JP2000034401A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain thermoplastic elastomer composition excellent in flexibility and resistance to flatting at high temperatures by compounding a specified amount of a specified ester elastomer and a specified amount of an olefin elastomer. SOLUTION: This composition comprises 100 pts.wt. ester elastomer being a block copolymer prepared by bonding 100 pts.wt. polyester copolymer comprising 50-95 wt.% repeating short-chain polyester component units of formula I and 50-5 wt.% repeating long-chain polyester component units of formula II to 50-500 pts.wt. polyether comprising repeating units of the formula: -R3-O- through 10-100 pts.wt. urethane bonding component of formula III or IV and 50-500 pts.wt. olefin elastomer consisting of a polyolefin resin and a rubber component dispersed therein. In the formula, R1 and R3 are each a 2-8C alkylene; R2 is a component comprising repeating units of the formula: -R-O- and having a number-average molecular weight of 500-5,000; R is R1; and R4 is a 2-15C alkylene, phenylene, a 2-15C alkylene, or a group composed of methylene and phenylene bonded to each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition capable of providing a thermoplastic elastomer having excellent flexibility and mechanical properties at high temperatures, especially excellent sag resistance at high temperatures.

[0002]

2. Description of the Related Art In recent years, due to increasing awareness of environmental issues,
The replacement of recyclable materials in various industrial fields is accelerating. Thermoplastic elastomer (TP
E) has been attracting attention for a long time because it exhibits rubber elasticity at room temperature but exhibits plasticity at high temperatures and can be molded normally, and is used in various applications in fields such as automobiles and various industries. became.

[0003] Among them, polyester-based elastomer (TPEE) has excellent mechanical strength, oil resistance, abrasion resistance, and flex fatigue resistance, and is therefore used in a wide range of industrial fields mainly in the field of automobiles. However, TPEE has the drawbacks that it has higher hardness than ordinary rubber and lacks flexibility, and lacks sag resistance due to large compression set at high temperatures, and its improvement has been desired.

In order to impart flexibility to the TPEE, it is conceivable to reduce the amount of the hard segment component responsible for physical crosslinking, but as a result, the blockability of the hard segment component is reduced and the melting point is lowered. There is a problem that the mechanical properties at high temperatures are deteriorated (Japanese Unexamined Patent Publication No.
No. 88632).

On the other hand, a polyolefin-based elastomer (v-TPO) obtained by so-called dynamic crosslinking can be a thermoplastic elastomer having excellent flexibility and sag resistance, but has a disadvantage of poor mechanical strength and oil resistance. is there. Therefore, in order to impart sag resistance to TPEE, simply add TP
Even if a composition in which EE is blended with v-TPO is obtained (see JP-A-9-316285), v-TPO must be blended within a range that does not impair the mechanical strength and oil resistance of TPEE. At present, it is difficult to obtain a TPEE having the original mechanical strength and oil resistance, and having sufficiently improved flexibility and sag resistance.

[0006]

DISCLOSURE OF THE INVENTION In view of the above, the present invention provides a thermoplastic elastomer composition having excellent flexibility and mechanical properties at high temperatures, especially excellent set resistance, and excellent mechanical strength and oil resistance. The purpose is to provide.

[0007]

Means for Solving the Problems The thermoplastic elastomer composition of the present invention comprises a repeating short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). Is, the short-chain polyester component is
A polyester copolymer (A) in which the long-chain polyester component is 50 to 5% by weight, and a polyether (B) comprising a repeating unit represented by the general formula (3);
A block copolymer comprising a polyester copolymer
(A) and polyether (B) have the general formula (4) or the general formula (5)
Is bonded by a urethane-binding component (C) represented by the formula: 50 to 500 parts by weight of a polyether (B) and a urethane-binding component, based on 100 parts by weight of a polyester-based copolymer (A).
(C) 10 to 100 parts by weight of an ester-based elastomer [1] and polyolefin resin (D) in rubber
(E) is an olefin-based elastomer [2] having a structure in which the olefin-based elastomer [2] is 50 to 100 parts by weight of the ester-based elastomer [1].
It is characterized by comprising 500 parts by weight.

[0008]

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[0009]

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[0010]

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[0011]

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[0012]

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The thermoplastic elastomer composition according to the second aspect is the thermoplastic elastomer composition according to the first aspect, wherein the polyolefin resin (D) is 20 to 80% by weight and the rubber (E) ) Is 80-20% by weight
Wherein the gel fraction in the olefin-based elastomer [2] is 20% by weight or more. The polyester copolymer (A) used in the present invention is composed of a repetition of a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). Examples of such a copolymer include a known polyether polyester elastomer obtained by reacting a dicarboxylic acid such as terephthalic acid and dimethyl terephthalate and / or an ester-forming derivative thereof, a low molecular weight diol, and a polyether. Can be used.

The low molecular weight diol for obtaining the polyester copolymer (A) used in the present invention includes, for example, ethylene glycol, 1,2-propanediol,
3-propanediol, 1,3-butanediol, 1,4 butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol and the like, which may be used alone, Two or more kinds may be used in combination. Examples of the polyether for obtaining the polyester copolymer (A) include, for example, polyethylene glycol,
Poly-1,3-propylene glycol, poly-1,2-propylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like can be mentioned. Among them, polytetramethylene glycol is preferable in terms of excellent mechanical properties and weather resistance, and commercially available products include “PTH” manufactured by BASF.
F "and" PTMG "manufactured by Mitsubishi Chemical Corporation.

The above polyether has a number average molecular weight of 500.
Of about 5000 it is used, and the number average molecular weight of R ₂ in the general formula (2) is 500 to 5,000. If it is less than 500, the resulting polyester copolymer (A) will have poor blocking properties, low melting point, and low mechanical strength at high temperatures of the ester elastomer [1]. When it is larger than 5,000, the compatibility with the polyether (B) becomes low, so that the degree of polymerization of the ester elastomer [1] does not increase, and an elastomer having sufficient strength cannot be obtained. Preferably, those having a number average molecular weight of 500 to 5000 are used.

The above polyester copolymer (A) can be polymerized by a known method. For example, terephthalic acid dimethyl ester with polyether and excess low molecular weight diol at 200 ° C in the presence of a catalyst
To carry out a transesterification reaction, followed by a polycondensation reaction at 240 ° C. under reduced pressure to obtain a polyester copolymer (A).

The proportion occupied by the short-chain polyester component in the components of the polyester-based copolymer (A) is 50 to 95% by weight, preferably 70 to 90% by weight. When the amount of the short-chain polyester component is less than 50% by weight, the melting point of the polyester copolymer (A) is low, which adversely affects the mechanical strength of the ester elastomer at high temperatures. If the content is more than 95% by weight, the degree of polymerization of the ester-based elastomer [1] does not increase due to low compatibility with the polyether (B), and an elastomer having sufficient strength cannot be obtained.

The polyether (B) used in the present invention comprises a repeating unit represented by the general formula (3).

[0019]

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Examples of such polyethers include polyethylene glycol, poly 1,3-propylene glycol, poly 1,2 propylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like. Among them, polytetramethylene glycol is preferable in terms of excellent mechanical properties and weather resistance, and commercially available products include "PTHF" manufactured by BASF and "PTF" manufactured by Mitsubishi Chemical.
MG "and the like. The ester-based elastomer [1] used in the present invention is the polyester-based copolymer described above.
A block copolymer of (A) and polyether (B), a polyester copolymer (A) and a polyether (B)
Are bound by a urethane binding component (C) represented by the general formula (4) or (5).

[0021]

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[0022]

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In order to obtain the ester elastomer [1] bonded by the urethane bonding component (C), the polyester copolymer (A) and the polyether (B) are combined with the general formula
The diisocyanate compound represented by (6) may be reacted.

[0024]

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The polyester copolymer (A) and the polyether (B) usually have a hydroxyl group at both ends, but may partially have a carboxyl group. At this time, when both terminal functional groups reacting with the diisocyanate compound are hydroxyl groups, the urethane binding component (C) of the general formula (4), and when one is a hydroxyl group and the other is a carboxyl group, the urethane of the general formula (5) Linked by the linking component (C). When the terminal functional group of the polyester-based copolymer (A) is a carboxyl group, it is considered that a small amount of a portion bonded by the urethane-binding component of the general formula (7) is also included.

[0026]

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The structure of the above diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule, and three or more diisocyanate compounds are provided as long as the fluidity of the produced polyester elastomer [1] is maintained. A compound having an isocyanate group may be used.

As the diisocyanate, for example,
Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate;
2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-
Hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated 4,
Examples include aliphatic diisocyanates such as 4'-diphenylmethane diisocyanate.

The ester-based elastomer [1] of the present invention contains 50 to 500 parts by weight of the polyether (B) and 10 to 100 parts by weight of the urethane binding component (C) based on 100 parts by weight of the polyester-based copolymer (A). It consists of a part. The reason is,
If the amount of the polyether (B) is less than 50 parts by weight, sufficient flexibility of the ester elastomer [1] cannot be obtained, and if it is more than 500 parts by weight, sufficient mechanical strength cannot be obtained. And preferably 100 to 300 parts by weight. When the amount of the urethane binding component (C) is less than 10 parts by weight, the ester elastomer [1] does not become a high molecular weight substance and has low mechanical strength, and when the amount is more than 100 parts by weight. Is because the ester-based elastomer [1] is inferior in flexibility, and is preferably composed of 30 to 70 parts by weight.

The polyester-based elastomer [1] in the present invention can be obtained, for example, by melt-mixing the polyester-based copolymer (A), the polyether (B) and the diisocyanate compound and reacting them. A preferred method of melt mixing includes, for example, a method of melt mixing in an extruder, and a preferable mixing temperature is 180 to 260 ° C.
When the temperature is lower than 180 ° C., the polyester copolymer (A) does not melt and has low reactivity, so that it is difficult to obtain an ester elastomer [1] as a high molecular weight polymer.
When the temperature exceeds 0 ° C., the polyester copolymer (A) and the diisocyanate are decomposed, and it is difficult to obtain an ester elastomer [1] having sufficient strength. A more preferred range of the melt mixing temperature is from 200 to 240 ° C.

The thermoplastic elastomer composition of the present invention comprises:
It comprises an ester-based elastomer [1] and an olefin-based elastomer [2] having a structure in which a rubber (E) is dispersed in a polyolefin resin (D). Preferred examples of the olefin-based elastomer [2] include a known dynamically crosslinked polyolefin resin composition obtained by melt-kneading polypropylene, EPDM, oil, a crosslinking agent, and the like.

Examples of the polyolefin resin (D) include polyethylene such as low-density polyethylene, linear low-density polyethylene, and high-density polyethylene, and polypropylene.

Examples of the rubber (E) include natural rubber, synthetic isoprene rubber, styrene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, acrylic rubber, silicone rubber, fluorine rubber, and olefin copolymer. Rubber and styrene copolymer rubber. Examples of the olefin copolymer rubber include ethylene propylene copolymer rubber (EPM), and particularly preferred is ethylene propylene diene copolymer rubber (EPDM) obtained by copolymerizing a third component having a double bond. The third component is ethylidene norbornene, dicyclopentadiene, 1,4-
Hexadiene and the like can be mentioned. Styrene-based copolymer rubbers include styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene-styrene triblock copolymer (SIS), hydrogenated polymer of SBS (SEBS), and hydrogenated polymer of SIS (SEPS) And the like.

In the olefin-based elastomer [2], preferably, the polyolefin resin (D) is composed of 20 to 80% by weight, the rubber (E) is composed of 80 to 20% by weight, and The rate is to be at least 20% by weight. If the polyolefin resin (D) is less than 20% by weight, the melt fluidity of the olefin-based elastomer [2] tends to deteriorate,
If the amount exceeds 80% by weight, flexibility and sag resistance tend to deteriorate, and if the gel fraction is less than 20% by weight, sag resistance tends to deteriorate. . Here, the gel fraction is one type of index indicating the degree of crosslinking,
The dry weight of the undissolved components after immersing the resin composition in toluene at 120 ° C. for 12 hours was converted into a percentage by the dry weight of the original resin composition. .

In the olefin-based elastomer [2], when the rubber (E) forms a continuous phase, the moldability decreases, so that the rubber (E) is dispersed in the polyolefin resin (D). Preferably, the particle size of the dispersed rubber is 50 μm
It is as follows. If it is larger than 50 μm, the tensile strength and elongation tend to decrease.

The above rubber (E) is a polyolefin resin (D)
Based olefin elastomer [2]
Is obtained, for example, by melt-kneading a polyolefin resin (D) and a rubber (E) by a known method. At this time, it is preferable to crosslink the rubber (E) in order to increase the gel fraction. Specifically, the olefin resin, the olefin-based copolymer rubber, and the crosslinking agent are melted and mixed, and kneading is continued at the crosslinking temperature until the crosslinking is completed. During kneading, aromatic, naphthenic or paraffinic oils may be added.

The crosslinking method is not particularly limited as long as it is a commonly applied method. For example, sulfur and sulfur using a vulcanization accelerator such as dibenzothiazyl disulfide (MTBS) or tetramethylthiuram disulfide (TMTD) can be used. Vulcanization method, 1,3-bis (t-butylperoxyisopropyl)
Dialkyl peroxides such as benzene, peroxyketals such as 2,2-di-t-butylperoxybutane, diacyl peroxides such as dibenzoyl peroxide, t-
Examples include a peroxide crosslinking method using an alkyl perester such as butyl peroxybenzoate, a phenol resin vulcanization method, and an ionizing radiation crosslinking method.

The thermoplastic elastomer composition of the present invention comprises:
The olefin elastomer [2] is composed of 50 to 500 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the ester elastomer [1]. If the amount of the olefin-based elastomer [2] is less than 50 parts by weight, the flexibility and set resistance of the thermoplastic elastomer composition will be deteriorated, and if it exceeds 500 parts by weight, the moldability will be deteriorated. In the thermoplastic elastomer composition of the present invention, in order to improve the blend state of the ester elastomer [1] and the olefin elastomer [2],
It is preferable that the rubber (E) in the olefinic elastomer [2] be modified in advance with a carboxylic acid or epoxy.

The thermoplastic elastomer composition of the present invention comprises:
For example, it can be obtained by melt-kneading the ester-based elastomer [1] and the olefin-based elastomer [2]. The kneading temperature is preferably from 180 to 260 ° C, more preferably from 200 to 240 ° C. If the temperature is lower than 180 ° C., it is difficult to melt the ester elastomer, so that it is difficult to obtain a uniform thermoplastic elastomer composition. If the temperature is higher than 260 ° C., the ester elastomer may be decomposed to deteriorate the physical properties.

A catalyst may be used during the melt mixing. Examples of the catalyst include stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate,
Dimethyltin maleate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine, naphthenate metal salt, octylate metal salt, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, antimony trioxide and the like are preferable. . Two or more of the above catalysts may be used in combination.

Stabilizers may be used in the thermoplastic elastomer composition of the present invention, for example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-t-
Hindered phenolic antioxidants such as butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane Agent: tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-
Butyl-α- (3-t-butyl-4-hydroxyphenyl)
-P-cumenylbis (p-nonylphenyl) phosphite,
Heat of dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythryltetrakis (3-laurylthiopropionate), ditridecyl 3,3'-thiodipropionate, etc. Stabilizers and the like.

The thermoplastic elastomer composition of the present invention comprises:
To the extent that practicality is not impaired during or after production, fibers,
Additives such as inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, inorganic substances, and higher fatty acid salts may be added. Examples of the fibers include inorganic fibers such as glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, and silicon / titanium / carbon fibers; and organic fibers such as aramid fibers.

Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl)
Phosphate, pentabromophenyl allyl ether and the like, and as the ultraviolet absorber, for example, P-
tert-butylphenyl salicylate, 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like.

Examples of the antistatic agent include N, N-
Bis (hydroxyethyl) alkylamine, alkyl allyl sulfonate, alkyl sulfanate and the like can be mentioned. Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, and talc, and examples of the inorganic substance include barium sulfate, alumina, and silicon oxide. As the higher fatty acid salt, for example, sodium stearate, barium stearate,
And sodium palmitate.

The thermoplastic elastomer composition of the present invention comprises:
A thermoplastic resin or rubber component other than those described above may be mixed to modify its properties before use. Examples of such a thermoplastic resin include polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polysulfone, and polyester. As the rubber component, for example, natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPDM), polychloroprene, butyl rubber, acrylic Examples include rubber, silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, PVC-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer.

(Action) Usually, it is difficult for the different polymer components to react with each other due to insufficient compatibility. However, in the present invention, the hard segment is represented by the general formula (1). A polyester copolymer (A) obtained by copolymerizing a long-chain polyether polyester component represented by the general formula (2), which is a soft segment component, with a short-chain polyester component, and a soft segment component. By using a polyether (B) composed of a repeating unit represented by the general formula (3), the compatibility between the two is improved and the mutual reaction is greatly improved.

As a result, an ester-based elastomer [1] having a high blockability of the hard segment component and the soft segment component was produced. In the ester-based elastomer [1] used in the present invention, the crystal formed by the short-chain polyester component constitutes a cross-linking point, thereby exhibiting properties as an elastomer.

The ester-based elastomer [1] is composed of a short-chain polyester component, ie, a portion having a high ratio of a hard segment component, and a long-chain polyether polyester component, ie, a portion having a high ratio of a soft segment component. Therefore, the short-chain polyester component is easier to crystallize than the conventional ester-based elastomer showing the same degree of flexibility, and as a result, a strong cross-linking point is formed and excellent mechanical properties at high temperatures can be exhibited. is there. Furthermore, the presence of a portion having a high proportion of polyether increases the molecular weight between cross-linking points, and as a result, can exhibit properties as a highly flexible elastomer material.

The thermoplastic elastomer composition of the present invention comprises:
Since such an ester-based elastomer [1] and an olefin-based elastomer [2] having excellent flexibility and sag resistance are blended, mechanical properties, heat resistance, abrasion resistance,
Not only excellent in bending fatigue resistance, but also excellent in flexibility and mechanical properties at high temperatures, it is extremely useful in practical use.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Various physical properties were measured using the following methods.

[Surface Hardness] According to JIS K6301, the surface hardness was measured at 23 ° C. using an A-type spring. [Tensile properties] Tensile strength and tensile elongation at room temperature (23 ° C) were evaluated according to JIS K6301. (Compression set) JI
According to S K6301, the set resistance was evaluated at 100 ° C. with a compression strain of 25%. [Oil resistance] Based on JIS K6301, the weight change rate when immersed in JIS No. 3 oil at 120 ° C for 72 hours was measured.

Preparation of ester-based elastomer [1] 100 parts by weight of dimethyl terephthalate, 1,4-butanediol
102 parts by weight, 48 parts by weight of polytetramethylene glycol (b) having a number average molecular weight of about 1000 (PTHF1000 manufactured by BASF), 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5-trimethyl-2,4 as a stabilizer , 6-Tris (3,5-di-
0.3 parts by weight of t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-t-butylphenyl) phosphite
0.3 parts by weight was added, and the reaction system was kept at 200 ° C. for 3 hours under nitrogen to carry out transesterification.

The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 mmHg or less in 20 minutes. As a result of a polycondensation reaction for 20 minutes in this state, 160 parts by weight of a white polyester copolymer (a) was obtained. 100 parts by weight of the polyester copolymer (a), 110 parts by weight of the above polytetramethylene glycol (b), 36 parts by weight of 4,4′-diphenylmethane diisocyanate were mixed with a twin-screw extruder (L / D = 40 mm, manufactured by Berstorf Co.) ), Kneading at 220 ° C (residence time
200 seconds) to obtain pellets of the ester elastomer. Press molding using the obtained pellets (press temperature
230 ° C.) to prepare a 2 mm thick sheet of ester-based elastomer (Es), and various physical properties were measured. The results are shown in Table 1.

Production of olefin elastomer [2] (1) 100 parts by weight of polypropylene (MA3) manufactured by Nippon Polychem, 300 parts by weight of ethylene-propylene copolymer (EP37C) manufactured by Japan Synthetic Rubber, 6 parts by weight of sulfur, zinc oxide 20 parts by weight and 12 parts by weight of tetramethylthiuram disulfide (TMTD) were kneaded (residence time 600 seconds) at 180 ° C. using a twin-screw extruder (L / D = 40 mm, manufactured by Berstorf) to obtain an olefin resin composition. A product pellet was obtained. Using the obtained pellets, a 2 mm thick sheet of an olefin-based elastomer (e) was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1. Gel fraction is 70%
Met.

(Part 2) 100 parts by weight of polypropylene (MA3) manufactured by Nippon Polychem, styrene-butadiene-styrene triblock copolymer (Asaprene T-420) 300 manufactured by Asahi Kasei
Parts by weight, 1,3-bis (t-butylperoxyisopropyl) benzene 8 parts by weight, and Diana Process Oil PW-90 300 parts by weight using a twin-screw extruder (L / D = 40 mm, manufactured by Berstorf Co.) The mixture was kneaded at 180 ° C (residence time: 600 seconds) to obtain pellets of the olefin resin composition. Using the obtained pellets, a 2 mm thick sheet of an olefin-based elastomer (s) was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1. Gel fraction is 50
%Met.

Example 1 Ester Elastomer (E
s) 100 parts by weight and 100 parts by weight of the olefin-based elastomer (e) are kneaded at 200 ° C. using a single screw extruder (residence time 180 °).
Seconds) to obtain pellets of the thermoplastic elastomer composition. Press molding using the obtained pellets (press temperature
230 ° C.) to prepare a 2 mm thick sheet, and various physical properties were measured. The results are shown in Table 1.

Example 2 Ester Elastomer (E
s) 100 parts by weight and 100 parts by weight of the olefin-based elastomer (s) are kneaded at 200 ° C. using a single screw extruder (residence time 180 °).
Seconds) to obtain pellets of the thermoplastic elastomer composition. Press molding using the obtained pellets (press temperature
230 ° C.) to prepare a 2 mm thick sheet, and various physical properties were measured. The results are shown in Table 1.

Comparative Example 1 Thermoplastic elastomer composition pellets were obtained in the same manner as in Example 1, except that only polyester elastomer (Hytrel 4767) manufactured by Du Pont-Toray Co., Ltd. was used as the ester elastomer. Press molding using the obtained pellets (press temperature
230 ° C.) to prepare a 2 mm thick sheet, and various physical properties were measured. The results are shown in Table 1. Press molding (press temperature 230 ° C) of this ester-based elastomer
A sheet having a thickness of mm was prepared, and various physical properties were measured. The results are shown in Table 1.

Comparative Example 2 Pellets were obtained under the same conditions as in Comparative Example 1 except that the above-mentioned elastomer (Es) was used as an ester-based elastomer, and 2 mm-thick sheets were prepared, and various physical properties were measured. . The results are shown in Table 1.

Comparative Example 3 Various physical properties of the olefin-based elastomer (e) having a thickness of 2 mm were measured. The results are shown in Table 1. (Comparative Example 4) 2 mm thick sheet olefin-based elastomer
Various physical properties of (s) were measured. The results are shown in Table 1.

[0061]

[Table 1]

[0062]

The thermoplastic elastomer composition of the present invention comprises a hard segment component comprising a short-chain polyester component represented by the following general formula (1) and a general formula (2) or (3):
An ester-based elastomer [1] having high blockability with the soft segment component represented by the formula [1] and having both flexibility and sag resistance at high temperatures, and an olefin-based elastomer [2] excellent in flexibility and sag resistance. Is constituted in the above range, a thermoplastic elastomer composition capable of providing a thermoplastic elastomer excellent in flexibility and mechanical properties at high temperatures, particularly excellent in set resistance and mechanical strength, also excellent in oil resistance. is there. In addition, the obtained thermoplastic elastomer exhibits rubber elasticity at normal temperature, but exhibits plasticity at high temperature, and can be molded normally, similarly to general thermoplastic elastomers. It is a useful composition.

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Claims (2)

[Claims] A short-chain polyester component represented by the following general formula (1) and a long-chain polyester component represented by the following general formula (2):
A block copolymer of a polyester copolymer (A) having 95% by weight and 50 to 5% by weight of the long-chain polyester component and a polyether (B) composed of a repeating unit represented by the general formula (3). A polymer, polyester-based copolymer (A)
And polyether (B) are bonded by a urethane bonding component (C) represented by the general formula (4) or (5),
Polyester (B) 50-500 parts by weight and urethane binding component (C) 10 per 100 parts by weight of polyester copolymer (A)
100 parts by weight of an ester elastomer [1] and an olefin elastomer [2] having a structure in which a rubber (E) is dispersed in a polyolefin resin (D). A thermoplastic elastomer composition comprising 50 to 500 parts by weight of an olefin-based elastomer [2] based on parts by weight. Embedded image Embedded image Embedded image Embedded image Embedded image 2. The thermoplastic elastomer composition according to claim 1, wherein in the olefin-based elastomer [2], the polyolefin resin (D) is 20 to 80% by weight and the rubber (E) is 80 to 20% by weight. A thermoplastic elastomer composition, wherein the gel fraction in the system elastomer [2] is 20% by weight or more.