JPH07247406A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer composition which comprises a specific polyether-ester block copolymer and a specific block copolymer, thus is useful for hoses and car interior or exterior articles because it is excellent in balance between moldability, weather resistance, low-temperature properties, mechanical strength and oil resistance. CONSTITUTION:This elastomer composition comprises (a) 5-95wt.% of a polyether-ester block copolymer which is prepared by copolymerization of (i) the dicarboxylic acid component as the short-chain dicarboxylic acid component of an aromatic dicarboxylic acid with the polyether glycol prepared by copolymerization of (ii) an aliphatic diol as the short-chain diol, (iii) the neopentyloxy structural units of formula I and (iv) the tetramethyleneoxy structural units of formula II as the long-chain diol components where the proportion of N is 5 to 100 mole %, both of the chain terminals are alcoholic hydroxy groups and the number-average molecular weight is 400 to 6,000 and (b) 95-5wt.% of a block copolymer which is composed of 2 or more blocks A of vinyl aromatic compound and block B of a terminal olefinic compound of 20% unsaturation and the content of the block A is 10-90wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic elastomer composition having excellent moldability, heat resistance, weather resistance, low temperature characteristics, mechanical strength and oil resistance. More specifically, the present invention provides
Copolymerization of aromatic dicarboxylic acid and its ester-forming derivative, dicarboxylic acid component, aliphatic diol and its ester-forming derivative, short-chain diol component, and polyether glycol having a special structure The present invention relates to a thermoplastic elastomer composition containing the novel polyester ester elastomer obtained by the above method and a styrenic saturated thermoplastic elastomer.

[0002]

2. Description of the Related Art Polyester ester block copolymers having a polybutylene terephthalate as a hard segment and a polyether glycol as a soft segment are mainly used for mechanical strength, heat resistance, impact resilience and abrasion resistance. As a polyester elastomer having rubber-like elasticity with excellent oil resistance, its application is expanding to electric / electronic parts, automobile parts, fibers, films, etc., and the market expansion is large among the thermoplastic elastomers.

However, such a polyester ester elastomer is inferior in hot water resistance because it has an ester bond in the main chain, and may not have sufficient weather resistance because it has an ether bond. Further, if the hard / soft ratio in the polyester ester elastomer is high, the flexibility is poor. Therefore, if the softness is increased to give the flexibility, oil resistance, heat resistance, weather resistance, mechanical properties, etc. There was a problem of decrease.

On the other hand, styrene-based thermoplastic elastomers are expanding their applications as elastomers that do not require vulcanization. Among them, styrene-based saturated thermoplastic elastomers, particularly at least two vinyl aromatic compound block A. And a block copolymer composed of at least one olefin compound block B having an unsaturation degree of not more than 20%,
Since the main chain / side chain has carbon / carbon unsaturated double bonds saturated by hydrogenation, it has excellent heat resistance, weather resistance, and rubber properties, and is used for various purposes.

However, on the other hand, there was a problem that the oil resistance, molding processability, high temperature mechanical properties, etc. were poor. Therefore, blend oil-resistant plastics such as polypropylene and polyphenylene ether to improve the oil resistance and molding processability of the styrene-based thermoplastic elastomer, and add paraffin oil etc. to adjust the hardness. It is generally widely practiced.

However, since the plastic having a relatively high glass transition temperature is basically blended with the elastomer, the low temperature performance inherent in the styrene thermoplastic elastomer is largely lost. In addition, some attempts have been made to combine the advantages of each other by melt-blending a polyester ester elastomer and a styrene thermoplastic elastomer. For example, a method of blending a styrene-based diene type block copolymer with a polyester elastomer (Japanese Patent Laid-Open No. 50-82162) or a hydrogenated diene-based copolymer (in order to improve its weather resistance and heat aging resistance) A method of blending a styrene-saturated thermoplastic elastomer containing (JP-A-3-43433, JP-A-4-108838, and JP-A-4-323).
No. 250) has already been published.

The soft segment of the polyetherester elastomer used in these compositions is usually poly (tetramethyleneoxy) glycol. Poly (tetramethyleneoxy) glycol is most commonly used because it has an excellent balance of physical properties when used as a polyester elastomer, but due to its linear structure, it causes crystallization in the low temperature region, At 0 ° C or lower, rubber properties become insufficient.

Further, conventionally known poly (ethyleneoxy) glycol, poly (propyleneoxy) glycol, and block polymers of poly (ethyleneoxy) glycol and poly (propyleneoxy) glycol. When-is a soft segment of a polyester ester elastomer, rubber properties, water resistance, heat resistance and weather resistance are inferior. Therefore, in order to impart low temperature rubber properties, water resistance and weather resistance by blending these known polyether ester elastomers with a styrene saturated thermoplastic elastomer, a relatively large amount of styrene saturated thermoplastic elastomer is required. It was necessary to blend elastomers and add plasticizers. Therefore, there is a problem that the oil resistance, high temperature mechanical strength, and abrasion resistance originally possessed by the polyester ester elastomer are sacrificed or the effect is not sufficient.

By the way, the inventors of the present invention have used a soft segment component, polyether glycol, as a neopentylene oxide structural unit (hereinafter abbreviated as N) represented by the following formula (1):
(4) A tetramethyleneoxy structural unit (hereinafter abbreviated as T) shown in (2), in which the N ratio is 5 to 100 mol%, and both terminals are alcoholic hydroxyl groups, and the number average is Polyethylene having a molecular weight of 400 to 6,000
It has been found that a novel polyester ester elastomer can be obtained by using terglycol, and a patent application has already been made (Japanese Patent Application Nos. 4-238701 and 4-4).
-23706).

[0010]

[Chemical 3]

[Chemical 4]

[0011]

DISCLOSURE OF THE INVENTION According to the present invention, the polyether ester elastomer having this specific structure is melt-blended with a styrene-saturated thermoplastic elastomer at a specific ratio to provide flexibility, moldability and weather resistance. It is an object of the present invention to provide a thermoplastic elastomer composition having an excellent balance of properties such as properties, mechanical strength and oil resistance, and having heat resistance and low temperature performance.

[0012]

The inventors of the present invention have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention includes: (A) (a-1) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and an ester-forming derivative thereof, and (a-2) a short-chain diol component is a fat. Tribe Geo-
And a short-chain diol component which is an ester-forming derivative thereof and (a-3) a long-chain diol component are N represented by the following formula (1).
And T represented by the following formula (2), wherein the ratio of N is 5 to 100 mol%, both ends are alcoholic hydroxyl groups, and the number average molecular weight is 400 to 6,000. 5 to 95% by weight of a poly (ether ester) block copolymer obtained by copolymerizing the above-mentioned poly (ether glycol) with (B) at least two vinyl aromatic compound blocks A
And a block copolymer 95 containing at least one olefin compound block B having an unsaturation degree not exceeding 20% and having a vinyl aromatic compound content of 10 to 90% by weight.
To provide a thermoplastic elastomer composition comprising from about 5% by weight.

[0013]

[Chemical 5]

[Chemical 6]

The present invention will be described in detail below. (A) Polyester ester block copolymer: (a-1) Short chain dicarboxylic acid component: As the aromatic dicarboxylic acid and its ester-forming derivative used for the polymerization of the polyetherester elastomer used in the present invention, ,
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 ester-forming derivatives thereof can be mentioned.

Further, alicyclic and aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid, and dimer acid, and ester-forming derivatives thereof can be used. You may use. These may be used alone or in combination of two or more. Preferable are terephthalic acid, isophthalic acid and naphthalene-2,6-dicarboxylic acid.

(A-2) Short-chain diol component As the aliphatic diol and its ester-forming derivative, diol having a molecular weight of 300 or less is usually used. For example, ethylene glycol, 1,3-propylene diol, 1,4-butane diol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, and these Examples thereof include ester-forming derivatives.

Further, 1,1-cyclohexanedimethano-
Alicyclic diols such as 1,4-cyclohexane dimethanol and tricyclodecane dimethanol, and ester-forming derivatives thereof; 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, and ester-forming derivatives thereof.
Suitably, ethylene glycol and 1,4-butanedio-
And ester-forming derivatives thereof.

A combination of the aromatic dicarboxylic acid and the ester-forming derivative (a-1) thereof with the aliphatic diol and the ester-forming derivative (a-2) thereof can be used as a polyether ester elastomer. A segmented or short chain polyester is constructed. A preferred combination is a combination of terephthalic acid or a terephthalic acid diester and ethylene glycol or 1,4-butanediol (polyethylene terephthalate, polybutylene terephthalate). More preferably, polybutylene terephthalate is used as the hard segment.

The reason for this is that polybutylene terephthalate has a large crystallization rate and excellent moldability, and even when it is used as a polyester ester elastomer, it has rubber elasticity, mechanical properties, heat resistance, chemical resistance and the like. Due to the well-balanced physical properties. It is also possible to use another dicarboxylic acid and its ester-forming derivative within 15 mol%, or another diol and its ester-forming derivative within 15 mol% to this combination.

(A-3) Long-chain diol component Polyether ester elastomer used in the present invention
The soft segment, that is, the polyether glycol constituting the long-chain polyester is composed of N represented by the formula (1) and T represented by the formula (2), and the proportion of N is 5 to 100 mol%. Where the both ends are alcoholic hydroxyl groups and the number average molecular weight is 400 to 6,000.
It is terglycol.

[0021] Preferably, for the N which is not at the end of the polyether glycol, the structural units adjacent to each other with N in between are always T, and when N is at the end, it has an alcohol at the end. -N having a hydroxyl group bonded to it has a structure in which the structural unit adjacent to N on the opposite side of the alcoholic hydroxyl group is always T, and N is 5 to 50 mol%.
Polyether glycol. This means that there is virtually no NN linkage.

Polyether glycols used in the production of the polyetherester elastomers used in the present invention.
Is a homocationic polymerization of 3,3-dimethyloxetane (3,3-DMO), a cationic copolymerization of 3,3-DMO and neopentyl glycol (NPG), 3,3-DMO.
And tetrahydrofuran (THF) cationic copolymerization,
Cationic terpolymerization of 3,3-DMO, NPG, and THF or pure tetramethylene glycol in the presence of a catalyst that is active in the presence of alcoholic hydroxyl groups using neopentyl glycol and tetrahydrofuran as raw materials. Can be produced under the reaction conditions in which the depolymerization of 1 proceeds.

A preferred embodiment of the polyether glycol used in the production of the polyester elastomer used in the present invention is Japanese Patent Application No. 4-238701 and Japanese Patent Application No. 4-2.
As described in No. 38706, the structural units adjacent to each other with N in between are always T, or when N is at the terminal, one of them is an alcoholic hydroxyl group, so the number of moles of N is always 50 mol. % Or less. In a copolymer composition in which N in the polyether glycol is less than 5 mol%, when this is used as a polyester ester elastomer, it may not be possible to obtain satisfactory physical properties particularly at low temperature performance, which is not preferable. .

When the content of the long-chain polyester of the polyester ester elastomer, that is, the soft segment is relatively small (10 to 50 wt%), the content of N in the polyether glycol is about 15 to 50 mol%. From the standpoint of performance, a large amount is preferable. On the other hand, when the content of the soft segment is relatively large (50 to 90 wt%), physical properties such as low temperature performance are sufficiently good even if the N content is as low as about 5 to 15 mol%.

The preferred method for producing the polyether glycol used for producing the polyether ester elastomer used in the present invention is to prepare a large amount 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 neopentyl glycol is charged and the depolymerization of pure tetramethylene glycol proceeds and a low THF concentration, that is, a high polymer concentration.

Heteropolyacids described in JP-A-60-20366 and salts of heteropolyacids are described in JP-A-61-2120830 as catalysts which are active in the presence of alcoholic hydroxyl groups. Can use these. At this time, the requirement that the molar ratio of water or diol to the catalyst is 10 or less is not necessary under the reaction conditions for providing the polyether glycol of the present invention. The catalyst showing activity in the presence of the alcoholic hydroxyl group is not particularly limited to the heteropolyacid, and benzenesulfonic acid, toluenesulfonic acid and the like can be used.

The copolymerization ratio of neopentyl glycol can be increased in a special reaction condition process which gives the preferred polyether glycol used in the preparation of the polyetherester elastomer used in the present invention. The reason is that even if the molar ratio of diol to the catalyst is 30, the polymerization can proceed, so that a large amount of neopentyl glycol can be charged.

Further, formation of a polymer molecular chain in which only THF is continuous is suppressed because the polymerization proceeds under the depolymerization conditions of pure poly (tetramethyleneoxy) glycol. In the preferred polyether glycol used in the present invention, the copolymerization ratio of neopentyl glycol is 50 mol% or less because the structure in which N and N are directly linked is ¹³ C-NMR.
It can be proved that the copolymerization ratio of neopentyl glycol does not exceed 50 percent. In addition, in order to set N to 50 mol% or more, 3,3-dimethyloxetane obtained by cyclizing neopentyl glycol may be used as a starting material.

The necessary requirements for preferably producing the polyether glycol used in the polyether ester elastomer used in the present invention are summarized into three requirements. First, the activity is exhibited in the presence of an alcoholic hydroxyl group. The use of a catalyst such as heteropoly acid or sulfonic acid, secondly the use of glycol as a copolymer glycol to prevent the propagation of depolymerization, that is, NPG, and thirdly, the copolymerization ratio becomes high. Pure PTMG in order to make polycondensation the main reaction
The reaction is proceeded at the temperature and the polymer concentration at which the depolymerization proceeds.

In order to proceed the polycondensation reaction at a preferable rate, the reaction temperature is 70 ° C. or higher, preferably 75 ° C. or higher. However, if the reaction temperature is raised too high, the reaction solution and the catalyst become strongly colored, which is not preferable. For example, when phosphotungstic acid is used as a catalyst, the coloring is usually severe when the temperature exceeds 110 ° C. The catalysts used in the present invention have been mentioned above. Among them, preferred catalysts include phosphotungstic acid, which is commercially available, has good stability at high temperatures, and has high reaction activity.

When a heteropolyacid such as phosphotungstic acid is used as a catalyst, the reaction solution is separated into a catalyst layer having a high catalyst concentration and a liquid layer containing the catalyst at a low efficiency of 1% or less as the reaction progresses. , The reaction is carried out in a two-layer dispersed state. If the stirring is stopped at the end of the reaction and the reaction is allowed to stand,
The heavy catalyst layer is divided into the lower part and the light liquid layer is divided into the upper part. The upper liquid layer is taken out, and THF, the oligomer and the dissolved catalyst are removed to obtain the target polymer. NPG and THF are newly supplied to the catalyst layer left below to start a new batch reaction. In this way, the present invention can be carried out 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, is preferable because the catalyst can be easily separated.

With respect to the amount of NPG charged relative to the amount of phosphotungstic acid or sulfonic acid used as a catalyst, it is suitable to charge 2 to 10 mol of NPG per equivalent of the catalyst. If the amount of NPG is small, the amount of polymer to be collected at the end of the reaction will be small, and if the amount of NPG is large, the polycondensation reaction will be slow and it will take a long time for the polymerization degree of the polymer to increase.

Water produced by polycondensation can be taken out and removed as vapor phase water 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 the water is removed, THF is also taken out, and it is necessary to replenish a large amount of fresh THF.

Since it is necessary to take out the gas phase of the reaction system in this way, the reaction liquid has a boiling temperature. To control the boiling temperature, that is, the reaction temperature to a predetermined level, it is easy to control the concentration of THF. As a specific operation, if the replenishment rate of THF is controlled so as to keep the liquid temperature at a predetermined level, the THF taken out together with water in the gas phase, the compositional change accompanying the progress of the reaction, and the TH caused by the polymerization
The consumption of F, the standard operation that can cope with all these changes, T
You have decided on HF.

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

The polyester glycol used in the production of the polyester elastomer used in the present invention has a number average molecular weight of 400 to 6,000. Four
If it is less than 00, the average chain length of the short-chain polyester (hard segment) usually becomes small, though it depends on the hard / soft ratio of the final polyether ester to be polymerized, and the melting point drops drastically, resulting in heat resistance. Since it is inferior, it is not preferable both when it is used as a material as a polyester elastomer as it is and when it is used as a composition. On the other hand, if it exceeds 6,000, the concentration of the terminal group in the polyether glycol per unit weight becomes low, and the polymerization becomes difficult, which is not preferable.

Considering the balance between the easiness of polymerization and the melting point, the number average molecular weight is preferably 800 to 4,000,
1,000 to 2,500 is more preferable. This number average molecular weight is measured by various methods such as GPC method. In the present invention, the terminal is acetylated with acetic anhydride, unreacted acetic anhydride is decomposed into acetic acid, and then back titration with an alkali (end group titration). Method) to obtain the hydroxyl value.

(A-4) Manufacturing conditions of the polyetherester block copolymer, etc .: All the polyetherglycol units (soft segment) occupying the entire polyetherester block copolymer (polyester ester elastomer) The amount of) is 5 to 90% by weight, and this value depends on the required physical properties of the final composition of the polyether ester elastomer and the styrenic saturated thermoplastic elastomer. In this case, the amount of the polyether glycol unit is the weight ratio of the soft segment, not the weight ratio of the charged polyether glycol in all the monomers.

Generally, the hard segment of the polyether ester elastomer is a short chain ester and the soft segment is a long chain ester, but the end of the polyether portion is linked to the dicarboxylic acid component by an ester bond. ,
It is connected to the hard segment. For convenience, a soft segment was a unit including a unit constituting an ester bond at one end of the polyether portion.

That is, in the case of the well-known polyester ether elastomer (hard segment: polybutylene terephthalate, soft segment: poly (tetramethyleneoxy) glycol) Formula (3)
Hard segment and soft segment are defined as shown in (4).

[0041]

[Chemical 7]

The ratio of this hard / soft segment is ¹
It can be accurately quantified by 1 H-NMR. When the amount of the soft segment is less than 5% by weight, the softness is poor, and satisfactory physical properties as an elastomer cannot be expected. Further, when this amount exceeds 90% by weight, the softness is considerably imparted, but at the same time, the average chain length of the hard segments is shortened, and the hard block which is a physical cross-linking point can resist external force. Without this, the mechanical strength is remarkably reduced and the composition cannot be supplemented. Moreover, since the melting point is considerably lowered, the heat resistance is also inferior, which is not preferable. A more preferred amount of soft segment is 25 to 75% by weight.

Polyether ester elastomer is used as a styrene saturated thermoplastic elastomer having a relatively large amount of vinyl aromatic compound bound (the amount of bound vinyl aromatic compound is 40%).
When the composition is about 1% by weight or more), it is preferable to use the above-mentioned polyester ester elastomer containing 50% by weight or more of the soft segment component.

The polyester ester elastomer obtained by polymerizing the components (a-1) to (a-3) can be produced by a known method. For example, a method of subjecting a lower alcohol diester of dicarboxylic acid, an excess amount of a low molecular weight glycol and an ether glycol to a transesterification reaction in the presence of a catalyst, and subsequently subjecting the resulting reaction product to polycondensation under reduced pressure, or A method in which a dicarboxylic acid is subjected to an esterification reaction of glycol and polyether glycol in the presence of a catalyst and then the resulting product is polycondensed, or a short-chain polyester (for example, polybutylene terephthalate) is prepared in advance. Then, any method such as a method of adding other dicarboxylic acid, diol or polyether glycol to this, or a method of adding other copolymerized polyester and randomizing by transesterification may be used.

As a catalyst common to the transesterification reaction or the esterification reaction and the polycondensation reaction, tetra (isopropoxy) titanate, tetraalkyl titanate typified by tetra (n-butoxy) titanate, Reaction products of these tetraalkyl titanates and alkylene glycols, partial hydrolysates of tetraalkyl titanates, metal salts of titanium hexaalkoxides, metal salts of titanium hexaalkoxides, of titanium Carboxylate,
Ti-based catalysts such as titanyl compounds are preferred.

Further, mono-alkyltin compounds such as mono-n-butylmonohydroxytin oxide, mono-n-butyltin triacetate, mono-n-butyltin monooctylate and mono-n-butyltin monoacetate; di-n -Butyltin oxide, di-n-butyltin diacetate,
Diphenyltin oxide, diphenyltin diacetate
And dialkyl (or diaryl) tin compounds such as di-n-butyltin dioctylate and the like.

In addition to these, 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. Particularly, when used alone, tetraalkyl titanate or antimony trioxide is preferable, and when used in combination, a combination of tetraalkyl titanate and magnesium acetate is preferable. The addition amount of the esterification or polycondensation catalyst is preferably 0.005 to 0.5% by weight, more preferably 0.03 to 0.2% by weight, based on the produced polymer. These catalysts may or may not be added again during the polycondensation reaction after being added at the start of transesterification or esterification reaction.

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

Further, if necessary, the polyether glycol used in the present invention may be partially substituted with other polyether glycol. As the polyether glycol used for such substitution, poly (ethyleneoxy) glycol, poly (propyleneoxy) glycol, poly (tetramethyleneoxy) glycol, poly (1,2-propyleneoxy) Glycol, block copolymer or random copolymer of ethylene oxide and propylene oxide, random copolymer of THF and 3-methyl THF, block copolymer or random copolymer of ethylene oxide and THF, poly (2-methyl-1,3-propylene) (Oxy) glycol, poly (propyleneoxy) diimidic diacid and the like can be mentioned.

The number average molecular weight of the polyether glycol used for these substitutions is 400 to 6,000, preferably 1,000 to 3,000. Preferred substituted polyether glycols include poly (tetramethyleneoxy) glycol. When poly (tetramethyleneoxy) glycol is used for substitution and the number average molecular weight (Mn) exceeds 1800, the molecular weight distribution [Mv / Mn: Mn is the number average molecular weight determined from the terminal hydroxyl group value, Mv Is the equation Mv = antilog (0.493lo
The viscosity average molecular weight is defined by gη + 3.0646). However, η may cause unfavorable results in low temperature performance due to crystallization depending on the melt viscosity at a temperature of 40 ° C represented by Poise].

The value of this molecular weight distribution (Mv / Mn) is 1.
It is preferable to use a narrow one of 6 or less. More preferably, it is 1.5 or less. However, the substituted polyether glycol is preferably used within the range of 90% by weight or less of the polyether glycol used in the present invention. When this value exceeds 90% by weight, although depending on the content of neopentyl oxide unit in the polyether glycol used in the present invention, generally satisfactory results are obtained in physical properties such as water resistance and low temperature performance. It may not be available, so it is necessary to select it according to the application.

The polymerization degree of the thus-polymerized polyester ester elastomer is generally expressed by relative solution viscosity (η _rel ) or intrinsic viscosity ([η]) and melt flow rate (MFR). In the present invention, it is expressed by MFR. In the present invention, the MFR of the polyether ester elastomer is 0.1 to 30 g / 10 minutes (load 2.16).
kg, 230 ° C .: hereinafter L condition), a high molecular weight polyether ester elastomer is obtained.

Polyester ester elastomers having an MFR of 30 or less have a good influence on the physical properties, particularly mechanical strength and flex fatigue resistance. When the MFR exceeds 30, the molecular weight is not sufficiently increased, and thus the mechanical properties (breaking strength, breaking elongation, etc.), flexural wear resistance, c-set, etc. are poor, so that the use is limited. Further, when the MFR is less than 0.1, these physical properties are good, but the melt viscosity is too high and it is difficult to dispense from the reactor, which is not realistic. Considering the balance between mechanical properties and the ease of paying out from the reactor, a more preferable MFR is 5 to 25 under the L condition.
g / 10 minutes.

The antioxidant may be added at any time during or after the production of the polyetherester elastomer, but especially at the time when the polyetherglycol is exposed to high temperatures, for example in the polycondensation reaction. At this point, in order to prevent the oxidative deterioration of the polyether glycol, it is desirable to add an antioxidant that does not hinder the polycondensation reaction and does not impair the function of the catalyst.

These antioxidants include phosphoric acid, phosphorous acid, aliphatic, aromatic or alkyl group-substituted aromatic esters and hypophosphorous acid derivatives; phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonone.
Dialkyl pentaerythritol diphosphite,
Phosphorus compounds such as dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds, thioether compounds, dithioate compounds, mercaptobenzimidazole compounds, thiocarbanilide compounds, thiodipropionic acid Compounds containing sulfur such as esters;
And tin-based compounds such as dibutyltin monoxide can be used. These may be used alone or in combination of two or more. The amount of these stabilizers added is 100 parts by weight of the polyether ester elastomer,
0.01 to 2 parts by weight is desirable.

If necessary, an ultraviolet absorber / light stabilizer may be added in the same manner. Examples of these ultraviolet absorbers include benzotriazole-based and benzophenone-based compounds. A radical scavenging light stabilizer such as a hindered amine compound is preferably used as the light stabilizer.

(B) Styrene-based saturated type (partially hydrogenated block copolymer) thermoplastic elastomer: The styrene-based saturated thermoplastic elastomer which is the component (B) of the present invention is a styrene-based diene type block copolymer. It is produced by hydrogenating the diene block of. The block copolymer of the styrene-saturated thermoplastic elastomer before hydrogenation is at least two vinyl aromatic compound polymer blocks,
At least one polymer block containing a conjugated diene as a main component
It contains one.

In the polymer block containing a conjugated diene as the main component, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 50/50, preferably 0/10.
It is a polymer block having a composition range of 0 to 40/60, and the distribution of vinyl aromatic compounds in this block is random, taper (monomer component increases or decreases along the molecular chain), one It may be in the form of a partial block or any combination thereof.

In the block copolymer before hydrogenation according to the present invention, 50 vinyl aromatic compounds are present in the transition portion between the vinyl aromatic compound polymer block and the polymer block mainly containing the conjugated diene compound. Although a copolymer portion of the vinyl aromatic compound and the conjugated diene compound may be present in an amount of more than 5% by weight, such a polymer portion is included in the polymer block containing the conjugated diene compound as a main component. In the above block copolymer, the weight ratio of the content of the vinyl aromatic compound and the content of the conjugated diene compound is
10/90 to 90/10, 20/80 to 85/1
A range of 5 is preferred.

As the vinyl aromatic compound constituting the block copolymer before hydrogenation, one or two of styrene, α-methylstyrene, p-methylstyrene and the like can be used.
One or more kinds are selected, and styrene is particularly preferable. As the conjugated diene compound, one kind or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene and the like, and among them, butadiene and / or isoprene are particularly preferable.

The above block copolymer has a number average molecular weight in the range of 20,000 to 500,000 and a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of 1.05.
A range of 10 is preferred. The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 1,2-vinyl bonds in the microstructure of the butadiene portion is preferably in the range of 10 to 80% in the total polybutadiene. When it is necessary for the hydrogenated block copolymer to have rubber elasticity, the 1,2-vinyl bond content is particularly preferably 25 to 55% of the total polybutadiene.

When the block copolymer contains two or more blocks mainly composed of a vinyl aromatic compound, the blocks may have the same structure, the content of the monomer component, and the molecules thereof. Each structure such as distribution in chain, molecular weight of block, and microstructure may be different. The above block copolymer is usually benzene,
It can be obtained by living anionic polymerization of a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as toluene, hexane or cyclohexane using an organolithium compound such as n-butyllithium as a catalyst.

Further, the block copolymer having a lithium active terminal obtained by the above method is subjected to a coupling reaction with a polyfunctional coupling agent such as carbon tetrachloride or silicon tetrachloride to give a branched or radial block copolymer. It is also possible to combine them. Further, the block copolymer can be used not only as one type but also as a mixture of two or more types.

By hydrogenating the above block copolymer by a known method, for example, the method described in Japanese Patent Publication No. 2-9041 to 9043, the aromatic double bond of the vinyl aromatic compound block A is substantially converted. Hydrogenated block copolymers can be synthesized in which at least 80% of the carbon / carbon unsaturated double bonds of the conjugated diene block are hydrogenated without hydrogenation. If the hydrogenation rate of the carbon / carbon unsaturated double bond in the conjugated diene block portion of the hydrogenated block copolymer is less than 80%, gelation, molecular chain breakage, etc. during melt kneading with the polyester elastomer will occur. Undesirable side reactions occur, and the heat aging resistance and weather resistance of the final thermoplastic elastomer composition are also insufficient, which is not preferable. Preferred hydrogenation rate is 9
It is 0% or more, more preferably 95% or more.

The residue of the polymerization and / or hydrogenation catalyst contained in the hydrogenated block copolymer is preferably removed by a treatment such as deashing. Depending on the metal species, it is 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less.

(C) Thermoplastic Elastomer Composition: In obtaining the thermoplastic elastomer composition of the present invention,
In order to improve the compatibility and dispersibility when blending with the component (A) polyetherester elastomer, the component (B) styrene-saturated thermoplastic elastomer is an acid anhydride group, a carboxyl group, An unsaturated compound having at least one functional group selected from a hydroxyl group, an amino group, an epoxy group, an oxazoline group, an imide group, an isocyanate group, a sulfonyl group and a sulfonate group was grafted or post-reacted. A modified styrenic saturated thermoplastic elastomer may be used.

Of these, styrene-saturated thermoplastic elastomers modified with unsaturated carboxylic acids and their derivatives are most preferable in view of performance. An example of producing the modified styrenic saturated thermoplastic elastomer will be described below. The block copolymer to be modified has no carbon / carbon unsaturated double bond at all, or the degree of unsaturation is 10% or less, the hydrogenation rate is 90% or more, preferably 3% or less, and the hydrogenation rate is 97% or more. In some cases, it can be obtained by radical addition in the presence of a commonly used radical initiator when modifying with a compound described below.

The method for producing these modified elastomers is not particularly limited in the present invention, but the obtained modified elastomer contains an unfavorable component such as gel,
A production method in which the melt viscosity is remarkably increased and the workability is extremely deteriorated is not preferable. As a preferable production method, for example, there is a method of reacting an unmodified hydrogenated block copolymer with an unsaturated carboxylic acid or a derivative thereof in the presence of an inert gas in an extruder, in the presence of a radical initiator. In addition, the unmodified hydrogenated block copolymer is toluene,
There is also used a method of dissolving in a solvent such as xylene and reacting with an unsaturated carboxylic acid or its derivative in the presence of a radical initiator. Unreacted unsaturated carboxylic acid or its derivative is preferably removed by an appropriate post-treatment such as vacuum degassing, extraction and precipitation.

When the hydrogenated block copolymer to be modified contains a large amount of carbon / carbon unsaturated double bonds in its molecule, or the degree of unsaturation exceeds 10% (hydrogenation rate is 90% or less).
In such cases, using the above method causes remarkable gelation,
It is not preferable because it deteriorates the physical properties of the final composition and the processability. In such a case, the modified elastomer is produced by heating and mixing the hydrogenated block copolymer and the unsaturated carboxylic acid or its derivative to "ene-react" with the carbon / carbon unsaturated double bond. At this time, if necessary, a stabilizer such as phenothiazine may coexist to prevent gelation due to heat.

The amount of the unsaturated carboxylic acid or its derivative bonded to the modified block copolymer is 0.05 to 5 parts by weight per 100 parts by weight of the block copolymer. Examples of the unsaturated carboxylic acid or its derivative used for modifying the styrene-saturated thermoplastic elastomer include maleic acid, maleic acid ester, maleic acid amide, maleic acid imide, maleic anhydride, fumaric acid, and fumaric acid ester. , Fumaric acid amide, fumaric acid imide, phthalic acid, itaconic acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, halogenated maleic acid ester, halogenated maleic acid amide, halogenated Maleic imide,
Acrylic acid, crotonic acid, methacrylic acid, cis-4-cyclohexane-1,2-dicarboxylic acid, its ester,
Its anhydrides, its amides, and its imides,

Endo-cis-bicyclo (2,2,1)-
5-heptene-2,3-dicarboxylic acid, its ester,
Its anhydride, its amide, and its imide, (meth)
Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate and (meth) acrylic acid amide. Maleic anhydride and glycidyl (meth) acrylate are particularly preferable.

In addition to these, a functional group-containing vinyl compound which is a non-unsaturated carboxylic acid compound such as vinyl glycidyl ether or vinyl oxazoline or a derivative thereof is also preferably used.
These modified styrenic saturated block copolymers are (B)
It is possible to replace all or part of the component styrenic saturated thermoplastic elastomer. In the melt-kneading process, the functional groups of the modified styrene block copolymer and the polyether ester block copolymer of the component (A) partially react to form a graft polymer, which is a polymer of both types.
It is thought that the compatibility of

The amount of the components (A) and (B) used in the present invention is (A) component / (B) component = 5 to 95/95 to 5% by weight, preferably 15 to 85/85. 15% by weight, more preferably 30 to 70/70 to 30% by weight
Is. If the amount of the component (A) used is less than 5% [the amount of the component (B) used exceeds 95% by weight], the oil resistance, moldability and mechanical strength of the resulting composition may be poor, which is not preferable. On the contrary, if the amount of the component (A) used exceeds 95% [the amount of the component (B) used is less than 5%], the composition obtained may be flexible depending on the weather resistance and the hard / soft segment ratio of the polyester elastomer. And the hot water resistance may be inferior, which is not preferable.

If necessary, a plasticizer may be added to the obtained composition. Examples of such plasticizers include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, Phthalates such as diisononyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris -Phosphoric acid esters such as chloroethyl phosphate and tris-dichloropropyl phosphate;

Trimellitic acid octyl ester, trimellitic acid isodecyl ester, trimellitic acid ester, dipentaerythritol ester, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, Fatty acid esters such as dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinocate; pyromellitic acid esters such as octyl pyromellitic acid ester, epoxidized soybean oil Epoxy plasticizers such as epoxidized linseed oil and epoxidized fatty acid alkyl ester; Polyether plasticizers such as adipic acid ether ester and polyether; Liquid rubbers such as liquid NBR, liquid acrylic rubber and liquid polybutadiene , Process oil and the like. These plasticizers can be used alone or in combination of two or more kinds. The amount of the plasticizer added is appropriately selected according to the required hardness and physical properties.
1 to 50 parts by weight is preferred per part by weight.

The thermoplastic elastomer composition of the present invention comprises:
Various extruders, Banbury mixers, kneaders, rolls,
Further, it can be obtained by melt-kneading with a combination of these. In the case of melt mixing with an extruder, the extrusion temperature may range from 120 ° C to 320 ° C and the residence time may range from 10 seconds to 150 minutes.
These processing conditions are appropriately selected depending on the ratio (a) / (b) and the addition amount of the plasticizer when added, and are not particularly limited.

Finally, existing antioxidants, light stabilizers and ultraviolet absorbers can be further added to the obtained composition, if necessary. Further, kaolin, silica, mica, titanium dioxide, alumina, calcium carbonate, calcium silicate, clay, kaolin, diatomaceous earth, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, in a range that does not impair the physical properties.
Fillers and reinforcing materials such as molybdenum disulfide, graphite, glass fiber and carbon fiber;

Lubricants or mold release agents such as zinc stearate and bisamide stearate: carbon black for coloring, ultramarine blue, titanium white, zinc white, red iron oxide, dark blue, azo pigments, nitro pigments, lake pigments. Dyes and pigments such as phthalocyanine pigments; flame retardants such as octabromodiphenyl and tetrabromobisphenol polycarbonate; foaming agents; thickeners such as epoxy compounds and isocyanate compounds; silicone oils and silicones Various known additives such as resin can be used.

The composition of the present invention also includes polypropylene, polyvinyl chloride, polycarbonate, PET, PB.
T, polyacetal, nylon 6, nylon 12, nylon 66, epoxy resin, vinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, PPS resin, polyethylene ether ketone, polyphenylene oxide,
Styrene-thermoplastic resin such as methyl (meth) acrylate resin; and other polyester elastomer (polyester ester elastomer, polyester ester elastomer), engineering elastomer such as polyamide elastomer, polyurethane elastomer, etc. It can be blended.

The addition amount of these thermoplastic resins and thermoplastic elastomers is 0 to 100 relative to 100 parts by weight of the total composition.
Parts by weight, preferably 0 to 50 parts by weight are selected. The thermoplastic elastomer composition of the present invention has an excellent balance of physical properties such as flexibility, moldability, weather resistance, mechanical strength and oil resistance, and also has heat resistance and low temperature performance, so that it is applied to various high-performance parts. obtain.

Applications of the thermoplastic elastomer composition of the present invention include airbag covers, instrument panel parts, bumper parts, side shields, joint boots, shift lever boots, handles, and moles. Auto parts, shoe soles,
Footwear such as skives and sandals, electric wire coating, connectors, electric parts such as cap plugs, hydraulic hoses, vacuum hoses, hoses for electric vacuum cleaners, coil tubes, garden hoes -Cubes or hoses such as laces, hot curlers, daily necessities such as hair brushes, materials such as O-rings, gaskets, packing rolls and the like are conceivable.

[0082]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited as long as its gist is not changed.
It is not limited to this. (Production Example 1) [Production Example of Soft Segment of Polyether Ester Elastomer (A)] Fractional distillation apparatus comprising one set such as fractionation tower, condenser, reflux valve, electromagnetic stirrer having anchor blades, and THF supply port 6.75 kg of neopentyl glycol and 19.5 kg of THF were charged into a reactor in which a lid of a stainless steel plate equipped with and a 200 liter stainless steel pot with a jacket through which a heat medium circulates are combined, and uniformly stirred. After dissolution, 45 kg of phosphotungstic acid hexahydrate is charged with stirring.

The temperature of the circulating heating medium is kept constant at 80 ° C., and the reaction start time is set when the temperature of the reaction liquid reaches 71 ° C. Thereafter, the temperature of the reaction liquid is controlled to 71 ° C. by supplying THF. After 40 minutes of reaction time, the temperature at the bottom of the fractionation tower was adjusted to about 6
Set to 9.5 ° C. and start distilling out hydrous THF. The water-containing THF in the lower part of the fractionating tower contained about 0.8% of water. The reaction is thus continued for 24 hours. The catalyst layer begins to separate from the middle of the reaction, changes into a dispersed state of droplets, and the viscosity increases. Stop stirring at the end of the reaction, and after 20 minutes,
Take out 83.3 kg of the upper liquid layer. About 30 l of catalyst layer remains.

As a result of analyzing 83.3 kg of the liquid layer taken out, it was found that the polymer contained 45% by weight and the catalyst contained 0.4% by weight as ash. Polymer, ie neopentyl glyco-
Poly Le copolymer (tetramethyleneoxy) glycolate - to quantify the hydroxyl value of Le, when determining the number-average molecular weight than this is 1,733, co of ¹ H-NMR from neopentylene oxide structural units (N) The polymerization ratio was 11 mol%.

(Production Example 2) [Synthesis of Polyether Ester Elastomer (A)] 1
Dimethyl terephthalate (manufactured by Mitsubishi Kasei Co., Ltd .; hereinafter the same) 1764 g, 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, same below) in a 5 liter reactor
1064 g, polyethylene glycol prepared in Preparation Example 1
3,000 g and Irganox 1010 (manufactured by Ciba-Geigy Co., Ltd.) were charged, and after nitrogen substitution, the temperature was raised to 200 ° C under a nitrogen atmosphere. Next, tetraisopropoxy titanate (Tokyo Kasei Co., Ltd., reagent first grade, the same applies hereinafter)
Was added. After holding for 30 minutes at the same temperature, the temperature was raised to 230 ° C., and the transesterification reaction was carried out for 2 hours at a stirring rotation speed of 150 rpm. The amount of methanol distilled out was 95% of the theoretical amount.

Then, the temperature was raised to 250 ° C., the pressure was reduced to 0.5 mmHg over 30 minutes at a stirring rotation speed of 50 rpm, and then the condensation reaction was carried out for about 4 hours until the torque did not increase. When it was extracted from the bottom of the reactor, a transparent viscous polymer was obtained. The elastomer obtained as pellets has an MFR of 24 and a ¹ H
The amount of soft segment determined from NMR was 60.4% by weight. The melting point of the obtained elastomer is 193 ° C.
(Peak temperature of DSC) and hardness (D) was 35.

Production Example 3 2469 g of dimethyl terephthalate charged in Production Example 2, 1,718 g of 1,4-butanediol, and 2,200 g of the polyether glycol obtained in Production Example 1 It carried out similarly except having used it. The condensation reaction time required until the torque did not increase was about 3 hours. The elastomer obtained had an MFR of 11 and a soft segment amount of 4 determined by ¹ H-NMR.
It was 4.7% by weight. The obtained elastomer had a melting point of 206 ° C. and a hardness (D) of 50.

The elastomers used in the examples and comparative examples of the present invention are shown below. (I) Polyether Ester Elastomer of Production Example 1; Hardness (D) = 35 Polyether Ester Elastomer of Production Example 2; Hardness (D) = 50 Hytrel 4767 manufactured by Toray DuPont; Hardness ( D) = 49 Toyobo Co., Ltd. Perprene P-40B; Hardness (D) = 30 (ii) Hydrogenated diene-based block copolymer Asahi Kasei Co., Ltd. Tuftec H-1041; Hardness (J
ISA) = 84 Asahi Kasei Corporation Tuftec M-1913 (acid-modified type); Hardness (JISA) = 84 Asahi Kasei Corporation Tuftec Z-513 (epoxy-modified type); Hardness (JISA) = 83

(Iii) Other Elastomers-Tafprene A (styrene / butadiene block copolymer) manufactured by Asahi Kasei Co., Ltd .; hardness (JISA) = 84 The evaluation items measured in Examples and Comparative Examples are as follows. explain. (A) (Hardness): Measured by Shore D hardness. (B) (MFR): Measured at 230 ° C. and a load of 2160 g. (C) (Tensile strength, elongation): JISK-6301 JI
A tensile test was conducted with a No. S3 dumbbell to record the tensile strength and the elongation.

(D) (10% modulus): JISK-
A tensile test was performed according to 6301 and the modulus at 10% elongation was recorded. (E) (Rigidity): According to JISK-6745, a Crush-Burg test was conducted to obtain the torsional rigidity. (F) (Needle penetration temperature): Weight 10g, temperature rising rate 5 ° C /
The temperature at which the detection rod (0.5φ) penetrated 0.1 mm was recorded when the TMA measurement was performed with a sample thickness of 2 mm.

(G) (Decomposition temperature): When DTA / TG measurement was carried out at a heating rate of 10 ° C./min, the onset temperature at the time of weight reduction of the TG curve was recorded. (F) (Oil resistance): After treated in JIS No. 3 oil at 70 ° C. for 7 days, a tensile test is performed according to JIS K-6301.
The tensile strength was determined and expressed as the rate of change (%) with respect to the tensile strength before the oil resistance test. (G) (Hot water resistance): After treated in distilled water at 100 ° C. for 7 days, a tensile test was performed according to JISK-6301 to determine the tensile strength, and the change rate (%) with respect to the tensile strength before the hot water test was shown. .

(H) (Injection moldability): 2 m by injection molding machine
When a m-thick sheet was formed, there was no appearance defect and the mold releasability was good. Hereinafter, the injection moldability was evaluated in the order of ◯ Δx. (× injection molding difficult)

(Examples 1 to 3) The polyether ester elastomer obtained in Production Example 1 and Tuftec M1913
At a ratio (% by weight) shown in Table 1 by a twin-screw extruder (temperature: 2
The mixture was kneaded at 20 ° C. and the number of revolutions was 200 rpm, and pelletized. The pellets thus obtained were vacuum dried at 80 ° C. for 5 hours and then injection-molded at a cylinder temperature of 220 ° C. to obtain a 2 mm thick sheet.

Comparative Example 1 The pellets of the polyether ester elastomer obtained in Production Example 1 were vacuum dried at 80 ° C. for 5 hours and then injection-molded at a cylinder temperature of 220 ° C. to obtain a 2 mm thick sheet.

Comparative Example 2 Tuftec M1913 pellets were compression molded at a temperature of 200 ° C. to obtain a 2 mm thick sheet. (Comparative Example 3) Pelprene P-40B pellets were injection-molded at a cylinder temperature of 210 ° C to obtain a 2 mm thick sheet.

Comparative Example 4 Perprene P-40B and Tuftec M1913 were kneaded at 70/30 (weight ratio) using a twin-screw extruder (temperature; 210 ° C., rotation speed; 150 rpm) and pelletized. The obtained pellets at 80 ° C,
After vacuum drying for 5 hours, injection molding was performed at a cylinder temperature of 210 ° C. to obtain a sheet having a thickness of 2 mm. The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 4 are summarized in Table 1 below.

[0097]

[Table 1]

The compositions of Examples 1 to 3 have greatly improved hot water resistance while maintaining the heat resistance, oil resistance and low temperature properties of the polyether ester elastomer. At the same time, it has a new rubber-like appearance, good moldability, and excellent product appearance. The polyester elastomer of Comparative Example 1 alone may be slightly inferior in hot water resistance and may have limited uses. The styrene-based elastomer of Comparative Example 2 is difficult to be injection-molded, and also has insufficient heat resistance and oil resistance, and it is sometimes difficult to use the elastomer alone. The composition of Comparative Example 4 is not sufficient in terms of physical properties at low temperature because the polyester elastomer is cured at low temperature.

(Examples 4 to 6) Polyether ester elastomer obtained in Production Example 2 and Tuftec H1041.
(Example 4), Tuftec M1913 (Example 5), and Tuftec Z513 (Example 6) were each 70/30.
Twin screw extruder (temperature: 240 ° C, rotation speed: 1)
50 rpm) was kneaded and pelletized. The obtained pellets were vacuum dried at 80 ° C. for 5 hours and then injection-molded at a cylinder temperature of 230 ° C. to obtain a 2 mm thick sheet.

(Comparative Example 5) Pellets of Hytrel 4767 were injection-molded at a cylinder temperature of 230 ° C to obtain 2 mm.
A thick sheet was obtained. (Comparative Example 6) Hytrel 4767 and Tuftec M191
3 in a twin screw extruder (temperature: 24; 70/30 (weight ratio))
The mixture was kneaded at 0 ° C. and the number of revolutions was 150 rpm, and pelletized. After vacuum-drying the obtained pellets at 80 ° C for 5 hours, injection molding is performed at a cylinder temperature of 230 ° C.
A mm thick sheet was obtained.

(Comparative Example 7) 70/30 of the polyether ester elastomer obtained in Production Example 2 and Tufprene A was used.
Twin screw extruder (temperature: 240 ° C, rotation speed: 1)
Attempts were made to knead using 50 rpm), but gelation occurred in the extruder and pellets could not be recovered. The evaluation results of Examples 4 to 6 and Comparative Examples 5 to 7 are summarized in Table 2 above.

[0102]

[Table 2]

The compositions of Examples 4 to 6 were excellent in low temperature physical properties, and the heat resistance at the needle penetration temperature was almost the same as that of the polyester elastomer alone (Comparative Example 5).
Further, when the decomposition temperatures are compared, it can be seen that the compositions of the examples are significantly increased, and decomposition reactions during melt processing do not easily occur. When a non-hydrogenated polymer was used as the styrene-based elastomer of Comparative Example 7, a gelling reaction occurred concurrently during kneading in the extruder, and pellets could not be obtained.

[0104]

The thermoplastic elastomer composition comprising the novel polyether ester elastomer of the present invention and the styrene saturated thermoplastic elastomer is excellent in moldability, flexibility, oil resistance, hydrolysis resistance, and heat resistance. It is a material with a wide operating temperature range because it has low-temperature performance. This thermoplastic elastomer composition is a material having excellent properties as described above, and can be suitably used for hoses, tubes, industrial parts, automobile interior / exterior parts, electric parts, daily necessities, etc.
It is an industrially very valuable material.

Claims (2)

[Claims] 1. A dicarboxylic acid component, wherein (A) (a-1) a short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and its ester-forming derivative, and (a-2) a short-chain diol component is an aliphatic component. The short-chain diol component, which is diol and its ester-forming derivative, and the (a-3) long-chain diol component are represented by the following formula:
It is composed of a neopentylene oxide structural unit (hereinafter abbreviated as N) shown in (1) and a tetramethyleneoxy structural unit (hereinafter abbreviated as T) shown in the following formula (2), and the ratio of N is 5 to 100 mol%. A polyether ester block copolymer obtained by copolymerizing a polyether with both end groups being alcoholic hydroxyl groups and having a number average molecular weight of 400 to 6,000 is used. 5 to 95% by weight, (B) at least two vinyl aromatic compound blocks A
And at least one block copolymer B having an unsaturation degree of not more than 20% and having a vinyl aromatic compound content of 10 to 90% by weight. Thermoplastic elastomer composition. [Chemical 1] [Chemical 2] 2. When N in the long chain diol component of (a-3) is not the terminal of the long chain diol, the structural units adjacent to each other across N are T, and N is at the terminal. In this case, it has a structure in which a hydroxyl group is bonded, the structural unit adjacent to N on the opposite side of the hydroxyl group is T, and N is 5 to 50 mol% of polyether glycol. A thermoplastic elastomer composition according to claim 1, characterized in that