JP2002212381A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which has excellent oil resistance, flexibility and low temperature impact resistance and further has excellent rubber elasticity, mechanical strength, heat resistance and the like. SOLUTION: This thermoplastic elastomer composition comprises 100 pts.wt. of an addition polymerization type block copolymer (I) comprising a block copolymer having a polymer block (A1) consisting mainly of an aromatic vinyl compound and a polymer block (B1) consisting mainly of a conjugated compound and/or its hydrogenated product; 30 to 250 pts.wt. of a softener for non-aromatic rubbers; a thermoplastic polyester based polymer (III) in an amount of 20 to 70 wt.% based on the total weight of the components (I), (II) and (III); and a polyester-based block copolymer (IV) having an addition polymerization-based block (D) comprising a block copolymer having a polymer block (A2) consisting mainly of an aromatic vinyl compound and a polymer block (B2) consisting mainly of a conjugated diene compound or its hydrogenation product and a thermoplastic polyester-based resin block (E), in an amount of 5 to 50 wt.% based on the total weight of the components (I), (II) and (III).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer which has excellent oil resistance, flexibility and low-temperature impact resistance, and has good rubber elasticity, mechanical strength and heat resistance.

[0002]

2. Description of the Related Art In recent years, various thermoplastic elastomers which are soft materials having rubber elasticity, do not require a vulcanization step, and have the same moldability as thermoplastic resins have been developed.
It is used in a wide range of fields such as automobile parts, home electric parts, electric wire coating, medical parts, footwear, sundries and the like. Among thermoplastic elastomer materials, an aromatic vinyl compound polymer block which is a styrene-based thermoplastic elastomer-a block copolymer composed of a conjugated diene compound polymer block, for example,
A block copolymer having a polystyrene-polybutadiene-polystyrene structure is useful as a soft material having excellent processability, but has poor heat resistance, weather resistance, oil resistance, and solvent resistance. is there. A hydrogenated thermoplastic elastomer obtained by hydrogenating a conjugated diene compound polymer block in a styrene-based thermoplastic elastomer has been known as one which improves such a defect. However, although the hydrogenated thermoplastic elastomer has improved weather resistance, it has not reached a level satisfactory in oil resistance and heat resistance as a vulcanized rubber substitute.

[0003] In order to improve the oil resistance and heat resistance of a styrene-based thermoplastic elastomer, a method of adding a resin or the like having excellent oil resistance and heat resistance has been conventionally proposed. Such prior art includes:
Method of adding polyphenylene ether resin (Japanese Patent Publication 6
-80124, JP-A-7-100184), a method of adding a polyester-based elastomer (JP-A-1-193352, JP-A-10-787)
No. 8). However, the styrene-based thermoplastic elastomer composition obtained by the above-described conventional method in which a polyphenylene ether resin is added does not have oil resistance that satisfies all of the vulcanized rubber substitute applications. Further, the styrene-based thermoplastic elastomer composition obtained by the above-mentioned conventional method in which a polyester-based elastomer is added has not yet reached satisfactory levels in oil resistance and mechanical strength.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a styrenic thermoplastic elastomer to have excellent oil resistance, flexibility and low-temperature impact resistance, and to provide mechanical strength, heat resistance and rubber elasticity. An object of the present invention is to provide a thermoplastic elastomer composition having excellent other properties.

[0005]

The present inventors have made various studies to achieve the above object. As a result, at least one styrene-based thermoplastic elastic polymer selected from a block copolymer having a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and a hydrogenated product thereof is obtained. for,
(B) a softener for non-aromatic rubber; (b) a thermoplastic polyester resin and / or a thermoplastic polyester elastomer; and (c) a polymer block mainly composed of an aromatic vinyl compound and a conjugated diene compound. When a block copolymer having a polymer block or an addition polymerization block composed of a hydrogenated product thereof and a polyester block copolymer having a thermoplastic polyester resin block are mixed at a specific ratio, the polyester block copolymer The coalesced material (c) works effectively as a compatibilizer between the styrene-based thermoplastic elastic polymer and the thermoplastic polyester-based resin and / or the thermoplastic polyester-based elastomer of (b) to be softened and oil-resistant. Good mechanical strength, heat resistance and elasticity, good solvent resistance and low temperature impact resistance Thermoplastic elastomer polymer composition has completed the present invention found that the resulting.

That is, the present invention relates to (1) (I) a block copolymer having a polymer block (A1) mainly composed of an aromatic vinyl compound and a polymer block (B1) mainly composed of a conjugated diene compound, and hydrogenated hydrogen. 100 parts by mass of at least one type of addition-polymerized block copolymer selected from additives [hereinafter referred to as “addition-polymerized block copolymer (I)”]; (II) softener for non-aromatic rubber [hereinafter (Hereinafter referred to as "softening agent for non-aromatic rubber (II)"] is from 30 to 250 parts by mass; (III) a thermoplastic polyester polymer [hereinafter referred to as "thermoplastic polyester polymer (III)"] is subjected to addition polymerization. 20 to 70% by mass based on the total mass of the block copolymer (I), the softener for non-aromatic rubber (II) and the thermoplastic polyester polymer (III); and (IV) aromatic vinyl Mainly comprising polymer block (A2) mainly composed of a conjugated diene compound polymer block (B2) addition polymerized block comprising a block copolymer or its hydrogenated product having a (D) from Le compounds,
A polyester block copolymer having a thermoplastic polyester resin block (E) [hereinafter referred to as “polyester block copolymer (IV)”] is obtained by adding an addition polymerization block copolymer (I) to a non-aromatic rubber. A thermoplastic elastomer composition characterized in that it is contained in an amount of 5 to 50% by mass with respect to the total mass of the softener (II) for use and the thermoplastic polyester polymer (III).

The present invention also provides (2) a triblock copolymer in which the addition-polymerized block copolymer (I) comprises a polymer block (A1) -polymer block (B1) -polymer block (A1). (3) a polymer in which the polymer block (B1) in the addition-polymerized block copolymer (I) is mainly composed of isoprene, butadiene, or a mixture of isoprene and butadiene. The thermoplastic elastomer composition of the above (1) or (2), which is a block and / or a hydrogenated product thereof; and (4) the polyester-based block copolymer (IV) comprises one addition-polymerized block (D) Thermoplastic thermoplastic resin according to any one of (1) to (3) above, which is a diblock copolymer comprising Elastomer composition; encompasses a preferred embodiment the.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the addition polymerization type block copolymer (I)
A block copolymer having at least one polymer block (A1) mainly composed of an aromatic vinyl compound and at least one polymer block (B1) mainly composed of a conjugated diene compound; Any of at least one block copolymer selected from hydrogenated products can be used. The addition-polymerized block copolymer (I) used in the present invention is generally represented by the following general formulas (i) to (iii) before hydrogenation.

[0009]

Embedded image A1- (B1-A1) n-B1 (i) A1-B1- (A1-B1) n-A1 (ii) B1-A1- (B1-A1) n-B1 (iii) , A1 represents a polymer block (A1) mainly composed of an aromatic vinyl compound, B1 represents a polymer block (B1) mainly composed of a conjugated diene compound, and n represents 0 or an integer of 1 or more. ]

The addition-polymerized block copolymer (I) used in the present invention is any of the above-mentioned block copolymers represented by the general formulas (i) to (iii) and / or a hydrogenated product thereof. And among them, general formula: A1-
Diblock copolymer represented by B1, General formula: A1-B
Triblock copolymers represented by 1-A1 and hydrogenated products thereof are preferably used from the viewpoint of easy production and availability, and triblock copolymers represented by the general formula: A1-B1-A1 Polymers and / or hydrogenated products thereof are more preferably used.

The aromatic vinyl compound constituting the polymer block (A1) in the addition polymerization type block copolymer (I) is, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, Methylstyrene, t-butylstyrene, 2,4-dimethylstyrene,
Examples thereof include vinyl aromatic compounds such as 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, and acetonaphthylene. The polymer block (A1) may be composed of only one kind of the above-mentioned aromatic vinyl compound or may be composed of two or more kinds, and is composed of styrene and α-methylstyrene, especially styrene. Is preferred.

The conjugated diene compound constituting the polymer block (B1) in the addition polymerization type block copolymer (I) includes isoprene, butadiene, hexadiene,
Examples thereof include 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene. The polymer block (B1) may be composed of one type of these conjugated diene compounds, or may be composed of two or more types. When the polymer block (B1) has structural units derived from two or more kinds of conjugated diene compounds, their bonding forms are random, block, tapered block, or a combination of two or more thereof. Can consist of

Among them, the polymer block (B1)
Is a polyisoprene block mainly composed of isoprene or a hydrogenated polyisoprene block in which part or all of its unsaturated bonds are hydrogenated; a polybutadiene block mainly composed of butadiene or an unsaturated bond thereof, from the viewpoint of improving the physical properties of rubber. Hydrogenated polybutadiene block partially or wholly hydrogenated; or isoprene / butadiene copolymer block mainly composed of isoprene and butadiene or hydrogenated isoprene / butadiene copolymer partially or wholly hydrogenated with unsaturated bonds. It is preferably a polymerization block. In particular, the polymer block (B1) is more preferably the above-described polyisoprene block, isoprene / butadiene copolymer block, and / or a hydrogenated block thereof.

The addition-polymerized block copolymer (I) used in the present invention is a block copolymer having the above-mentioned block structure and generally having no functional group such as a hydroxyl group at a molecular terminal. In the addition-polymerized block copolymer (I), the ratio of the polymer block (A1) to the entire addition-polymerized block copolymer (I) is preferably 5 to 75% by mass, and more preferably 10 to 65% by mass. Is more preferable. When the proportion of the polymer block (A1) is less than 5% by mass, the mechanical strength of the obtained thermoplastic elastomer composition tends to decrease, while when it exceeds 75% by mass, the flexibility tends to be impaired.

The addition-polymerized block copolymer (I) used in the present invention has a number average molecular weight of 50,000 to 50.
Preferably in the range of 20,000,
More preferably, it is in the range of 0 to 350,000.
The number average molecular weight of the addition polymerization type block copolymer (I) is 5
If it is less than 000, the oil resistance and the solvent resistance of the obtained thermoplastic elastomer composition are liable to decrease, while
If it exceeds 000, the fluidity of the obtained thermoplastic elastomer composition becomes poor and the moldability tends to be poor. In addition, the number average molecular weight in this specification is a number average molecular weight in terms of polystyrene by a GPC method.

In the addition-polymerized block copolymer (I) used in the present invention, the unsaturated bond in the polymer block (B1) may be unhydrogenated, partially hydrogenated, or All may be hydrogenated.
However, since the obtained thermoplastic elastomer composition has good weather resistance and heat resistance, the hydrogenation rate of the unsaturated bond in the polymer block (B1) is 80%.
% Or more, more preferably 90% or more, and even more preferably 95% or more.
The method for producing the addition-polymerized block copolymer (I) used in the present invention is not particularly limited, and it can be produced by a conventionally known method.

In general, a mineral oil-based rubber softener called a process oil or an extender oil used for softening, increasing the volume of a rubber, and improving processability is a combination of an aromatic ring, a naphthene ring and a paraffin chain. Mixture. In the total carbon number, the carbon number of the paraffin chain accounts for 50% or more, and the aromatic carbon number and the naphthene ring carbon number are both 3
Those having 0% or less are referred to as paraffinic, and those having 30 to 45% of naphthenic ring carbon atoms, less than 50% of carbon atoms in the paraffin chain, and 30% or less aromatic carbon atoms are referred to as naphthenic, When the number of aromatic carbon atoms is more than 30%, the number of carbon atoms of the paraffin chain is less than 50%, and the number of carbon atoms of the naphthene ring is 3
Those with less than 0% are called aromatic.

As the softener for non-aromatic rubber (II) used in the present invention, among the above-mentioned softeners for mineral oil rubber, process oils referred to as paraffins and naphthenes are referred to. Process oils are used. Besides these, white oil, mineral oil, oligomers of ethylene and α-olefin, low molecular weight polybutadiene, low molecular weight polybutadiene, paraffin wax, liquid paraffin, and the like can be used. In the present invention, one or more of the above-mentioned ones can be used, and among them, a paraffin-based process oil is preferably used.

The softener (II) for a non-aromatic rubber used in the present invention has a kinematic viscosity at 37.8 ° C. of 20 to 50.
0 mm ² / s (20-500 cst), pour point is -1
It is preferable that the flash point is in the range of 0 to -15 ° C and the flash point of 170 to 300 ° C. Since aromatic process oils permeate the aromatic vinyl compound blocks in the addition-polymerized block copolymer (I) and polyester-based block copolymer (IV) used in the present invention, they are not suitable for use in the present invention. Not suitable.

In the present invention, as the thermoplastic polyester polymer (III), a thermoplastic polyester resin [hereinafter referred to as “thermoplastic polyester resin (IIIa)”],
And polyester-based thermoplastic elastomer [hereinafter referred to as “polyester-based thermoplastic elastomer (IIIb)”], and one or more of them can be used.

Thermoplastic polyester resin (IIIa)
In general, polycondensation reaction or transesterification reaction of dicarboxylic acid and / or its ester-forming derivative with diol and / or its ester-forming derivative, polycondensation reaction of hydroxycarboxylic acid, ring-opening polymerization of lactone, Thermoplastic polyester resin produced by a combination of reactions. Specific examples of the thermoplastic polyester resin (IIIa) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, p-hydroxybenzoic acid polyester, and polyarylate And the like, and one or more of these can be used. Among them, polybutylene terephthalate and / or polyethylene terephthalate are preferably used.

Polyester thermoplastic elastomer (II
As Ib), any of the conventionally known polyester-based thermoplastic elastomers can be used. As a specific example, a block copolymer composed of an aromatic polyester block (C1) and a non-aromatic polyester block (C2); a block copolymer composed of an aromatic polyester block (C1) and a polyether block (C3); Examples include a block copolymer composed of an aromatic polyester block (C1), a non-aromatic polyester block (C2), and a polyether block (C3), and one or more of these can be used. .

Polyester thermoplastic elastomer (II
The aromatic polyester block (C1) which can be a constituent block of Ib) generally comprises an aromatic polyester oligomer produced by a condensation reaction or a transesterification reaction between an aromatic dicarboxylic acid component and a diol component. , Polyethylene terephthalate oligomer, polypropylene terephthalate oligomer,
Polytetramethylene terephthalate oligomer, polypentamethylene terephthalate oligomer, and the like can be given.

The above-mentioned non-aromatic polyester block (C2) which can be a constituent block of the thermoplastic polyester-based thermoplastic elastomer (IIIb) is generally composed of an aliphatic and / or alicyclic dicarboxylic acid component and an aliphatic diol component. An aliphatic polyester oligomer produced by a condensation reaction or a transesterification reaction, or an aliphatic polyester oligomer synthesized from an aliphatic lactone or an aliphatic monoolcarboxylic acid. Specific examples of the aliphatic polyester oligomer constituting the non-aromatic polyester block (C2) include alicyclic rings such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and dicyclohexyl-4,4′-dicarboxylic acid. One or more of aliphatic dicarboxylic acids such as dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid and / or ester-forming derivatives thereof and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, etc. One of the aliphatic diols
Aliphatic polyester oligomer obtained by reaction with at least one species; poly ε-caprolactone oligomer; poly ω-
Oxycaproic acid oligomers and the like can be mentioned.

Polyester thermoplastic elastomer (II
Examples of the above-mentioned polyether block (C3) which can be a constituent block of Ib) include polyether oligomers having an average molecular weight of about 400 to about 6000, particularly poly (alkylene oxide) glycol.
Specific examples of the poly (alkylene oxide) glycol include polyethylene glycol, poly (1,2- and / or
Or 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block copolymer or random copolymer of ethylene oxide and propylene oxide, a block copolymer of ethylene oxide and tetrahydrofuran, or And random copolymers. When using a polyester thermoplastic elastomer (IIIb) as the thermoplastic polyester polymer (III),
A block copolymer composed of an aromatic polyester block (C1) and a polyether block (C3) and / or a block copolymer composed of an aromatic polyester block (C1) and a non-aromatic polyester block (C2) are flexible. It is preferably used from the viewpoint of ease of production.

The polyester block copolymer (IV) used in the present invention comprises a polymer block (A2) mainly composed of an aromatic vinyl compound unit and a polymer block (B2) mainly composed of a conjugated diene polymer or a hydrogenated hydrogen thereof. It is a block copolymer having an addition-polymerized block (D) made of an additive and a thermoplastic polyester-based resin block (E). Polyester block copolymer (IV)
May be any block copolymer in which at least one addition polymerization block (D) and at least one thermoplastic polyester resin block (E) are bonded. Among them, a diblock copolymer in which one addition-polymerized block (D) and one thermoplastic polyester-based resin block (E) are bonded,
It is preferable from the viewpoints of excellent compatibility between the addition-polymerized block copolymer (I) and the thermoplastic polyester-based polymer (III), ease of production, and the like.

The addition-polymerized block (D) in the polyester-based block copolymer (IV) is a polymer block in which at least one polymer block (A2) and at least one polymer block (B2) are bonded. However, it is preferably a copolymer block comprising at least one polymer block (B2) and at least two polymer blocks (A2).

Examples of the vinyl aromatic compound for forming the polymer block (A2) constituting the addition polymerization block (D) include styrene, α-methylstyrene,
Examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, and vinylanthracene, and the polymer block (A2) is obtained from one or more of these. Can be formed. Among them, it is preferable to be formed from styrene and / or α-methylstyrene.

Examples of the conjugated diene compound for forming the polymer block (B2) constituting the addition polymerization block (D) include, for example, isoprene, 1,3-butadiene, 2,3-dimethyl-1, 3-butadiene, 1,3
-Pentadiene, 1,3-hexadiene, etc., and the polymer block (B2) can be formed from one or more of these. Among them, it is preferable to be formed from 1,3-butadiene and / or isoprene. Polymer block (B
When 2) is formed from two or more types of conjugated diene compounds, the arrangement of each monomer unit may be any of random, block, and tapered block shapes.

The addition polymerization system block (D) may contain a structural unit derived from an aromatic vinyl compound in a proportion of 10 to 90% by mass based on the mass of the addition polymerization system block before hydrogenation. Preferably, it is contained in a proportion of 20 to 70% by mass. When the proportion of the unit derived from the aromatic vinyl compound in the addition-polymerized block (D) is less than 10% by mass, the heat resistance of the thermoplastic elastomer composition of the present invention is likely to be reduced, while 90% by mass. If it exceeds 300, the impact resistance of the thermoplastic elastomer composition of the present invention tends to decrease.

The polymer block (B2) constituting the addition polymerization block (D) is preferably hydrogenated so that the degree of unsaturation based on the conjugated diene compound becomes 10% or less. When the degree of unsaturation of the polymer block (B2) is less than 10%, the heat resistance and weather resistance of the obtained thermoplastic elastomer composition will be good.

In the addition polymerization block (D), the number average molecular weight of the polymer block (A2) forming the block is preferably in the range of 5,000 to 50,000,
The number average molecular weight of the polymer block (B2) is 10,000.
It is preferably in the range of ~ 100,000. The number average molecular weight of the addition polymerization block (D) is 15,000.
It is preferably in the range of １５０150,000.

The thermoplastic polyester resin block (E) constituting the polyester block copolymer (IV)
In general, polycondensation reaction or transesterification reaction of dicarboxylic acid and / or its ester-forming derivative with diol and / or its ester-forming derivative, polycondensation reaction of hydroxycarboxylic acid, ring-opening polymerization of lactone, It is made of a thermoplastic polyester resin produced by a combination of reactions. Specific examples of the thermoplastic polyester resin forming the thermoplastic polyester resin block (E) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, p -Hydroxybenzoic acid-based polyester, polyarylate and the like can be mentioned, and the thermoplastic polyester-based resin block (E) can be formed from one or more of these. Among them, it is preferable to be formed from polybutylene terephthalate and / or polyethylene terephthalate. Further, the thermoplastic polyester resin block (E) constituting the polyester block copolymer (IV) is formed from a thermoplastic polyester resin having an intrinsic viscosity [η] of 0.6 to 1.0. Is preferred.

The method for producing the polyester block copolymer (IV) is not particularly limited, and it can be produced by any method. The polyester-based block copolymer (IV) is, for example, a polyester-based resin and an addition-polymerized block copolymer having a functional group capable of reacting with the polyester-based resin in the molecule [Polymer block (A2) and polymer block (B2) and an addition-polymerized block copolymer having a functional group] are kneaded under melting conditions, followed by solid-phase polymerization, and the resulting polyester-based reaction product is used as a polyester-based block. It can be obtained by extracting and recovering the copolymer (IV).

At this time, melt kneading of the polyester resin and the addition polymerization block copolymer having a functional group capable of reacting with the polyester resin in the molecule is carried out by a single screw extruder,
It can be performed using a melt kneading device such as a twin screw extruder, a kneader, and a Banbury mixer. Melt kneading conditions can be appropriately selected depending on the type of the polyester resin to be used, the type of the addition polymerization type block copolymer having a functional group capable of reacting with the polyester type resin in the molecule, the type of the apparatus, and the like. However, it is usually preferable to knead at a temperature of 180 to 300 ° C. for about 3 to 15 minutes. In addition, solid-phase polymerization after melt-kneading, solidifies the resin obtained by melt-kneading a polyester-based resin and an addition-polymerized block copolymer having a functional group capable of reacting with the polyester-based resin in the molecule, After granulation, it can be transferred to a suitable solid-state polymerization reactor, dried or crystallized at a temperature of 120 to 180 ° C. as a pretreatment, and then subjected to solid-phase polymerization. The solid-state polymerization reaction is generally carried out by raising the temperature of the resin obtained above to 5 to 6 degrees below the melting point of the polyester resin.
It is preferable to carry out the reaction under an inert gas stream or in a vacuum while maintaining the temperature at about 0 ° C. lower. Solid-state polymerization may be performed in either a batch system or a continuous system, by appropriately adjusting the residence time and processing temperature in the solid-state polymerization reaction device,
The desired degree of polymerization and reaction rate can be obtained.

In the above, extraction and recovery of a polyester-based block copolymer (IV) from a polyester-based reaction product obtained by solid-phase polymerization may be performed, for example, by subjecting the polyester-based reaction product to a mixed solvent of hexafluoroisopropanol / chloroform. And the solution is poured into tetrahydrofuran to precipitate.The precipitate is collected and dissolved in chloroform.The insoluble matter is removed from the chloroform solution by filtration or the like, and the chloroform solution is concentrated and dried. To recover the polyester-based block copolymer (IV) as a solid component.

Further, the polyester-based reaction product obtained by the above-mentioned solid-phase polymerization includes a polyester-based block copolymer (IV), a polyester-based resin, and an addition compound having a functional group capable of reacting with the polyester-based resin in the molecule. It is mainly composed of a mixture of a polymer block copolymer [an addition polymer block copolymer having a polymer block (A2) and a polymer block (B2) and having a functional group]. Therefore, by calculating the content of the polyester-based block copolymer (IV) contained in the polyester-based reaction product, the content of the polyester-based block copolymer (IV) in the polyester-based reaction product can be reduced. The polyester-based copolymer containing the polyester-based block copolymer (IV) without extracting and recovering the polyester-based block copolymer (IV) from the polyester-based reaction product while adjusting so as to fall within the scope of the present invention. The reaction product may be used as it is in the preparation of the thermoplastic elastomer composition of the present invention.

The above-described polyester-based reaction product containing the polyester-based block copolymer (IV) [that is, the polyester-based block copolymer (IV), the polyester-based resin, and the functional group capable of reacting with the polyester-based resin are molecules. The polyester-based reaction product mainly composed of an addition-polymerized block copolymer contained therein is, for example, an addition polymer having a functional group capable of reacting with a polyester-based resin in a molecule in addition to the above-described method by melt kneading. Can also be produced by conducting a polycondensation reaction of a polyester resin in the presence of In this case as well, the polyester-based block copolymer (IV) is extracted and recovered from the polyester-based reaction product obtained by the reaction in the same manner as described above, or the polyester-based block copolymer (IV) is extracted and recovered. Alternatively, the thermoplastic elastomer composition of the present invention may be produced using the polyester-based reaction product obtained by the reaction as it is.

The polyester-based block copolymer (IV) [or the polyester-based block copolymer (IV)
And the above-mentioned polyester-based reaction product], the addition-polymerized block copolymer having a functional group capable of reacting with a polyester-based resin includes a polymer block (A2) and a polymer block (B2). A block copolymer having a functional group and being an addition-polymerized block copolymer having a functional group is preferably used. The functional group in that case is not particularly limited as long as it is a functional group capable of reacting with the polyester resin, for example, a hydroxyl group, a carboxyl group, an ester group, an amide group, an amino group, an epoxy group, a thiol group, a thioester group, Examples thereof include a cyclic imino ether group such as a 2-oxazoline group, and an acid anhydride group such as a succinic anhydride-2-yl group and a succinic anhydride-2,3-diyl group. These addition-polymerized block copolymers having a functional group include, for example, copolymerization of a monomer having no functional group with a monomer having a functional group, and addition of a monomer having a functional group to an addition polymer having an active terminal. It can be produced by a reaction or a radical reaction between a monomer having a functional group and an addition polymer.

In the above-described addition-polymerized block copolymer having a functional group capable of reacting with the polyester-based resin, the above-mentioned functional group is located in the molecular main chain or the side chain of the addition-polymerized block copolymer or in the molecule. It may be located at any of the termini. A preferred block form of the polyester-based block copolymer (IV) is a diblock-shaped polyester-based block in which one addition-polymerized block (D) and one thermoplastic polyester-based resin block (E) are bonded. In order to produce the copolymer (IV), it is preferred that the addition-polymerized block copolymer has a functional group at one end. Further, the content of the functional group in the addition-polymerized block copolymer is preferably 0.5 to 1 per molecule on average, and more preferably 0.7 to 1 per molecule.

The thermoplastic elastomer composition of the present invention comprises:
The softening agent for non-aromatic rubber (II) is used in an amount of 30 to 100 parts by mass of the above addition-polymerized block copolymer (I).
250 parts by mass; thermoplastic polyester polymer (III)
With an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II) and a thermoplastic polyester polymer (II).
20 to 70% by mass with respect to the total mass of I) and a polyester-based block copolymer (IV), an addition-polymerized block copolymer (I) and a softener for non-aromatic rubber (II)
And the thermoplastic polyester-based polymer (III) in an amount of 5 to 50% by mass based on the total mass.

When the amount of the softening agent for non-aromatic rubber (II) is less than 30 parts by mass per 100 parts by mass of the addition-polymerized block copolymer (I), the resulting thermoplastic elastomer composition is obtained. Is inferior in flexibility and poor in fluidity, which is not practical. On the other hand, if the compounding amount of the non-aromatic rubber softener (II) exceeds 250 parts by mass, the non-aromatic rubber softener (II) bleeds out, resulting in a sticky or sticky final product. And the mechanical properties are also reduced. In the thermoplastic elastomer composition of the present invention, the amount of the non-aromatic rubber softener (II) is 50 to 100 parts by mass of the addition-polymerized block copolymer (I).
Preferably it is 200 parts by mass.

The blending amounts of the thermoplastic polyester polymer (III) are the same as those of the addition polymerization block copolymer (I), the softener for non-aromatic rubber (II) and the thermoplastic polyester polymer (III). If the amount is less than 20% by mass relative to the total mass of the thermoplastic elastomer composition, oil resistance and molding processability of the obtained thermoplastic elastomer composition will decrease, while if it exceeds 70% by mass, the hardness of the thermoplastic elastomer composition will be too high. As a result, flexibility is lost and a product having excellent elasticity cannot be obtained. The blending amount of the thermoplastic polyester-based polymer (III) is the total mass of the addition-polymerized block copolymer (I), the softener for non-aromatic rubber (II), and the thermoplastic polyester-based polymer (III). Is preferably 25 to 65% by mass. In particular, when a thermoplastic polyester resin is used as the thermoplastic polyester polymer (III),
It is preferable that the blending amount of the thermoplastic polyester resin is 25 to 60% by mass based on the total mass of the user.

The blending amount of the polyester block copolymer (IV) is such that the addition polymerization block copolymer (I), the softener for non-aromatic rubber (II), and the thermoplastic polyester polymer (III) If it is less than 5% by mass, the effect of the polyester-based block copolymer (IV) as a compatibilizer becomes difficult to be exhibited, and the mechanical strength of the obtained thermoplastic elastomer composition decreases. In addition, delamination (delamination) easily occurs during injection molding. On the other hand, the blending amount of the polyester-based block copolymer (IV) is such that the addition-polymerized block copolymer (I), the softener for non-aromatic rubber (II) and the thermoplastic polyester-based polymer (III) are mixed. When the amount exceeds 50% by mass based on the total mass, the melt fluidity of the obtained thermoplastic elastomer composition is lowered, and the surface of a molded product obtained by molding the thermoplastic elastomer composition is roughened, This causes a decrease in the adhesiveness. In particular, the thermoplastic elastomer composition of the present invention comprises a polyester-based block copolymer (IV), an addition-polymerized block copolymer (I), a softener for a non-aromatic rubber (II), and a thermoplastic polyester-based copolymer. The content is preferably 10 to 45% by mass, more preferably 15 to 40% by mass, based on the total mass of the polymer (III).

The thermoplastic elastomer composition of the present invention comprises:
Along with the above components, if necessary, styrene resins such as α-methylstyrene resin, other thermoplastic resins such as polyphenylene ether resin, inorganic fillers such as calcium carbonate, talc, mica, and carbon black, flame retardants, It may contain an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a colorant, a release agent, an antiblocking agent, an antistatic agent, a foaming agent, a fragrance, and the like.

The method for preparing the thermoplastic elastomer composition of the present invention is not particularly limited, and any method and apparatus used in the production of ordinary thermoplastic resin compositions and thermoplastic elastomer compositions can be used. For example, it can be prepared using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll, a Brabender, various kneaders, and the like. Melt kneading temperature is generally 200 to 300.
The temperature can be selected from the range of 230 ° C to 270 ° C.

The thermoplastic elastomer composition of the present invention comprises:
It can be molded in the same manner as a normal thermoplastic resin or thermoplastic elastomer, and can be molded into various molded articles by, for example, injection molding, extrusion molding, calender molding, press molding, blow molding, or the like.

The thermoplastic elastomer composition of the present invention comprises:
Its excellent oil resistance, flexibility, low temperature impact resistance, rubber elasticity,
Utilizing properties such as mechanical properties and heat resistance, it can be effectively used for various applications. Specifically, for example, automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers,
Automotive functional parts such as rack & pinion boots, remote control switches, home appliances parts such as various rolls and key tops of OA equipment, underwater products such as underwater glasses and underwater camera covers, various cover parts, airtightness, waterproofness, soundproofing Parts with various packings for the purpose of safety and vibration proofing, curling cord electric wire covering, electricity such as belt, hose, tube, etc.
It can be used for a wide variety of applications such as electronic components and sports equipment.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Various physical property tests in the following Examples and Comparative Examples were performed as follows.

(1) Hardness: JIS-A hardness was measured according to JIS K-6253. (2) Tensile strength and tensile elongation: JIS K-6251
A dumbbell No. 5 test piece was prepared by injection molding, and its tensile strength (MPa) and tensile elongation (%) were measured. (3) Compression set: Based on JIS K-6262,
The compression set (%) when compressed at 70 ° C. for 22 hours was measured. (4) Low-temperature impact resistance: Using the thermoplastic elastomer composition obtained in the following Examples or Comparative Examples, using an injection molding machine (“IS-55EPN” manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 55t). A 110 mm × 110 mm × 2 mm thick sheet-like test piece was formed, and the test piece was placed in an atmosphere of −40 ° C., a 500 g sphere was dropped from 1 m above, and the surface condition at that time was visually observed. When no change occurred, the low-temperature impact resistance was evaluated as good (O), and when cracks and / or delamination (delamination) occurred, the low-temperature impact resistance was poor (X). Was evaluated. (5) Oil resistance (swelling ratio): 11 in the same manner as in (4) above.
A sheet-like test piece having a thickness of 0 mm x 110 mm x 2 mm was formed, and the test piece was formed into a sheet in accordance with JIS K-6258.
It was immersed in No. 2 oil at 0 ° C. for 72 hours, and the swelling ratio (%) was determined from the following equation.

[0051]

Swelling rate (%) = {(W ₁ −W ₀ ) / W ₀ } × 100 [where W ₀ is the weight (g) of the test piece before immersion in oil,
W ₁ indicates the weight (g) of the test piece after immersion in oil at 120 ° C. for 72 hours. ]

The contents of each component used in the following Examples and Comparative Examples are as follows. ○ Addition polymerization block copolymer (I) : “Septon 4077” manufactured by Kuraray Co., Ltd. (triblock copolymer composed of hydrogenated polystyrene-isoprene / butadiene copolymer-polystyrene; number average molecular weight = 260,000; styrene) (Content = 30% by mass) ○ Softener for non-aromatic rubber (II) : “Diana Process PW-380” manufactured by Idemitsu Kosan Co., Ltd. [paraffin-based process oil; kinematic viscosity = 381.6 cst (40 ° C) and 30 .10 cst (100 ° C.); average molecular weight = 746;
Ring analysis: CN 27.0% and CP 73.0%] ○ Thermoplastic polyester-based polymer (III) : ・ Thermoplastic polyester-based resin (IIIa): “KL263F” (polybutylene terephthalate resin) manufactured by Kuraray Co., Ltd. ・ Polyester-based Thermoplastic elastomer (IIIb): "Hytrel 4047" manufactured by Toray DuPont (polyester-polyether block copolymer, JIS K721)
5 surface hardness 40D)

Reference Example 1 [Production of Polyester Block Copolymer (IV)] (1) The following hydrogenated SBIS-OH was used as a block copolymer of an addition polymerization block (D). A polyester block copolymer (IV) is produced by the following method (2) using "KL263F" [polybutylene terephthalate resin (PBT)] manufactured by Kuraray as a resin for the thermoplastic polyester resin block (E). did. [Hydrogenated SBIS-OH] Polystyrene block (number average molecular weight: 6000) / 1 hydrogenated copolymer block of 1,3-butadiene and isoprene (number average molecular weight: 28,000) / polystyrene block (number average molecular weight: 6000) Triblock copolymer having a hydroxyl group as a functional group capable of reacting with a polyester resin (number average molecular weight 4
0000) (hydroxyl content in hydrogenated SBIS-OH = 0.9 / molecule; styrene content before hydrogenation = 30% by mass; 1,3-butadiene and isoprene before hydrogenation in copolymer block Molar ratio of 1,3-butadiene to isoprene = 1/1, 1,4-bond amount in 1,3-butadiene unit = 95%, 3,4-bond amount = 5%; 1,3-butadiene and isoprene Degree of unsaturation = 5%; Mw / Mn = 1.11)

(2) (i) Addition polymerization block (D)
Dry blending of 100 parts by mass of hydrogenated SBIS-OH for use and 100 parts by mass of "KL263F" (PBT) manufactured by Kuraray Co., Ltd. for a thermoplastic polyester resin block (E), and a twin screw extruder (manufactured by Toshiba Machine Co. TEM-3
5B "), melt-kneading under the conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm,
Extruded and cut to obtain pellets. The pellets were transferred to a solid-state polymerization apparatus having a gas inlet, an exhaust port, a vacuum coupler, and the like, and treated at 120 ° C. for about 4 hours under nitrogen gas introduction to perform drying and crystallization. Thereafter, the internal pressure of the solid-state polymerization apparatus was reduced to about 0.2 mmHg and the temperature was raised to 200 ° C. to start the solid-state polymerization reaction. After about 12 hours of solid phase polymerization, nitrogen gas was supplied to return the system to normal pressure. (Ii) The reaction product obtained by the solid-phase polymerization is converted into hexafluoroisopropanol / chloroform (1/1 volume).
And the solution was poured into tetrahydrofuran to form a precipitate, and the precipitate was collected.
The precipitate thus obtained was heated under reflux in chloroform, filtered off, and the PBT / hydrogenated SBIS block copolymer was isolated by concentrating and drying the chloroform solution to dryness. (Iii) PBT / hydrogenated SBIS isolated in (ii) above
When ¹ H-NMR measurement of the block copolymer was performed,
Peaks derived from the chemical structure of PBT (8.1, 4.1,
2.2 ppm peak) and peaks derived from the chemical structure of hydrogenated SBIS-OH (7.0, 6.6, 0.7-2.
0 ppm) and the hydrogenated SBIS used
The chemical shift of the peak of the methylene proton adjacent to the hydroxyl group at the molecular end observed in -OH was shifted. Further, GPC measurement showed that the precipitate showed a single molecular weight distribution, and its number average molecular weight was determined by the number average molecular weight of PBT used as a raw material and hydrogenated SBIS.
It was almost equal to the sum of the number average molecular weights of -OH. Therefore, from those results, the product obtained by the above operation was identified as a diblock copolymer composed of one PBT block and one hydrogenated SBIS block.

Examples 1 to 6 (1) The above addition-polymerized block copolymer (I), softener for non-aromatic rubber (II) and thermoplastic polyester polymer (III) The polyester-based block copolymer (IV) produced with the property 1 was blended in an amount (parts by mass) shown in Table 1 below, and a twin-screw extruder (“TEM-35” manufactured by Toshiba Machine Co., Ltd.)
B "), the mixture was melt-kneaded at a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, extruded, cut and pelletized to produce pellets of a thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in the above (1), test specimens for each of the above-mentioned physical property tests were prepared, and the respective physical properties were measured or evaluated by the above-mentioned methods. As shown in Table 1.

Comparative Example 1 (1) The above addition-polymerized block copolymer (I), non-aromatic rubber softener (II) and thermoplastic polyester-based polymer (III) were prepared as shown in Table 2 below. At a cylinder temperature of 250 ° C. and a screw rotation speed of 2 using a twin-screw extruder (“TEM-35B” manufactured by Toshiba Machine Co., Ltd.).
The mixture was melt-kneaded under the conditions of 00 rpm, extruded, cut and pelletized to produce pellets of the thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in the above (1), test specimens for each of the above-mentioned physical property tests were prepared, and the respective physical properties were measured or evaluated by the above-mentioned methods. As shown in Table 2. When the thermoplastic elastomer composition of Comparative Example 1 was observed with an electron microscope, compatibilization between components was not sufficiently performed, and delamination (delamination) was severe.

<< Comparative Example 2 >> (1) The above-mentioned addition-polymerized block copolymer (I), softener (II) for non-aromatic rubber and thermoplastic polyester-based polymer (III), and Reference Example 1 The amount (parts by mass) of the polyester-based block copolymer (IV) produced in (1) shown in Table 2 below
And a twin screw extruder (“TEM-35” manufactured by Toshiba Machine Co., Ltd.)
B "), the mixture was melt-kneaded at a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, extruded, cut and pelletized to produce pellets of a thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in the above (1), test pieces for each of the above-mentioned physical property tests were produced. Therefore, physical properties were not tested.

Comparative Example 3 (1) The above-mentioned addition-polymerized block copolymer (I), softening agent for non-aromatic rubber (II) and thermoplastic polyester polymer (III), and Reference Example 1 The amount (parts by mass) of the polyester-based block copolymer (IV) produced in (1) shown in Table 2 below
And a twin screw extruder (“TEM-35” manufactured by Toshiba Machine Co., Ltd.)
B "), the mixture was melt-kneaded at a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, extruded, cut and pelletized to produce pellets of a thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in the above (1), test pieces for performing each test were prepared, and all of the obtained test pieces had severe surface roughness and warpage. Was not large enough to be used. Therefore, physical properties were not tested.

Comparative Example 4 (1) The above-mentioned addition-polymerized block copolymer (I), softener (II) for non-aromatic rubber and thermoplastic polyester-based polymer (III), and Reference Example 1 The amount (parts by mass) of the polyester-based block copolymer (IV) produced in (1) shown in Table 2 below
And a twin screw extruder (“TEM-35” manufactured by Toshiba Machine Co., Ltd.)
B "), the mixture was melt-kneaded at a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, extruded, cut and pelletized to produce pellets of a thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in (1) above, test pieces for performing each test were prepared, and all of the obtained test pieces were softened for non-aromatic rubber. Since the bleed of the agent (II) was so severe that it could not be used, no physical property test was conducted.

Comparative Example 5 The above-mentioned addition-polymerized block copolymer (I), softener (II) for non-aromatic rubber and thermoplastic polyester-based polymer (III) were prepared in Reference Example 1. The polyester-based block copolymer (IV) was blended in the amount (parts by mass) shown in Table 3 below, and supplied to a twin-screw extruder (“TEM-35B” manufactured by Toshiba Machine Co., Ltd.) to obtain a cylinder temperature of 25.
Extrusion and pelletization were attempted by melt-kneading at 0 ° C. and a screw rotation speed of 200 rpm, but the pellets were not formed, so that subsequent tests were not performed.

Comparative Examples 6 to 8 (1) The above addition-polymerized block copolymer (I), softener for non-aromatic rubber (II) and thermoplastic polyester-based polymer (III) The polyester-based block copolymer (IV) produced with the property 1 was blended in an amount (parts by mass) shown in Table 1 below, and a twin-screw extruder (“TEM-35” manufactured by Toshiba Machine Co., Ltd.)
B "), the mixture was melt-kneaded at a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, extruded, cut and pelletized to produce pellets of a thermoplastic elastomer composition. (2) Using the pellets of the thermoplastic elastomer composition obtained in the above (1), test specimens for each of the above-mentioned physical property tests were prepared, and the respective physical properties were measured or evaluated by the above-mentioned methods. As shown in Table 3.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

As can be seen from the results in Table 1 above, Example 1
The thermoplastic elastomer compositions of (1) to (6), an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II),
By containing the thermoplastic polyester-based polymer (III) and the polyester-based block copolymer (IV) in an amount within the range specified in the present invention, both have excellent low-temperature impact resistance and oil resistance, Moreover, it is excellent in rubber elasticity, flexibility and mechanical properties.

On the other hand, as can be seen from the results in Table 2 above, the thermoplastic elastomer composition of Comparative Example 1 does not contain the polyester-based block copolymer (IV), and therefore has a tensile strength and a tensile elongation. The mechanical properties represented by degrees are inferior to those of Examples 1 to 6, and also inferior in low-temperature impact resistance and oil resistance. As can be seen from the results in Table 2, the thermoplastic elastomer composition of Comparative Example 2 was composed of an addition-polymerized block copolymer (I), a softener for a non-aromatic rubber (II), and a thermoplastic polyester-based polymer. Coalescing (II
I) and a polyester-based block copolymer (IV) containing the polyester-based block copolymer (IV)
Is more than the range specified in the present invention, flow marks on the surface of the molded product are remarkable, and a molded product having practical value cannot be obtained.

Further, as can be seen from the results in Table 2, the thermoplastic elastomer composition of Comparative Example 3 was composed of an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II), Contains polyester-based polymer (III) and polyester-based block copolymer (IV), but the content of softener for non-aromatic rubber (II) is less than the range specified in the present invention As a result, the surface of the molded product becomes rough,
Moreover, the warpage of the molded article is large, and a molded article having practical value cannot be obtained. In addition, as seen from the results in Table 2, Comparative Example 4
The thermoplastic elastomer composition of (1) comprises an addition-polymerized block copolymer (I), a softening agent for non-aromatic rubber (II), a thermoplastic polyester-based polymer (III) and a polyester-based block copolymer (IV) However, since the content of the softener for non-aromatic rubber (II) is larger than the range specified in the present invention, the softener for non-aromatic rubber (II) 2) The bleed-out is severe, and a molded product having practicality cannot be obtained.

Further, as can be seen from the results in Table 3, the thermoplastic elastomer composition of Comparative Example 5 was composed of an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II), and a thermoplastic elastomer. Although it contains a polyester-based polymer (III) and a polyester-based block copolymer (IV), the content of the thermoplastic polyester-based polymer (III) is less than the range specified in the present invention. In addition, pelletization of the thermoplastic elastomer composition cannot be performed. As can be seen from the results in Table 3, the thermoplastic elastomer composition of Comparative Example 6 was composed of an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II), and a thermoplastic polyester-based polymer. Coalescing (II
A thermoplastic polyester-based polymer (III) containing (I) and a polyester-based block copolymer (IV)
Is higher than the range specified in the present invention, so that the hardness is high, the tensile elongation is low, the compression set is large, the rubber elasticity is poor, and the low-temperature impact resistance is also poor. .

As can be seen from the results in Table 3, the thermoplastic elastomer composition of Comparative Example 7 was composed of an addition-polymerized block copolymer (I), a softener for non-aromatic rubber (II), and a thermoplastic elastomer. Although it contains a polyester-based polymer (III) and a polyester-based block copolymer (IV), the content of the thermoplastic polyester-based polymer (III) is larger than the range specified in the present invention. High hardness, low tensile elongation, high compression set, and poor rubber elasticity. As can be seen from the results in Table 3, the thermoplastic elastomer composition of Comparative Example 8 was composed of an addition-polymerized block copolymer (I), a softener for a non-aromatic rubber (II), and a thermoplastic polyester-based polymer. Although it contains the copolymer (III) and the polyester-based block copolymer (IV), the content of the thermoplastic polyester-based polymer (III) is smaller than the range specified in the present invention. And low oil resistance.

[0070]

Industrial Applicability The thermoplastic elastomer composition of the present invention is excellent in oil resistance, flexibility and low-temperature impact resistance, and is also excellent in rubber elasticity, mechanical strength and heat resistance. It can be effectively used for a wide range of applications such as industrial parts, home electric parts, and electric / electronic parts.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AC03X AE04X AE05X BB05X BP01W BP03Z CF00Y CF00Z CF05Y CF06Y CF07Y CF08Y CF10Y CF16Y CF17Y FD02X GC00 GM00 GM01 GQ00 GQ01

Claims (4)

[Claims] (I) at least one selected from a block copolymer having a polymer block (A1) mainly composed of an aromatic vinyl compound and a polymer block (B1) mainly composed of a conjugated diene compound, and a hydrogenated product thereof; (II) 30 to 250 parts by mass of a softening agent for non-aromatic rubber; (III) Addition polymerization of the thermoplastic polyester-based polymer to the above-mentioned (I). 20 to 70% by mass with respect to the total mass of the system block copolymer, the softener for non-aromatic rubber (II) and the thermoplastic polyester polymer (III); A block copolymer having a polymer block (A2) mainly composed of an aromatic vinyl compound and a polymer block (B2) mainly composed of a conjugated diene compound, or a hydrogenated product thereof. Addition polymerized block and (D),
The polyester-based block copolymer having a thermoplastic polyester-based resin block (E) is obtained by combining the addition-polymerized block copolymer of (I), the softener for non-aromatic rubber of (II), and the (III) 5 to 50% by mass with respect to the total mass of the thermoplastic elastomer-based polymer and the thermoplastic elastomer composition. 2. The addition-polymerized block copolymer (I) is a polymer block (A1) -polymer block (B)
The thermoplastic elastomer composition according to claim 1, which is a triblock copolymer composed of 1) -polymer block (A1). 3. The polymer block (B1) in the addition polymerization type block copolymer (I) is a polymer block mainly composed of isoprene, butadiene or a mixture of isoprene and butadiene and / or a hydrogenated product thereof. The thermoplastic elastomer composition according to claim 1. 4. The polyester block copolymer (IV) is a diblock copolymer comprising one addition polymerization block (D) and one thermoplastic polyester resin block (E). Item 4. The thermoplastic elastomer composition according to any one of Items 1 to 3.