fiber, etc. can be exemplified, and as the antioxidant, phenyl-α-naphthylamine, p-isopropoxydiphenylamine, N, N′-diphenylethylenediamine, nonylated Amine antioxidants such as diphenylamine; 2,6-di-tert-butylphenol;
Styrenated phenol, butylhydroxyanisole,
4,4'-hydroxydiphenyl, 2,2-methylene-bis- (4-
Methyl-6-cyclohexyl phenol), tetrakis-
(Methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate) methane, tri- (2-
Methyl-hydroxy-5-ditert-butylphenyl)
Examples thereof include phenyl-based antioxidants such as butane.

The thermoplastic elastomer composition of the present invention comprises:
It is particularly limited in fields where conventional thermoplastic elastomers have been used, for example, in the fields of automobile parts (interior materials, exterior materials, bumpers, etc.), electric components (vacuum cleaners, washing machines, etc.), electronic components, mechanical mechanism components, and the like. And automotive parts such as interior seats, bellows, tubes, mudguards, boots, etc .; industrial machinery parts such as pressure-resistant hoses, fuel oil hoses, gaskets, and diaphragms; It is useful for various molded articles such as building materials, footwear soles and the like. The thermoplastic elastomer composition of the present invention is particularly suitable for applications requiring oil resistance, and is suitable, for example, for automobile parts requiring oil resistance.

[0040]

According to the present invention, a thermoplastic elastomer composition having particularly excellent oil resistance and mechanical properties is provided. Further, a molded article obtained by using this composition is excellent in oil resistance, mechanical strength, and rubber elasticity, and thus can be widely used for automobile parts, electric parts, electronic parts, mechanical mechanism parts and the like.

[0041]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The measuring method used in the examples of the present invention is as follows. (1) Tensile test (strength, elongation) A dumbbell-type test piece punched from a 1 mm-thick press sheet was tested at 23 ° C, a span interval of 30 mm, and a tensile speed of 30 mm / min in accordance with ASTM D638. (2) Oil resistance (ΔV) A rectangular press sheet having a thickness of 3 mm was immersed in JIS No. 3 oil at 50 ° C. for 7 days in accordance with JIS K6301,
The rate of volume increase (percent) after immersion relative to before immersion was measured. (3) Rubber elasticity (PS) According to JIS K6301, a dumbbell-type test piece punched out from a 1 mm-thick press sheet is held at 100 ° C for 10 minutes at 23 ° C by a tensile tester, and the load is removed for 10 minutes. Later residual strain was measured. (4) Melt flow rate (MFR) 250 ° C. in accordance with ASTM D1238-65T,
2. Measured under a load of 16 kg.

[0043]

Example 1 [Preparation of maleic anhydride-modified ethylene / 1-octene copolymer] Ethylene / 1-octene copolymer (1) produced in the presence of a metallocene catalyst (MFR = 14 g)
/ 10 min, density = 886 kg / m ³ ) 1 part by weight of maleic anhydride (MAH) and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane in 100 parts by weight .1 parts by weight and melt-kneaded at 230 ° C. with a 30 mmφ twin screw extruder to obtain a maleic anhydride-modified ethylene / 1-octene copolymer (hereinafter referred to as “EOR-1”). . The resulting modified product had a maleic anhydride content (modified amount) of 0.5% by weight.

[Preparation of EOR-1 / Nylon 6 Composition] 90 parts by weight of EOR-1 obtained above was mixed with nylon 6 (relative viscosity = 2.30, melting point = 225 ° C., terminal amino group concentration =
4.4 × 10 ⁻⁵ eq / g, terminal carboxyl group concentration =
7.3 × 10 ⁻⁵ eq / g, hereinafter referred to as “Ny6-1”. ) Was blended in an amount of 10 parts by weight and melt-kneaded at 240 ° C. using a 20 mmφ twin screw extruder to obtain a thermoplastic elastomer composition.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0046]

Example 2 [Preparation of EOR-1 / Ny6-1 composition] In Example 1, the amount of EOR-1 was changed to 80 parts by weight,
A thermoplastic elastomer composition was obtained in the same manner as in Example 1, except that the amount of y6-1 was changed to 20 parts by weight.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0048]

Example 3 [Preparation of EOR-1 / copolymerized nylon 6 composition] In Example 2, Ny6-1 was converted to nylon 6/6.
A thermoplastic elastomer composition was obtained in the same manner as in Example 2, except that the copolymer was changed to 6 copolymer (relative viscosity = 2.50, melting point = 205 ° C, hereinafter referred to as “copolymer Ny6-1”). Was.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0050]

Example 4 [Preparation of EOR-1 / Nylon 6 Composition] In Example 2, Ny6-1 was converted to nylon 6 having a high terminal amino group concentration (relative viscosity = 2.35, terminal amino group concentration =
9.0 × 10 ⁻⁵ eq / g, terminal carboxyl group concentration =
4.6 × 10 ⁻⁵ eq / g, hereinafter referred to as “Ny6-2”. ) To obtain a thermoplastic elastomer by the same operation as in Example 2.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0052]

Example 5 [Preparation of maleic anhydride-modified ethylene / 1-octene copolymer] In Example 1, the ethylene / 1-octene copolymer (1) was replaced with the ethylene / 1-octene copolymer (2).
(MFR = 47 g / 10 min, density = 888 kg / m ³ ) except that the maleic anhydride-modified ethylene / 1-octene copolymer (hereinafter referred to as “E
OR-2 ". ) Got. The resulting modified product had a maleic anhydride content (modified amount) of 0.3% by weight.

[Preparation of EOR-2 / Ny6-1 composition] A thermoplastic elastomer was obtained in the same manner as in Example 2, except that EOR-1 was changed to EOR-2.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0055]

Comparative Example 1 [Preparation of maleic anhydride-modified ethylene / 1-butene copolymer] In Example 1, the ethylene / 1-octene copolymer (1) was replaced with the ethylene / 1-butene copolymer (1) (MF
R = 12 g / 10 min, density = 888 kg / m ³ ), except that the maleic anhydride-modified ethylene / 1-butene copolymer (hereinafter referred to as “EBR-1”) was obtained in the same manner as in Example 1.
It is described. ) Got. The resulting modified product had a maleic anhydride content (modified amount) of 0.6% by weight.

[Preparation of EBR-1 / Ny6-1 Composition] A thermoplastic elastomer was obtained in the same manner as in Example 2 except that EOR-1 was changed to EBR-1.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0058]

Comparative Example 2 [Preparation of maleic anhydride-modified ethylene / 1-octene copolymer] In Example 1, ethylene / 1-octene copolymer (1) was replaced with ethylene / 1-octene copolymer (3)
(MFR = 16 g / 10 min, density = 875 kg / m ³ ), except that the maleic anhydride-modified ethylene / 1-octene copolymer (hereinafter referred to as “E
OR-3 ". ) Got. The resulting modified product had a maleic anhydride content (modified amount) of 0.4% by weight.

[Preparation of EOR-3 / Ny6-1 Composition] A thermoplastic elastomer was obtained in the same manner as in Example 2 except that EOR-1 was changed to EOR-3.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the above-mentioned test methods. Table 1 shows the measurement results.

[0061]

Comparative Example 3 [Preparation of maleic anhydride-modified ethylene / 1-octene copolymer] In Example 1, EOR-1 was replaced with ethylene / 1-octene copolymer (4) (MFR = 57 g / 10
And the density were changed to 897 kg / m ³ ) to obtain a maleic anhydride-modified ethylene / 1-octene copolymer (hereinafter referred to as “EOR-4”) in the same manner as in Example 1. Was. The resulting modified product had a maleic anhydride content (modified amount) of 0.4% by weight.

[Preparation of EOR-4 / Ny6-1 Composition] A thermoplastic elastomer was obtained in the same manner as in Example 2 except that EOR-1 was changed to EOR-4.

The obtained thermoplastic elastomer composition was press-molded under predetermined conditions, and the physical properties were measured according to the test methods described above. Table 1 shows the measurement results.

[0064]

[Table 1]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Matsunaga 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Hideo Matsuoka Minato-ku, Nagoya-shi, Aichi 9 in Oe Town, Nagoya Office, Toray Co., Ltd. (72) Inventor Kazuki Miyamoto 1 in 9 Nagoya Office, Oe Town, Minato-ku, Nagoya City, Aichi Prefecture (72) Inventor, Shigeru Okita Aichi F-term (reference) 4F071 AA10 AA15 AA15X AA21X AA54 AA78 AA82 AF02 AF13 AH07 AH12 BA01 BB03 BB05 BB06 BC07 4J002 BB201 BB211 BN052 CD171 CL012 CL01 010

Claims (2)

[Claims] (1) (A) ethylene and α having 6 or more carbon atoms
-Copolymer with olefin, acid anhydride group, epoxy group,
A functional group-containing ethylene copolymer modified with a vinyl monomer containing at least one functional group selected from a carboxyl group and a carboxylic acid ester and having a density in the range of 878 to 893 kg / m ³ ; , (B) a polyamide resin, containing the functional group-containing ethylene copolymer (A) at a rate of 98 to 55% by weight, and containing the polyamide resin (B) at a rate of 2 to 45% by weight. A thermoplastic elastomer composition characterized in that: 2. A molded article comprising the thermoplastic elastomer composition according to claim 1.