JP2001279067A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer excellent in flexibility, weather resistance, heat resistance, oil resistance, low temperature properties, strength and moldability. SOLUTION: A thermoplastic elastomer composition composed of the following components (A), (B) and (C) (A) A thermoplastic polyester elastomer: 100 pts.wt. (B) A modified olefin resin having epoxy groups or groups of its derivative in a molecule: 3-100 pts.wt. (C) A gummy elastomer selected from the group consisting of olefin and/or styrene thermoplastic elastomers: 10-900 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to various types of molded articles having excellent scratch resistance (scratch resistance) and excellent flexibility, heat resistance, oil resistance, low temperature properties, weather resistance, strength, and moldability. The present invention relates to a thermoplastic elastomer composition that can be used as a material for a molded product.

[0002]

2. Description of the Related Art Thermoplastic elastomers having excellent productivity have been increasingly used for automotive parts, home electric parts, medical parts and miscellaneous goods, for which vulcanized rubber has hitherto been mainly used. Examples thereof include olefin-based elastomers composed of an ethylene-propylene copolymer and polypropylene, polyurethane elastomers, and soft polyvinyl chloride.

However, at present, these molding materials have drawbacks in terms of scratch resistance, flexibility, workability, economy, and recyclability. That is, olefin-based elastomers are relatively inexpensive and have excellent weather resistance and heat resistance, but are inferior in flexibility and scratch resistance. Further, the polyester elastomer has excellent scratch resistance, but has a drawback that it has a large specific gravity and is expensive. In addition, soft polyvinyl chloride is relatively inexpensive and has excellent weather resistance and scratch resistance, but has the drawback of poor flexibility at low temperatures and poor recyclability.

Some proposals have also been made for elastomer compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). . For example, JP-A-50-14742, JP-A-52-65551,
JP-A-58-206644 discloses compositions in which a hydrogenated block copolymer is blended with a rubber softener and an olefin resin. However, these compositions, like the olefin-based elastomers, also had poor scratch resistance.

[0005] Further, some proposals have been made on compositions using polyester-based elastomers.
For example, see JP-A-6-207086, JP-A-6-207086
No. 28419, JP-A-6-240446, JP-A-9-132700, JP-A-9-227760
JP-A-10-7878 discloses a thermoplastic elastomer composition in which a polyester elastomer is blended with various other elastomers or a modified (having a functional group) elastomer. However, these compositions have a problem that the compatibility of various components is insufficient or a crosslinking reaction occurs extremely, resulting in poor moldability. Further, the cost was not satisfactory, for example, a large amount of expensive modified elastomer was used.

[0006]

SUMMARY OF THE INVENTION The present invention has been made on the background of the above-mentioned conventional technical problems, and has been developed in consideration of the heat, excellent in flexibility, weather resistance, heat resistance, oil resistance, low-temperature characteristics, strength and moldability. A plastic elastomer is provided.

[0007]

That is, the present invention relates to a thermoplastic elastomer composition comprising the following components (A), (B) and (C). (A) Thermoplastic polyester elastomer: 100 parts by weight (B) Modified olefin resin having an epoxy group or its derivative group in a molecule: 3 to 100 parts by weight (C) Group consisting of olefin-based and / or styrene-based thermoplastic elastomer Rubber-like elastic material selected from: 1
0 to 900 parts by weight

Hereinafter, the present invention will be described in detail. The thermoplastic polyester elastomer used as the component (A) of the present invention generally includes styrene, olefin,
Compared to general-purpose thermoplastic elastomers such as vinyl chloride,
Excellent heat resistance, cold resistance, oil resistance, and toughness, but relatively expensive. For this reason, applications are mainly focused on functional products such as automobiles, general industries, and electric / electronic devices.

The thermoplastic polyester elastomer of the present invention is a polyester block copolymer having a high melting point hard segment composed of an aromatic polyester unit and a low melting point soft segment composed of an aliphatic polyether unit and / or an aliphatic polyester unit. . Those whose soft segments are aliphatic polyether units are polyester polyether block copolymers, and those whose soft segments are aliphatic polyester units are polyester polyester block copolymers. This is a general-purpose type with good balance of cold resistance, chemical resistance, moldability, etc., and polyester polyester type is particularly excellent in heat resistance, weather resistance and mechanical strength.

Typical low melting point soft segment constituents of the polyester polyether block copolymer of the present invention include polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and mixtures thereof. And copolymerized polyether glycols obtained by copolymerizing these polyether constituents.
The low-melting point soft segment constituting component of the polyester polyester block copolymer of the present invention includes an aliphatic or alicyclic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic or alicyclic having 2 to 10 carbon atoms. Polyesters composed of aliphatic glycols such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene decanate, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, etc. Aliphatic polyesters and two aliphatic dicarboxylic acids or 2
Aliphatic copolyesters made using the same glycols can be mentioned. Further, as the low melting point soft segment constituent component, a polyester polyether type block copolymer obtained by combining the above aliphatic polyester and aliphatic polyether can also be mentioned.

Preferred examples of the polyester polyether type block copolymer of the present invention include (a) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and / or an ester-forming derivative thereof; A) an aliphatic diol which is a short-chain diol component, (c) a long-chain diol component comprising a tetramethylene oxide structural unit (hereinafter abbreviated as T) represented by the following formula (1), and both terminals are alcoholic hydroxyl groups; It is a polyester polyether block copolymer (hereinafter, referred to as copolymer I) obtained by copolymerizing a polyether glycol having an average molecular weight of 400 to 6,000.

[0012]

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The component (a), that is, the aromatic dicarboxylic acid and its ester-forming derivative include terephthalic acid,
Isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid and / or these Ester-forming derivatives and the like.

Also, alicyclic or aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecandic acid, dimer acid and / or ester-forming derivatives thereof. May be used. These may be used alone or in combination of two or more. Preferably, terephthalic acid, isophthalic acid, and naphthalene-2,6-dicarboxylic acid are used.

As the component (b), that is, an aliphatic diol, a diol having a molecular weight of 300 or less is usually used. For example, ethylene glycol, 1,3-propylene diol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol and the like can be mentioned.

Also, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedimethanol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p- Hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4 (2-hydroxy) phenyl] sulfone,
1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and the like. Preferably, ethylene glycol and 1,4-butanediol are used.

The combination of the above-mentioned aromatic dicarboxylic acids and / or their ester-forming derivatives with an aliphatic diol constitutes the hard segment of copolymer I, that is, a short-chain polyester, and the preferred combination is terephthalic acid or terephthalic acid. A combination of an acid diester with ethylene glycol or 1,4-butanediol (polyethylene terephthalate, polybutylene terephthalate). More preferably, polybutylene terephthalate is preferably used for the hard segment.

The reason for this is that polybutylene terephthalate has a high crystallization rate and is excellent in moldability. Even when the copolymer I is used, a good balance of physical properties such as rubber elasticity, mechanical properties, heat resistance and chemical resistance is provided. It depends on what you do.
Other dicarboxylic acids and / or ester-forming derivatives thereof may be used in the combination, up to 15 mol%, or other diols up to 15 mol%.

The component (c) forming the low melting point soft segment, that is, the polyether glycol constituting the long-chain polyester is composed of T, both ends are alcoholic hydroxyl groups, and have a number average molecular weight of 400 to 6, 000.

Further, the copolymer I of the present invention includes:
The long-chain diol component (c) is composed of T represented by the following formula (1) and neopentylene oxide structural unit (hereinafter abbreviated as N) represented by the following formula (2), and the ratio of N is 5 to 50 mol. %, Preferably 10 to 20% by mole of a polyether having an alcoholic hydroxyl group at both terminals and a polyether glycol having a number average molecular weight of 400 to 6,000. Combination I can also be suitably used.

[0021]

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[0022]

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When a copolymerized polyether of T and N is used as the long-chain diol component (c), the low-temperature properties, rubber elasticity, flexibility and softness of the elastomer composition of the present invention are particularly excellent. preferable.

As the component (c) of the present invention, there is no particular limitation on the method for producing a polyether glycol in which the polyether glycol constituting the long-chain polyester is T. For example, tetrahydrafuran may be used in the presence of a heteropolyacid catalyst. The diol obtained by ring-opening polymerization below is mentioned.

Further, as the component (c), the polyether glycol used for producing the copolymer I of the present invention using the polyether glycol comprising T and N as the polyether glycol constituting the long-chain polyester is 3, Homo-cationic polymerization of 3-dimethyloxetane (3,3-DMO), 3,3-DMO and neopentyl glycol (hereinafter N
PG), cation copolymerization of 3,3-DMO and tetrahydrofuran (hereinafter abbreviated as THF), terpolymerization of 3,3-DMO, NPG and THF, or NPG and THF as raw materials It can be produced under the reaction conditions in which the depolymerization of pure tetramethylene glycol proceeds in the presence of a catalyst exhibiting activity in the presence of an alcoholic hydroxyl group.

When the copolymer composition in which N in the polyether glycol is less than 5 mol% is used as the copolymer I, it is not preferable because physical properties satisfying particularly low-temperature performance may not be obtained. On the other hand, if the N content in the polyether glycol exceeds 50 mol%, the glass transition temperature of the thermoplastic polyester elastomer increases, and the low-temperature properties deteriorate, which is not preferable.

A preferred method for producing polyether glycol used for producing the copolymer I is as follows: a large amount of neopentyl glycol is charged in the presence of a catalyst which is active in the presence of an alcoholic hydroxyl group; The reaction is carried out at a high temperature at which depolymerization proceeds and a low THF concentration, that is, a high polymer concentration. As a catalyst showing activity in the presence of an alcoholic hydroxyl group, JP-A-60-1985
No. 20366 discloses a heteropoly acid disclosed in JP-A-61-12.
No. 0830 describes salts of heteropolyacids, but these can be used. At this time, the requirement that the molar ratio of water or diol to the catalyst is 10 or less is unnecessary under the reaction conditions for providing the polyether glycol of the present invention.

The catalyst which shows activity in the presence of an alcoholic hydroxyl group is not particularly limited to a heteropolyacid, and benzenesulfonic acid, toluenesulfonic acid and the like may be used. The reason why the copolymerization ratio of neopentyl glycol can be increased in a special reaction condition method that gives a preferable polyether glycol used in the production of the copolymer I used in the present invention is that the molar ratio of diol to catalyst is Even if it is 30, the polymerization can proceed, so that a large amount of neopentyl glycol can be charged. Further, the formation of a polymer molecular chain consisting of only THF is suppressed because the polymerization proceeds under the depolymerization conditions of pure poly (tetramethyleneoxy) glycol.

The requirements for producing the polyether glycol used in the copolymer I preferably include the following three requirements. First, a catalyst which is active in the presence of an alcoholic hydroxyl group, such as a heteropolyacid or sulfonic acid, is used. That, secondly, to use a glycol that inhibits the propagation of depolymerization, that is, NPG, as a copolymerized glycol, and thirdly, to make polycondensation in which the copolymerization ratio is high as a main reaction,
The reaction proceeds at a temperature and a polymer concentration at which depolymerization of pure poly (tetramethyleneoxy) glycol proceeds.

In order to carry out the polycondensation reaction at a preferable rate, the reaction temperature must be 70 ° C. or higher, preferably 75 ° C. or higher. However, if the reaction temperature is too high, the coloring of the reaction solution or the catalyst becomes strong, which is not preferable. For example, in the case where phosphotungstic acid is used as a catalyst, coloring usually becomes severe above 110 ° C.

Although the catalysts used in the present invention have been mentioned above, preferred catalysts among them include phosphotungstic acid which is commercially available, has good stability at high temperatures and high reaction activity. When a heteropolyacid such as tungstophosphoric acid is used as a catalyst, as the reaction proceeds, the reaction solution is composed of a catalyst layer having a high catalyst concentration and one catalyst.
%, And the reaction is carried out in a two-layer dispersed state. If the stirring is stopped at the end of the reaction and the mixture is allowed to stand, the heavy catalyst layer separates below and the light liquid layer separates above. The upper liquid layer is taken out, and THF, oligomers and dissolved catalyst are removed to obtain a target polymer. A new batch of NPG and THF is supplied to the catalyst layer left below, and a new batch reaction is started. In this way, the copolymer I serving as a raw material of the present invention can be obtained while repeatedly using the catalyst.

When sulfonic acid is used as a catalyst, a catalyst that does not dissolve in the reaction solution, such as Nafion,
Separation of the catalyst is simple and preferred. The amount of NPG to be used is preferably 2 to 10 moles of NPG per 1 equivalent of the catalyst with respect to the amount of the phosphotungstic acid or sulfonic acid used as the catalyst. If the amount of NPG is small, the amount of the polymer to be collected at the end of the reaction decreases, and if the amount of NPG is large, the polycondensation reaction is slow and it takes a long time to increase the degree of polymerization of the polymer.

The water produced by the polycondensation can be taken out and removed as gaseous phase moisture in the reaction system. The composition of the gas phase is mostly THF, and the water content of the gas phase is 0.4 to 2.0 wt.
% Is usually included. Therefore, when removing water, THF is taken out together, and it is necessary to replenish new THF by that much. Since it is necessary to take out the gas phase of the reaction system, the reaction solution is at the boiling temperature. In order to control the boiling temperature, that is, the reaction temperature, to a predetermined value, it is an easy method to control the concentration of THF. As a specific operation, TH is adjusted so that the liquid temperature is maintained at a predetermined value.
If the replenishment rate of F is to be controlled, THF taken out together with vapor-phase water, composition change accompanying the progress of the reaction and consumption of THF due to polymerization, and a standard operation capable of coping with all these changes are defined for THF. It is gained.

The THF concentration in the reaction solution varies depending on the reaction pressure and the reaction temperature, that is, the boiling pressure and temperature. Therefore, THF
The concentration can be controlled by the reaction pressure under the condition of the reaction temperature. The concentration of water in the reaction solution is in dynamic equilibrium with the concentration of water in the gas phase of the reaction system. Therefore, the water concentration in the reaction solution is
It can be controlled by the water concentration in the gas phase of the reaction system.

The number average molecular weight of the polyether glycol used for the production of the copolymer I is 400 to 6,000, preferably 800 to 3,000, and more preferably 1.0 to 1.0.
Those having a value of 00 to 2,000 are used. When it is less than 400, the average chain length of the short-chain polyester (hard segment) usually decreases, depending on the hard / soft segment ratio of the final copolymer I to be polymerized. It is not preferable to use the copolymer I as a material as it is or to use it as a composition. On the other hand, if it exceeds 6,000, the terminal group concentration in the polyether glycol per unit weight becomes low, and it becomes difficult to polymerize.

The total amount of the polyether glycol units (soft segments) in the copolymer I used in the present invention is 20 to 90% by weight, preferably 30 to 80% by weight,
More preferably, it is 40 to 70% by weight. In this case, the amount of the polyether glycol unit refers to the weight ratio of the soft segment, not the weight ratio of the charged polyether glycol in all monomers.

In general, the hard segment of the copolymer I is a short-chain ester and the soft segment is a long-chain ester, but the terminal of the polyether portion is linked to a dicarboxylic acid component by an ester bond, and is linked to the hard segment. ing. A unit including a unit constituting an ester bond at one end of the polyether portion was defined as a soft segment for convenience.

The ratio of this hard / soft segment is ¹
It can be accurately quantified by H-NMR. If the amount of the soft segment is less than 20% by weight, the softness is inferior, and particularly, the soft feeling of the steering of the present invention is impaired, which is not preferable. On the other hand, if the amount exceeds 90% by weight, the material becomes too soft, and the followability with the metal core is inferior.

The copolymer I can be produced by a known method. For example, a lower alcohol diester of a dicarboxylic acid, a transesterification reaction of an excessive amount of a low molecular weight glycol and a polyether glycol in the presence of a catalyst, followed by polycondensation of the resulting reaction product under reduced pressure, or a dicarboxylic acid and a glycol and A method in which polyether glycol is subjected to an esterification reaction in the presence of a catalyst, and then the resulting product is subjected to polycondensation. Alternatively, a short-chain polyester (for example, polybutylene terephthalate) is prepared in advance, and then another dicarboxylic acid, diol or Any method such as a method of adding ether glycol or adding another copolymerized polyester and performing randomization by transesterification may be employed.

As a catalyst common to the transesterification reaction or esterification reaction and the polycondensation reaction used for producing the copolymer I, tetra (isopropoxy) titanate,
Tetraalkyl titanates represented by tetra (n-butoxy) titanate, reaction products of these tetraalkyl titanates with alkylene glycols, partially hydrolyzed tetraalkyl titanates, metal salts of titanium hexaalkoxides, carboxylic acids of titanium Titanium-based catalysts such as salts and titanyl compounds are preferred. Also, monoalkyltin compounds such as mono-n-butylmonohydroxytin oxide, mono-n-butyltin triacetate, mono-n-butyltin monooctylate, mono-n-butyltin monoacetate, di-n-butyltin oxide, di-n-butyltin diacetate And dialkyl (or diaryl) tin compounds such as diphenyltin oxide, diphenyltin diacetate, and di-n-butyltin dioctylate.

In addition, metals such as Mg, Pb, Zr and Zn, metal oxides and metal salt catalysts are useful. These catalysts may be used alone or in combination of two or more.

The addition amount of the esterification or polycondensation catalyst is preferably from 0.005 to 0.5% by weight, more preferably from 0.03 to 0.2% by weight, based on the produced polymer. These catalysts may be added at the beginning of the transesterification or esterification reaction and may or may not be added again during the polycondensation reaction.

Further, as a part of the dicarboxylic acid or glycol, a polycarboxylic acid, other functional hydroxy compound, oxyacid or the like may be copolymerized. The other functional component effectively acts as a high viscosity component, and its copolymerizable range is 3 mol% or less. Those that can be used as such a polyfunctional component include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, butanetetracarboxylic acid, glycerin, pentaerythritol and their esters, acid anhydrides, and the like. Can be.

Further, if necessary, the polyether glycol may be partially substituted with another polyether glycol. Examples of the polyether glycol used for such substitution include poly (ethyleneoxy) glycol,
Poly (propyleneoxy) glycol, poly (tetramethyleneoxy) glycol, poly (1,2-propyleneoxy) glycol, a block or random copolymer of ethylene oxide and propylene oxide, THF and 3-
Examples include a random copolymer of methyl THF, a block or random copolymer of ethylene oxide and THF, poly (2-methyl-1,3-propyleneoxy) glycol, poly (propyleneoxy) diimidodiacid, and the like.

The preferred number average molecular weight of the polyether glycol used for these substitutions is from 400 to 6,000, particularly preferably from 1,000 to 3,000. Preferred substituted polyether glycols include poly (tetramethyleneoxy) glycol. When poly (tetramethyleneoxy) glycol is used for substitution, if the number average molecular weight (Mn) exceeds 1,800, the molecular weight distribution [Mv / Mn: Mn is the number average molecular weight determined from the terminal hydroxyl value, and Mv is the formula Mv = Anti log (0.493
log η + 3.0646). However, η is the melt viscosity at a temperature of 40 ° C. expressed in poise.] Depending on the case, crystallization may occur to give an undesirable result in low-temperature performance.

When the value of the molecular weight distribution (Mv / Mn) is 1.
It is more preferable to use a material as narrow as 6 or less. More preferably, it is 1.5 or less. Preferably, however, the substituted polyether glycol is used in a range of not more than 90% by weight of the polyether glycol used in the present invention. If this value exceeds 90% by weight, depending on the content of the neopentyl oxide unit in the polyether glycol used in the present invention, in general, satisfactory results in physical properties such as water resistance and low temperature performance cannot be obtained. Therefore, selection according to the application is necessary.

The polymerization degree of the copolymer I thus polymerized is generally expressed by a relative solution viscosity (η rel), an intrinsic viscosity ([η]), and a melt flow rate (MFR). In the invention, the melt flow rate (230 ° C.,
2.16 kg weight, hereinafter abbreviated as MFR).

The MFR is 0.5 to 100 g / 10 min, preferably 5 to 50 g / 10 min, more preferably 10 to 3 g.
0 g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the injection moldability is poor and short shots are caused, which is not preferable. On the other hand, if the MFR exceeds 100 g / 10 minutes, the mechanical properties (e.g., breaking strength, elongation at break), abrasion, compression set (C-Set) and the like are inferior.

The modified olefin resin having an epoxy group or a derivative thereof in the molecule, which is the component (B) of the present invention, comprises:
Each of the resulting thermoplastic elastomer compositions exhibits its effect as a compatibilizing agent for compatibilizing the thermoplastic polyester elastomer as the component (A) and the rubber-like elastic material as the component (C) described later. Improves the dispersibility of components.
As a result, not only the scratch resistance of the obtained thermoplastic elastomer and the appearance of the molded product can be improved, but also a molded product without peeling can be obtained. In particular, by reacting the epoxy group with a tough, oil-resistant thermoplastic polyester elastomer, the rubbery elastic body of component (C), which is soft and has poor oil resistance, is embedded in a continuous layer of the thermoplastic polyester elastomer. It is preferable to form a strong sea-island structure, and a tougher thermoplastic elastomer composition having more excellent oil resistance can be obtained. In this case, the particle diameter of the component (C) is preferably 1.4 μm or less in average particle diameter.

That is, as an embodiment of the thermoplastic polyester elastomer composition of the present invention, there is provided a thermoplastic polyester elastomer composition having a so-called sea-sea structure in which the component (C) and the component (A) are both continuous layers. Component (A) is a continuous phase, and component (C) is dispersed in component (A) with an average particle size of 1.4 μm or less.
More preferably, it has a sea-island structure. In this case, the component (A) which is a continuous layer is a sea portion, and the component (C) dispersed in the component (A) is an island portion. Also,
Even when a sea-island structure having the component (C) as an island portion is formed, when the average particle size of the island component is 1.4 μm or less, the mechanical properties, wear resistance, and oil resistance are further improved. Therefore, it is more preferable that the modified olefin resin used in the present invention is used as the component (B) and that the component (C) forms a fine sea-island structure having island portions having an average particle size of 1.4 μm or less. In this case, a thermoplastic polyester elastomer composition having greatly improved mechanical properties, abrasion resistance and oil resistance can be obtained.

The modified olefin resin used as the component (B) in the present invention is obtained by bonding a molecular unit containing an epoxy group or a derivative thereof to various olefin resins. Examples of various polyolefin resins before modification used as the component (B) include polyethylene resins and polypropylene resins. Examples of the polyethylene resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms. Ethylene and carbon number 3
To -8, α-olefins in the copolymer include propylene, butene-1, isobutene, pentene-1, hexene-1, 4-methylpentene-1, and octene-1. And the like. Also, α-
The olefin content is less than 20% by weight.

The polypropylene resin is a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms (hereinafter abbreviated as propylene resin). In the case of a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms, the α-olefin in the copolymer may be ethylene, butene-1, isobutene, pentene-
1, hexene-1, 4-methylpentene-1, octene-1 and the like. The ratio of α-olefin is 2
Less than 0% by weight is used.

Examples of other polyolefin resins include ethylene-methyl acrylate copolymer (EM
A), copolymers of ethylene and organic acid esters, such as ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and polybutene , Poly-4-methyl-pentene-1, novolten resin, polycyclohexadiene, and hydrogenated products thereof. Among these resins, a polyethylene resin is particularly preferred because the resulting elastomer composition has excellent strength and oil resistance.

The epoxy-modified olefin resin of the present invention includes a method of copolymerizing ethylene and an epoxy compound having an unsaturated double bond such as glycidyl methacrylate, and a method of copolymerizing an unmodified olefin resin with an unsaturated double bond such as glycidyl methacrylate. Or an addition reaction of an epoxy compound having the following formula, or by reacting the remaining unsaturated bond with peracetic acid or the like.

As an example of the method for producing the epoxy-modified olefin resin of the present invention, an olefin monomer and a compound containing an epoxy group or its derivative group are copolymerized using a commonly used radical initiator or Ziegler catalyst. There is a method to make it. Further, it can be obtained by co-existing a compound containing an epoxy group or a derivative group thereof with a commonly used radical initiator and adding a radical to the olefin resin.

As a method for producing a compound having an epoxy group or a derivative thereof by radical addition to an olefin resin, for example, a radical initiator is allowed to coexist in an extruder in the presence of an inert gas, and an unmodified olefin resin and an epoxy group or There is a method of reacting with the derivative group. Further, a method is also used in which an unmodified olefin resin is dissolved in a solvent such as toluene or xylene, and reacted with an epoxy group or a derivative group thereof in the presence of a radical initiator. Unreacted epoxy or its derivative is preferably removed by a suitable post-treatment such as vacuum degassing, extraction and precipitation.

The content of the compound containing an epoxy group or its derivative group in the polymer is 0.1 to 20 parts by weight, preferably 3 to 15 parts by weight, more preferably 8 to 12 parts by weight. If the content of the epoxy group or its derivative group is too large, the fluidity of the composition decreases, and a problem arises that the moldability deteriorates. On the other hand, if the content of the epoxy group or its derivative group is too small, the effect of improving the compatibility between the component (A) and the component (C) of the present invention becomes insufficient. Therefore, the above-described range of the additional amount is desirable.

The amount of the component (B) used in the present invention is 3 to 100 parts by weight, preferably 5 to 30 parts by weight, more preferably 8 to 100 parts by weight based on 100 parts by weight of the component (A) of the present invention.
20 parts by weight. When the amount of the component (B) is less than 3 parts by weight, the effect of improving the compatibility is not sufficient, and a composition excellent in strength, scratch resistance, appearance, and oil resistance cannot be obtained. Further, even when used in a large amount exceeding 100 parts by weight, the compatibility effect reaches a plateau, and the fluidity is rather remarkably reduced. Similarly, the composition is not excellent in strength, scratch resistance, appearance, and oil resistance. It is not preferable.

Next, as the rubbery elastic body which is the component (C) of the present invention, ethylene-propylene copolymer, ethylene-propylene / 5-ethylidene norbornene copolymer,
Ethylene-α-olefin copolymers such as ethylene-propylene / 5-methylnorbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-butene copolymer, ethylene-octene copolymer (α-
Olefin-based elastomers such as those having an olefin ratio of 20% by weight or more), and compositions (including dynamic vulcanizates) of these elastomers and the above-described olefin-based resins; styrene-butadiene block copolymers; Styrene-based elastomers such as styrene-isoprene block copolymers and hydrogenated products thereof are exemplified.
Examples of the rubbery elastic body which is the component (C) of the present invention include diene elastomers such as polybutadiene, polyisoprene, random copolymers of polybutadiene and polystyrene, and hydrogenated products thereof; natural rubber; balata rubber; Suloprene rubber; silicone rubber; nitrile rubber, fluorine rubber; urethane rubber; Among these elastomers, olefin-based elastomers and styrene-based elastomers are particularly preferred because the resulting elastomer composition is excellent in moldability, rubber elasticity and scratch resistance. Particularly preferably, an olefin-based elastomer of an ethylene-α-olefin copolymer having an α-olefin ratio of 20% by weight or more and a styrene-based elastomer obtained by hydrogenating styrene and a diene block copolymer are used as the component (C) of the present invention. When used, a thermoplastic elastomer composition having more excellent strength and oil resistance can be obtained.

Commercial products of the above-mentioned olefin-based elastomers include "Thermolan" manufactured by Mitsubishi Chemical Corporation, "Millastomer" manufactured by Mitsui Petrochemical Industries, Ltd., and "Sumitomo TP" manufactured by Sumitomo Chemical Co., Ltd.
E "," Santoprene "manufactured by AES," Engage "manufactured by Dow Chemical Co., Ltd .; commercially available styrene elastomers include" Toughtec "manufactured by Asahi Kasei Kogyo," Lavalon "manufactured by Mitsubishi Chemical, and Shell Japan "Clayton G" manufactured by Kuraray Co., Ltd., "Septon" and "High Blur", "Dynalon" manufactured by Nippon Synthetic Rubber Co., Ltd., and the like.

The above-mentioned polyolefin resin can be added to the thermoplastic elastomer composition of the present invention, if necessary.

Further, the composition of the present invention may optionally contain a plasticizer. Examples of such a plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate: tricresyl phosphate, triethyl phosphate, Tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-
Phosphates such as dichloropropyl phosphate: octyl trimellitate, isodecyl trimellitate, trimellitate, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate,
Dioctyl azelate, dioctyl sebacate, di-2
Fatty acid esters such as ethylhexyl sebacate and methylacetyl ricinocate: pyromellitic esters such as octyl pyromellitic acid: epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl esters: Polyether plasticizers such as adipic acid ether ester and polyether: liquid N
Liquid rubbers such as BR, liquid acrylic rubber and liquid polybutadiene: non-aromatic paraffin oils and the like.

These plasticizers can be used alone or in combination of two or more. The addition amount of the plasticizer is appropriately selected according to the required hardness and physical properties, but is preferably 0 to 50 parts by weight per 100 parts by weight of the composition.

Further, the thermoplastic elastomer composition of the present invention may contain an inorganic filler, a stabilizer, a lubricant, a coloring agent, a silicone oil, a foaming agent, a flame retardant and the like. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, and carbon black. Examples of the stabilizer include a hindered phenol-based antioxidant, a phosphorus-based heat stabilizer, a hindered amine-based light stabilizer, and a benzotriazole-based UV absorber. Examples of the lubricant include stearic acid, stearic acid esters, and metal salts of stearic acid.

In general, any method known in the art for blending polymer components may be used to prepare the thermoplastic elastomer composition of the present invention. In order to obtain the most homogeneous blend, a method of melt-kneading using various kinds of kneading machines such as commonly used mixing rolls, kneaders, Banbury mixers and extruders is desirable. Before melt-kneading, these compounds are dry-blended in advance using a mixer such as a Henschel mixer, tumbler or ribbon blender, and the mixture is melt-kneaded to obtain a homogeneous elastomer composition.

As the molding method of the thermoplastic elastomer composition of the present invention, injection molding, extrusion molding, compression molding and the like can be applied, but it has a feature that it is particularly excellent in moldability during injection molding. When performing injection molding, a normal plastic molding machine can be used, and an injection molded product can be obtained in a short time. In addition, the thermoplastic elastomer composition of the present invention has an advantage that the sprue portion and the runner portion can be recycled because of excellent thermal stability.

[0067]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the examples and comparative examples, the test methods used for various evaluation methods are as follows.

(1) Shore D hardness [-]: ASTM D
2240, D type, measured at 23 ° C.

(2) Melt flow rate (MFR) [g
/ 10 min]: ASTM D1238, 230 ° C, 2.1
It was measured under a load of 6 kg.

(3) Tensile strength [kgf / cm ² ]: J
IS K6251, No. 3 dumbbell, and a sample used a 2 mm-thick press sheet.

(4) Elongation [%]: JIS K6251,
A No. 3 dumbbell and a sample used a 2 mm-thick press sheet.

(5) Rebound resilience [%]: JIS K625
5, Lupke pendulum type, 23 ° C.

(6) Embrittlement temperature [° C.]: JIS K626
1. Gehman torsion test, t100 temperature.

(7) Scratch resistance and gloss retention [%]: A flat plate having a smooth surface was formed by injection molding. A flat plate is placed horizontally, and a cotton cloth to which a load of 40 g / cm ² is applied is placed.
Reciprocated twice. The glossiness of the friction surface is determined according to JIS K7105.
(E1), and the retention ratio from the glossiness (E0) before friction; (E1 / E0) × 100 (%) was determined.

(8) Crack drop test: A flat plate having a surface grain (matte, edging depth of about 20 microns) was formed by injection molding. The plate was left in an oven at 100 ° C. for 168 hours. After being taken out of the oven, the surface condition was visually observed, and those having no change were evaluated as ○, slightly glossy as Δ, and glossy as ×.

(9) Formability: A flat plate having a length of 150 mm, a width of 100 mm and a thickness of 2 mm was molded by an injection molding machine under the following conditions (gate; side gate having a cross section of 10 × 2 mm). Observe the appearance of the molded product, such as flow mark and gloss, by visual observation.
Poor ones were marked as x. Cylinder temperature C1: 200
° C, C2: 210 ° C, C3: 210 ° C, nozzle temperature: 2
00 ° C, injection speed: low, mold temperature: 40 ° C

(10) Evaluation of Peelability A flat plate was formed in the same manner except that the injection speed was increased under the above-mentioned injection molding conditions. The case where the peeling phenomenon occurred in the gate portion was visually evaluated as poor, and the case where the peeling phenomenon was not observed was evaluated as good.

(11) Evaluation of oil resistance A press sheet having a thickness of 2 mm was used as a sample. JIS sample
After immersion in No. 3 swelling oil at 70 ° C for 168 hours, the presence or absence of the elution of the component (C) is visually observed, and the degree of the elution of the component (C) is classified into three ranks: none, trace amount, and large amount. Classified.

(12) Evaluation of dispersion state of component (C) A pressed sheet having a thickness of 2 mm was used as a sample. -10 samples
After freezing and breaking at 0 ° C. or lower and immersing in cyclohexane for 16 hours to elute the component (C), the fracture surface is gold-deposited and dispersed in the component (A) with a scanning electron microscope (C). ) The dispersion state of the components was observed. When the sea-island structure in which the component (C) was an island was confirmed, the average particle size of the island was measured.

The components used in the examples and comparative examples are as follows. Component (A); Thermoplastic Polyester Elastomer The following components were used as the polyoxyalkylene glycol used in the soft segment of the thermoplastic polyester elastomer in the components (A) -1 and 2 described below. (1) Neopentyl glycol copolymer poly (tetramethyleneoxy) glycol (copolymer of T and N, both ends of which are alcoholic hydroxyl groups): manufactured by Asahi Kasei Corporation
Mn = 1480, Mv / Mn = 1.73, N content = 1
2 mol% (2) poly (tetramethyleneoxy) glycol: PTG-1,800, manufactured by Hodogaya Chemical Co., Ltd., Mn = 182
8, Mv / Mn = 2.11

Component (A) -1: A 15-liter conical reactor (VCR) manufactured by Mitsubishi Heavy Industries, Ltd. was charged with dimethyl terephthalate (manufactured by Mitsubishi Kasei KK, the same applies hereinafter) 1520.
g, 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, the same applies hereinafter), 1060 g, 3200 g of the above-mentioned polyoxyalkylene glycol (1), Irganox 1
Then, 15 g of 010 (manufactured by Ciba Geigy) was charged, and after replacing with nitrogen, the temperature was raised to 200 ° C. in a nitrogen atmosphere. Then, 1.5 g of tetraisopropoxytitanate (Reagent 1st grade, manufactured by Tokyo Chemical Industry, same hereafter) was added. And 30 to 200 ° C
After maintaining the temperature for 230 minutes, the temperature was raised to 230 ° C.
The transesterification reaction was performed for 2 hours while stirring at pm. The amount of methanol distilled out was 94% of the theoretical amount. Then, the temperature was raised to 250 ° C., and the pressure was reduced to 0.5 mmHg over 30 minutes while stirring at a rotation speed of 50 rpm.
Thereafter, the condensation reaction was carried out for about 3 hours until no increase in torque occurred.

When the content of the reactor was extracted from the lower part, a polyester block copolymer was obtained as a transparent viscous polymer. This was pelletized by strand cutting and vacuum dried at 70 ° C. for 12 hours. The carbon black master pellet (Royal Black RB 900
5) is 1 part by weight, and Irganox 1010 is 0.1 part by weight. 1 part by weight, 0.15 part by weight of dilauryl thiopropionate (DLTP, manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and TINUVIN
327 (manufactured by Ciba Geigy) in 0.1 parts by weight
A thermoplastic polyester elastomer was obtained by melt blending at 30 ° C. with an extruder.

The thermoplastic polyester elastomer had a Shore D hardness of 32 and an MFR of 23 g / 10 minutes.

Component (A) -2: In the same manner as in the synthesis of (A) -1, except that 2070 g of dimethyl terephthalate, 1440 g of 1,4-butanediol, and 2750 g of polyoxyalkylene glycol of (1) were charged. Transesterification and condensation reactions were performed. The kind of the additive and the mixing ratio were similarly measured. The resulting thermoplastic polyester elastomer has a Shore D hardness of 40 and an MFR of 21 g /
10 minutes.

Component (A) -3: Perprene P-40B manufactured by Toyobo Co., Ltd. The hard segment is polybutylene terephthalate, the soft segment is polytetramethylene glycol having a molecular weight of about 2,000, and the weight ratio of the soft segment is about 7
0% by weight of a thermoplastic polyester elastomer.

Component (A) -4: Perprene P-40H, manufactured by Toyobo Co., Ltd. The hard segment is polybutylene terephthalate, the soft segment is polytetramethylene glycol having a molecular weight of about 1,000, and the weight ratio of the soft segment is about 7
0% by weight of a thermoplastic polyester elastomer.

Component (B): Modified olefin resin Component (B) -1: Number average molecular weight 55,000, molecular weight distribution 1.08, bound styrene content 20% by weight, 1,2-vinyl of polybutadiene part before hydrogenation Styrene having a bond amount of 35% by weight and a hydrogenation rate of 99% of polybutadiene /
A hydrogenated block copolymer of a butadiene block copolymer was synthesized by the method described in JP-A-60-220147, and glycidyl methacrylate was used in an extruder at 2% by weight based on the weight of the hydrogenated block copolymer. Added.

Component (B) -2: Epoxy-modified polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Bond First E, glycidyl methacrylate 12% by weight copolymerized polyethylene, MF
R: 3 g / 10 minutes)

Component (B) -3: Epoxy-modified polyethylene vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B, glycidyl methacrylate 12% by weight, vinyl acetate 5% by weight copolymerized polyethylene, MFR: 7 g /
10 minutes)

Component (B) -4: Polymethyl methacrylate graft product of an epoxy-modified polyethylene copolymer (Modiper A4200 manufactured by NOF Corporation, glycidyl methacrylate 15 weight% copolymerized polyethylene 100 weight parts, methyl methacrylate was added to 43 parts by weight of graft polymerized, MFR: 0.6 g / 10 min)

Component (B) -5: Epoxy-modified polyethylene copolymer grafted with polybutyl acrylate methyl methacrylate copolymer (Modiper A manufactured by NOF Corporation)
4300, glycidyl methacrylate 15 weight% copolymerized polyethylene 100 weight parts, polybutyl acrylate and methyl methacrylate 43 weight parts graft polymerized)

Component (B) -6: Maleic acid-modified polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Bondyne AX8390, maleic anhydride 32% by weight copolymerized polyethylene, MFR:
7g / 10min)

Component (B) -7: Polybutyl acrylate methyl methacrylate copolymer graft of ethylene ethyl acrylate copolymer (modipa A5300 manufactured by NOF Corporation, 100 parts by weight of ethyl acrylate 20% by weight copolymerized polyethylene) , 43 parts by weight of polybutyl acrylate and methyl methacrylate graft polymerized)

Component (B) -8: Maleic acid-modified hydrogenated styrene-butadiene block copolymer (Tuftec M1943, manufactured by Asahi Kasei Corporation, maleic anhydride 2% by weight grafted hydrogenated styrene-butadiene block copolymer)

Component (C): rubber-like elastic material Component (C) -1: number average molecular weight 75,000, molecular weight distribution 1.10, bound styrene content 20% by weight, 1,2- of the polybutadiene portion before hydrogenation A hydrogenated block copolymer of a styrene / butadiene block copolymer having a vinyl bond content of 38% by weight and a hydrogenation rate of the polybutadiene portion of 99% was synthesized by the method described in JP-A-60-220147.

Component (C) -2: number average molecular weight 150,0
00, molecular weight distribution 1.20, bound styrene content 32% by weight, 1,2-vinyl bond content of polybutadiene part before hydrogenation 38% by weight, hydrogenation rate of polybutadiene part 99
% Of a styrene / butadiene block copolymer was synthesized by the method described in JP-A-60-220147.

Component (C) -3: Ethylene / butene copolymer (Tuffmer P-028 manufactured by Mitsui Petrochemical Industries, Ltd.)
0, MFR; 5.0, density; 0.88)

Component (C) -4: a polyolefin-based elastomer comprising an ethylene / propylene copolymer and a polypropylene component (manufactured by Mitsubishi Chemical Corporation, Thermolan 360)
1, density: 0.88, JIS A hardness (JIS K63
01); 70)

Component (C) -5: number average molecular weight of 120,0
00, molecular weight distribution 1.20, bound styrene amount 35% by weight, polybutadiene portion before hydrogenation had a 1,2-vinyl bond amount of 35% by weight, and polybutadiene portion had a hydrogenation rate of 99.
% Of a styrene / butadiene block copolymer was synthesized by the method described in JP-A-60-220147.

Examples 1 to 11 As thermoplastic polyester elastomers (A) -1,
Using (A) -2 and (B)-as a modified olefin resin
1, (B) -2, and (C)-as a rubbery elastic body
1, (C) -2, (C) -3, and (C) -4 were blended with a Henschel mixer at the respective ratios shown in Tables 1, 2, and 3, and then biaxially extruded in the same direction at a diameter of 45 mm. 22 by machine
The mixture was melt-kneaded at 0 ° C. to obtain pellets of the elastomer composition. Tables 1 and 2 show the results of physical properties and molding processability.
3 is shown.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

Comparative Examples 1 to 4 Using (A) -1 as the thermoplastic polyester elastomer, (B) -1 as the modified olefin resin and (C) -1 as the rubber-like elastic material, the ratios shown in Table 4 were used. At
Kneading and evaluation were performed in the same manner as in Example 1. The results are shown in Table 4. From this result, it is clear that the composition outside the range of the present invention has any bad physical properties.

[0105]

[Table 4]

Examples 13 to 15 (A) -1 was used as a thermoplastic polyester elastomer, (B) -1 was used as a modified olefin resin, (C) -2 was used as a rubbery elastic material, and polypropylene (Japanese) was used. Polyolefine Co., Ltd., block type PP, MK711, MFR; 30) and hydrocarbon oil (Idemitsu Kosan Co., Ltd., Diana Process Oil PW380) were added, and the mixture was mixed with a Henschel mixer at each ratio shown in Table 5. After blending, the mixture was mixed with a 45 mm diameter
The mixture was melt-kneaded at 0 ° C. to obtain pellets of the elastomer composition. Table 5 shows the results of the physical properties and the molding processability.

[0107]

[Table 5]

Examples 16 to 30 (A) -3 as a thermoplastic polyester elastomer
Using (A) -4 and (B)-as a modified olefin resin
2, (B) -3, (B) -4, and (B) -5, and (C) -5 as a rubber-like elastic body.
Was blended with a Henschel mixer at the respective ratios shown in Table 1, and then melt-kneaded at 200 ° C. with a 45 mm-diameter twin screw extruder to obtain pellets of the elastomer composition. The results of the physical properties are shown in Tables 6, 7 and 8.

[0109]

[Table 6]

[0110]

[Table 7]

[0111]

[Table 8]

Comparative Examples 5 to 9 (A) -3 was used as the thermoplastic polyester elastomer, and (B) -6 and (B)-were used as the modified olefin resins.
7, (B) -8, and (C) -5 as a rubbery elastic body
And kneaded at the respective ratios shown in Table 9 in the same manner as in the methods of Examples 15 to 29, and evaluated. The results are shown in Table 9. From this result, it is clear that the composition outside the range of the present invention has any bad physical properties.

[0113]

[Table 9]

[0114]

The thermoplastic elastomer composition obtained according to the present invention has scratch resistance, strength, heat resistance, oil resistance,
Because of its excellent flexibility and moldability, it can be suitably used in the fields of automobile parts, home appliance parts, toys, miscellaneous goods, etc., but instrument panels, armrests, and handles that require a product appearance because of their particularly excellent scratch resistance It can be suitably used for interior parts of automobiles such as horn pads and interior and exterior parts of automobiles such as window moldings and bumpers. Further, since the surface of the molded article is excellent in scratch resistance and molding workability, the coating step which has been conventionally required can be eliminated, so that high productivity and low cost can be realized.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 67/02 C08L 67/02

Claims (8)

[Claims] 1. A thermoplastic elastomer composition comprising the following components (A), (B) and (C). (A) Thermoplastic polyester elastomer: 100 parts by weight (B) Modified olefin resin having an epoxy group or its derivative group in the molecule: 3 to 100 parts by weight (C) Group consisting of olefin-based and / or styrene-based thermoplastic elastomer Rubber-like elastic material selected from: 1
0 to 900 parts by weight 2. The elastomer composition according to claim 1, wherein the modified olefin resin is an olefin resin obtained by copolymerizing or grafting glycidyl methacrylate. 3. The thermoplastic elastomer composition according to claim 1, wherein the styrene-based thermoplastic elastomer is a hydrogenated styrene-based thermoplastic elastomer. 4. The thermoplastic elastomer composition according to claim 3, wherein the hydrogenated styrene-based thermoplastic elastomer is a hydrogenated block copolymer obtained by hydrogenating styrene and a diene block copolymer. 5. The thermoplastic elastomer composition according to claim 1, wherein the olefin-based thermoplastic elastomer is an ethylene-α-olefin copolymer. 6. The heat according to claim 1, wherein the thermoplastic polyester elastomer is a block copolymer of the following (a) a short-chain dicarboxylic acid component, (b) a short-chain diol component, and (c) a long-chain diol component. Plastic elastomer composition. (A) a dicarboxylic acid component wherein the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and / or an ester-forming derivative thereof; (b) a short-chain diol component is an aliphatic diol; and (c) a long-chain diol component is the following formula (1). A polyether glycol having a tetramethylene oxide structural unit represented by the following formula, both terminals of which are alcoholic hydroxyl groups, and having a number average molecular weight of 400 to 6,000. 7. A long chain diol component (c) having a tetramethylene oxide structural unit represented by the following formula (1) (hereinafter abbreviated as T):
And a neopentylene oxide structural unit (hereinafter abbreviated as N) represented by the following formula (2), wherein the ratio of N is 5 to 50 mol%
The thermoplastic elastomer composition according to claim 6, wherein the polyether is a polyether glycol having alcoholic hydroxyl groups at both ends and a number average molecular weight of 400 to 6,000. Embedded image 8. The component (A) is a continuous phase, and (C)
The thermoplastic elastomer composition according to claim 1, wherein the component has a sea-island structure in which the component has an average particle size of 1.4 µm or less and is dispersed in the component (A).