JP2001002768A - Polyester elastomer resin and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having a high tear strength at a high temperature, abrasion resistance, resistance to fatigue from flexing and blow moldability by making the melt viscosity index of a specific polyether ester block copolymer have a specified value. SOLUTION: This resin comprises a polyether ester block copolymer constituted of (A) a high-melting crystalline polymer segment composed of a crystalline aromatic polyester unit (e.g. polybutylene terephthalate) and (B) a low-melting polymer segment composed of an aliphatic polyether unit [e.g. poly(tetramethylene oxide) glycol] having a molecular weight distribution dispersion value (α) represented by the formula α=Mv/Mn<=1.9 (Mv is a number-average molecular weight; Mn is a viscosity-average molecular weight) and has <=10 g/10 minutes melt viscosity index (250 deg.C, 2,160 g load).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester elastomer resin having high tear strength at high temperatures, excellent abrasion resistance and bending fatigue resistance, high melt viscosity, and good blow moldability. High tear strength, excellent wear resistance, flex fatigue resistance, low and high temperature properties, heat aging resistance, oil resistance, grease resistance, high melt viscosity, good blow moldability, especially flexible The present invention relates to a polyester elastomer resin composition suitable for molding applications such as boots.

[0002]

2. Description of the Related Art A polyetherester block copolymer having a crystalline aromatic polyester unit such as polybutylene terephthalate unit as a hard segment and an aliphatic polyether unit such as poly (alkylene oxide) glycol as a soft segment is known. Excellent in extrudability, injection moldability, high mechanical strength, rubber properties such as impact resistance, elastic recovery, flexibility, low and high temperature properties, water resistance, etc., and thermoplastic processing Because of its ease of use, applications are expanding to automotive parts, electric and electronic parts, fibers, films, and the like.

[0003] Although the polyetherester block copolymer has the above-mentioned excellent properties, the abrasion resistance, bending fatigue resistance, tear strength at high temperatures, etc. are not always at satisfactory levels, and are further improved. What is done is required. In addition, although the low-temperature and high-temperature properties are superior to other thermoplastic elastomers, in reality, further improvements are required to enable use under more severe conditions.

In view of such circumstances, many attempts have been made to improve the abrasion resistance, flex fatigue resistance, tear strength at high temperatures, low-temperature and high-temperature properties of polyetherester block copolymers. And, for example,
JP-A-655552 discloses a composition for a sliding material in which a polyester elastomer is blended with a solid lubricant, a higher alcohol, a higher fatty acid and the like. Further, Japanese Patent Application Laid-Open No.
Japanese Patent No. 75364 discloses a resin composition having excellent abrasion resistance in which a thermoplastic polyurethane elastomer and a compound having an epoxy group and a hydrolyzable silyl group in a molecule are mixed with a polyester elastomer. Further, JP-A-5-279557 discloses a slidable resin composition in which a polyester resin is blended with a specific substituted amide, and JP-A-8-208951 discloses that a polyester elastomer contains silicone. A wear-resistant resin composition containing a resin and a reactive silicone oil is disclosed.

Japanese Patent Application Laid-Open No. 8-151508 discloses that a polyetherester block copolymer has 1 carbon atom.
A resin composition comprising 0 to 40 sodium aliphatic mono- or polycarboxylates, a diphenylamine-based compound, and a hindered phenol-based antioxidant is disclosed.

Further, JP-A-54-158497 and JP-A-60-55027 disclose polyester elastomers obtained by copolymerizing high molecular weight poly (tetramethylene oxide) glycol having a narrow molecular weight distribution. .

However, Japanese Patent Application Laid-Open Nos. 52-65552, 4-275364, 5-27
Although the resin compositions disclosed in Japanese Patent Application Laid-Open No. 9557 and JP-A-8-208951 are certainly resin compositions having improved wear resistance and slidability, bending fatigue resistance and tearing at high temperatures are considered. The strength, low and high temperature properties, etc. are insufficient.

The resin composition disclosed in Japanese Patent Application Laid-Open No. Hei 8-151508 is certainly a resin composition having excellent bending fatigue resistance, and can be blow-molded. Are insufficient in tear strength, low temperature and high temperature properties.

Furthermore, the resin compositions disclosed in JP-A-54-158497 and JP-A-60-55027 are certainly excellent in low-temperature and high-temperature characteristics.
Flexural fatigue resistance, tear strength at high temperatures, heat aging resistance,
It has insufficient oil resistance and low melt viscosity, and is not suitable for blow molding.

[0010]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Accordingly, an object of the present invention is to provide a polyester elastomer resin having high tear strength at high temperature, excellent wear resistance and bending fatigue resistance, high melt viscosity, and good blow moldability, High tear strength, excellent wear resistance, flex fatigue resistance, low and high temperature properties, heat aging resistance, oil resistance, grease resistance, high melt viscosity, good blow moldability, especially flexible An object of the present invention is to provide a polyester elastomer resin composition suitable for molding applications such as boots.

[0012]

In order to achieve the above object, the polyester elastomer resin of the present invention comprises a high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a molecular weight distribution dispersion. A polyetherester block copolymer (A) composed of a low-melting polymer segment (b) composed of an aliphatic polyether unit having a value α in a range represented by the following formula (I), and according to ASTM D1238, Temperature 250
° C, melt viscosity index (MFR) measured under a load of 2160 g
(Value) is 10 g / 10 minutes or less.

Further, the polyester elastomer resin composition of the present invention has a high melting point crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a molecular weight distribution dispersion value α represented by the following formula (I). ASTM comprising a polyetherester resin composition (X) containing a polyetherester block copolymer (A) as a main component composed of a low-melting polymer segment (b) comprising an aliphatic polyether unit, A polyester elastomer resin composition having a melt viscosity index (MFR value) of 10 g / 10 min or less measured at a temperature of 250 ° C. and a load of 2160 g according to D1238.

Molecular weight distribution dispersion value α = Mv / Mn ≦ 1.9 (I)
(However, Mn is the number average molecular weight, Mv is the viscosity average molecular weight defined by the following formula (II). In the following formula, μ is the melt viscosity at 40 ° C. expressed in poise.) Mv = antilog (0.494 log μ + 3.0646) (II) In the polyester elastomer resin composition, the polyetherester block copolymer composition (X) is added to 100 parts by weight of the polyetherester block copolymer (A). On the other hand, at least one selected from a difunctional or higher functional epoxy compound (B), a difunctional or higher functional isocyanate compound (C), and an alkali or alkaline earth metal salt of a fatty acid (D) is used in an amount of 0.01 to 1 respectively.
0 parts by weight, wherein the polyetherester block copolymer composition (X) is based on 100 parts by weight of the polyetherester block copolymer (A) and is composed of α-olefin and 3 carbon atoms. An ionomer resin (E) in which a copolymer of α, β-unsaturated carboxylic acid of 1 to 8 is added with a metal ion of 1 to 3 valences, and an α-olefin and α,
The polyetherester block copolymer composition (X) further contains 1 to 25 parts by weight of an olefin copolymer (F) composed of a glycidyl ester of β-unsaturated acid. Aromatic amine antioxidants (G), hindered phenol antioxidants (H),
Sulfur-based antioxidant (I) and phosphorus-based antioxidant (J), each containing 0.01 to 5 parts by weight in any of the following combinations: [(G) alone, (H) + Combination of (I), (H) +
(J) combination, (H) + (I) + (J) combination,
(G) + (H) + (I) combination, (G) + (H) +
Combination of (J), Combination of (G) + (H) + (I) + (J)] The above-mentioned polyester elastomer resin composition 100
The polyamide resin (K) 0.1
And the high-melting crystalline polymer segment (a), which is a component of the polyetherester block copolymer (A), is a polybutylene terephthalate unit and / or polybutylene An aliphatic polyether that is composed of phthalate units and that constitutes the low-melting polymer segment (b) that is a component of the polyetherester block copolymer (A);
A poly (tetramethylene oxide) glycol unit, and a low-melting-point polymer segment (b) which is a component of the polyetherester block copolymer (A).
Has a number average molecular weight of 13
The molecular weight distribution dispersion value α of the aliphatic polyether constituting the low-melting polymer segment (b), which is a component of the polyetherester block copolymer (A), is 1.85 or less. That the molecular weight distribution dispersion value α of the aliphatic polyether constituting the low melting point polymer segment (b), which is a component of the polyetherester block copolymer (A), is 1.8 or less; The copolymerization amount of the low-melting polymer segment (b) in the polyester block copolymer (A) is 10 to 80.
% Of the low-melting-point polymer segment (b) in the polyetherester block copolymer (A).
Is 30 to 70% by weight, ASTM
The melt viscosity index (MFR value) measured at a temperature of 250 ° C. and a load of 2160 g is 8 g / 10 min or less according to D1238, and at a temperature of 25 according to ASTM D1238.
Melt viscosity index (MFR) measured at 0 ° C. under a load of 2160 g
Value) is 5 g / 10 min or less, the bifunctional or higher epoxy compound (B) is a glycidyl ester compound, the polyamide resin (K) is a copolymerized polyamide resin, and used for blow molding. Being a polyester elastomer resin composition and being a molding composition for flexible boots, both are preferable conditions, and by applying these conditions, it is possible to expect to obtain a more excellent effect. .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The high-melting crystalline polymer segment (a) of the polyetherester block copolymer (A) used in the present invention is composed of a crystal formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. Aromatic polyester units, preferably polybutylene terephthalate units derived from terephthalic acid or dimethyl terephthalate and 1,4-butanediol, and / or naphthalene-2,6-dicarboxylic acid or naphthalene-2,7- Polybutylene naphthalate units derived from dicarboxylic acids or their dimethyl ester compounds and 1,4-butanediol. In addition, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-
Dicarboxylic acid components such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, and ester-forming derivatives thereof. And a diol having a molecular weight of 300 or less, for example, 1,4
-Aliphatic diols such as butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol and decamethylene glycol; alicyclics such as 1,4-cyclohexanedimethanol and tricyclodecane dimethylol; Diol, 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, 4,
Polyesters derived from aromatic diols such as 4'-dihydroxy-p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl, or copolymers of two or more of these dicarboxylic acid components and diol components It may be a polyester unit. Also, 3
It is also possible to copolymerize a polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component and the like having a functionality of at least 5 mol%.

The low melting point polymer segment (b) of the polyester block copolymer (A) used in the present invention comprises an aliphatic polyether unit. Specific examples of such an aliphatic polyether include poly (ethylene oxide)
Glycol, poly (propylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of poly (propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Among these aliphatic polyethers,
Poly (tetramethylene oxide) glycol, an ethylene oxide adduct of poly (propylene oxide) glycol, and the like are preferable because the resulting polyester block copolymer has excellent elastic properties. Further, the number average molecular weight of these low melting point polymer segments is preferably about 1300 to 3500 in a copolymerized state. In the present invention, the low melting polymer segment (b) is
It is composed of an aliphatic polyether unit having a molecular weight distribution dispersion value α in a range represented by the following formula (I).

Molecular weight distribution dispersion value α = Mv / Mn ≦ 1.9 (I) (where Mn is a number average molecular weight and Mv is a viscosity average molecular weight defined by the following formula (II). μ is the melt viscosity at 40 ° C. expressed in poise.) Mv = antilog (0.494 log μ + 3.0646) (II) That is, the molecular weight distribution dispersion value α is 1.9 or less, preferably 1.85 or less. More preferably, one having 1.8 or less is used. When the molecular weight dispersion value α of the aliphatic polyether unit exceeds 1.9, especially when the number average molecular weight of the aliphatic polyether is large, or when the low melting point polymer segment (b)
When the copolymerization amount of the polyetherester block copolymer is large, the polyetherester block copolymer (A) is not a transparent or translucent homogeneous copolymer at the time of melting, and becomes cloudy at the time of melting. It becomes a heterogeneous copolymer having a pearly luster. In such a case, the tear strength at a high temperature of the polyester elastomer resin composition decreases,
Abrasion resistance, bending fatigue resistance, low-temperature and high-temperature properties, etc. also deteriorate. It also becomes difficult to reach a sufficiently high melt viscosity that allows blow molding.

The copolymerization amount of the low melting point polymer segment (b) in the polyetherester block copolymer (A) used in the present invention is from 10 to 80% by weight, more preferably from 30 to 70% by weight. Is preferred.

The polyetherester block copolymer (A) used in the present invention can be produced by a known method. For example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low-molecular-weight glycol, and a low-melting polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the obtained reaction product. Alternatively, a dicarboxylic acid, an excess amount of glycol and a low melting polymer segment component are subjected to an esterification reaction in the presence of a catalyst, and the resulting reaction product is polycondensed. Further, any method such as a method in which a high-melting-point crystalline segment is prepared in advance, and a low-melting-point segment component is added thereto to randomize by transesterification, may be used.

In order to obtain the polyester elastomer resin of the present invention, the melt polymerization method of the polyetherester block copolymer (A) is terminated on the way, and is discharged once in the form of a strand and cut, and then the pellet is formed. The polymerization may be continued at a temperature lower than the melting point of the ether ester block copolymer under reduced pressure by a solid phase polymerization method to increase the viscosity.

In order to obtain the polyester elastomer resin composition of the present invention, the polyetherester block copolymer (A) is added to a difunctional or higher functional epoxy compound (B), a difunctional or higher functional isocyanate compound (C), One or more selected from alkali or alkaline earth metal salts (D) may be blended to increase the viscosity.

Specific examples of the bifunctional or higher functional epoxy compound (B) include bisphenol A type epoxy resin formed by a condensation reaction of bisphenol A and epichlorohydrin, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol. Diglycidyl ether compounds of glycols such as diglycidyl ether, 1,6-hexanediol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane Polyglycidyl ether,
Polyglycidyl ether compounds of polyols such as diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl hexahydrophthalate ,
Naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester Glycidyl ester,
Diglycidyl ester compounds of dicarboxylic acids such as diglycidyl ester of dodecane dicarboxylic acid, diglycidyl ester of octadecane dicarboxylic acid, and diglycidyl ester of dimer acid; polyglycidyl of polycarboxylic acids such as triglycidyl ester of trimellitic acid and tetraglycidyl ester of pyromellitic acid Ester compounds and the like. Among these, a bifunctional epoxy compound having two glycidyl groups in the compound is preferable. Glycidyl ester compounds are particularly preferred. In the polyester elastomer resin composition of the present invention, an epoxy curing catalyst is not basically used, but if necessary, an epoxy curing catalyst may be used together with a bifunctional or more functional epoxy compound (B). Examples of such an epoxy curing catalyst include an aliphatic polyamine, an aromatic polyamine, an alicyclic polyamine, an aromatic acid anhydride, a cyclic aliphatic acid anhydride, an imidazole compound, and a tertiary amine compound.

Bifunctional or higher functional isocyanate compound (C)
Specific examples include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexyl methane diisocyanate. Can be Among them, diphenylmethane diisocyanate is preferably used.

Examples of alkali or alkaline earth metal salts (D) of fatty acids include decanoic acid, undecanoic acid, lauric acid, sebacic acid, myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, oleic acid, Dodecanecarboxylic acid, octadecylsuccinic acid, octadecenylsuccinic acid, docosandicarboxylic acid,
Examples include salts of sodium, potassium, lithium, barium, calcium, magnesium and the like such as dimer acid and montan wax acid. Among them, an aliphatic mono- or polycarboxylate having 10 to 40 carbon atoms is preferably used.

At least one selected from a bifunctional or higher functional epoxy compound (B), a bifunctional or higher functional isocyanate compound (C), and an alkali or alkaline earth metal salt of a fatty acid (D) is a polyetherester block copolymer. Coalescing (A) 1
0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight is added to 00 parts by weight. If the compounding amount is less than 0.01 part by weight, the degree of improvement of the desired effect is small, and if the compounding amount exceeds 10 parts by weight, gelation occurs due to stagnation during melting during molding and molding is not preferable.

In order to obtain the polyester elastomer resin composition of the present invention, an α-olefin and an α, 3 to 8 carbon atom are added to the polyetherester block copolymer (A).
An ionomer resin (E) in which a copolymer of β-unsaturated carboxylic acid is added with a metal ion having 1 to 3 valences, and an olefin copolymer (F) comprising an α-olefin and a glycidyl ester of α, β-unsaturated acid ) May be blended.

Α-olefin and α, β- having 3 to 8 carbon atoms
The α-olefin in the ionomer resin (E) in which a copolymer of unsaturated carboxylic acid is added with a metal ion having 1 to 3 valences is ethylene, propylene, butene-1, etc.
Of these, ethylene is preferred. In addition, carbon number 3-8
As the α, β-unsaturated carboxylic acid, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid and the like are used, and these alkyl esters may be copolymerized. Of these, acrylic acid and methacrylic acid are preferably used. The copolymerization amount of the α, β-unsaturated carboxylic acid component in the copolymer is preferably 0.2 to 25 mol%,
Particularly preferably, it is 1 to 10 mol%. The ionomer resin (B) is an ionic copolymer in which a carboxylic acid group in the copolymer is ion-crosslinked with a carboxylic acid group in the copolymer by adding a trivalent metal ion to the copolymer composed of the above components.
Suitable mono- to trivalent metal ions for the formation of ionic crosslinks are sodium, potassium, lithium, magnesium,
Examples include calcium, zinc, aluminum, ferrous and ferric ions. The introduction of ionic crosslinks into the copolymer is achieved by reacting the copolymer with a hydroxide, methoxide, ethoxide, carbonate, nitrate, formate, acetate, oxide, etc. of a metal having a valency of 1-3. You. Preferably, at least 10% of the carboxylic acid groups in the copolymer are neutralized by metal ions.

Examples of the α-olefin in the olefin copolymer (F) comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid include ethylene, propylene and butene-1. It is preferably used. Examples of the glycidyl ester of an α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used. The copolymerization amount of the α, β-unsaturated glycidyl ester is preferably in the range of 0.1 to 20 mol%. If it is 40 mol% or less, unsaturated monomers copolymerizable with the above copolymer, for example, vinyl ethers, vinyl acetate, vinyl esters such as vinyl propionate, acrylic acid such as methyl, ethyl, propyl, and butyl; Methacrylic acid esters, acrylonitrile, styrene and the like may be copolymerized.

Α-olefin and α, having 3 to 8 carbon atoms,
An ionomer resin (E) in which a copolymer of β-unsaturated carboxylic acid is added with a metal ion having 1 to 3 valences, and an olefin copolymer (F) comprising an α-olefin and a glycidyl ester of α, β-unsaturated acid ) Is 1 to 25 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyetherester block copolymer (A). If the amount is less than 1 part by weight, the improvement of the intended effect is small, and if it exceeds 25 parts by weight, oil resistance, grease resistance and flex fatigue deteriorate.

The polyester elastomer resin composition of the present invention comprises an aromatic amine antioxidant (G), a hindered phenol antioxidant (H), a sulfur antioxidant (I), a phosphorus antioxidant ( J) 0.01 to 5 respectively
When the parts by weight are blended in any of the following combinations, a further excellent polyester elastomer resin composition can be obtained. [(G) alone, (H) + (I) combination, (H) +
(J) combination, (H) + (I) + (J) combination,
(G) + (H) + (I) combination, (G) + (H) +
Combination of (J), Combination of (G) + (H) + (I) + (J)] Specific examples of the aromatic amine antioxidant (G) include phenylnaphthylamine and 4,4′-dimethoxydiphenylamine , 4,4'-bis (α, α-dimethylbenzyl) diphenylamine and 4-isopropoxydiphenylamine, among which diphenylamine compounds are preferred.

Specific examples of the hindered phenolic antioxidant (H) which is one of the components used in the polyester elastomer resin composition of the present invention include 2,4-dimethyl-6-t-butylphenol, 6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p- Cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2′-methylene-bis-4-methyl-6 −
t-butylphenol, 2,2′-methylene-bis (4
-Ethyl-6-t-butylphenol), 4,4'-methylene-bis (6-t-butyl-o-cresol),
4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-
6-cyclohexylphenol), 4,4′-butylidene-bis (3-methyl-6-t-butylphenol),
4,4'-thiobis (6-t-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-t
-Butylbenzyl) sulfide, 4,4′-thiobis (6-t-butyl-o-cresol), 2,2′-thiobis (4-methyl-6-t-butylphenol), 2,
6-bis (2'-hydroxy-3'-t-butyl-5 '
-Methylbenzyl) -4-methylphenol, 3,5-
Diethyl ester of di-t-butyl-4-hydroxybenzenesulfonic acid, 2,2'-dihydroxy-3,3 '
-Di (α-methylcyclohexyl) -5,5′-dimethyl-diphenylmethane, α-octadecyl-3 (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,
3,5-triazine, hexamethylene glycol-bis [β- (3,5-di-t-butyl-4-hydroxyphenol) propionate], N, N′-hexamethylene-bis (3,5-di-t -Butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-bis-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], dioctadecyl ester of 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid,
Tetrakis [methylene-3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] methane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3
5-di-t-butyl-4-hydroxyphenyl) isocyanurate, and tris [β- (3,5-di-t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate. Among them, those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane are preferable.

The sulfur type antioxidant (I) is a compound containing sulfur such as thioether type, dithioate type, mercaptobenzimidazole type, thiocarbanilide type, thiodipropion ester type and the like. Among them, thiodipropion ester-based compounds are preferable.

The phosphorus antioxidant (J) includes phosphorus such as phosphoric acid, phosphorous acid, hypophosphorous acid derivative, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite and the like. Compound. Among these, a compound having a sulfur atom together with a phosphorus atom in a molecule and a compound having two or more phosphorus atoms in a molecule are preferable.

The amount of each of these antioxidants (G) to (J) is 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polyetherester block copolymer (A). To 3 parts by weight, more preferably 0.1 to 1 part by weight
Parts by weight. If it is less than 0.01 part by weight, the degree of improvement of the intended effect is small, and if it is rubbed with 5 parts by weight, blooming occurs and the mechanical strength of the polyester elastomer resin composition is undesirably reduced.

The polyester elastomer resin composition of the present invention, when blended with a polyamide resin (K), can be a further excellent polyester elastomer resin composition. The polyamide resin (K) used in the polyester elastomer resin composition of the present invention is a polymer compound having an amide bond in the molecular chain, and is composed of a polymer from lactam, adipic acid, sebacic acid, dodecanedioic acid and the like. And a polymer of a salt obtained by a reaction with ethylenediamine, hexamethylenediamine, metaxylenediamine, or the like, or a polymer from ω-aminocarboxylic acid. These may be copolymers or two or more different polymers may be used in combination. Among these polyamide resins, a higher effect can be obtained when a copolymerized polyamide resin is used.

The amount of the polyamide resin (K) is 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0 to 100 parts by weight based on 100 parts by weight of the polyetherester block copolymer (A). 0.5 to 5 parts by weight. If the compounding amount of the polyamide resin (K) is less than 0.1 part by weight, the degree of improvement of the intended effect is small, and if it exceeds 20 parts by weight, the flexibility and rubbery properties inherent in the polyetherester block copolymer are obtained. It is not preferable because properties are impaired.

Various additives can be further added to the polyester elastomer resin composition of the present invention as long as the object of the present invention is not impaired. For example, molding auxiliaries such as known nucleating agents and lubricants, ultraviolet absorbers and hindered amine compounds such as light stabilizers, hydrolysis resistance improvers, coloring agents such as pigments and dyes, antistatic agents, conductive agents, and flame retardants , A reinforcing agent, a filler, a plasticizer, a release agent, and the like.

The method for producing the polyester elastomer resin composition of the present invention is not particularly limited. For example, a raw material in which an antioxidant is blended with a polyether ester block copolymer or a polyether ester block copolymer is used. A raw material in which a high viscosity agent such as a bifunctional or higher epoxy compound and other predetermined antioxidants are blended into the coalesced material, or a high viscosity including a bifunctional or higher functional epoxy compound in a polyetherester block copolymer. A method in which a raw material obtained by blending an agent, a predetermined antioxidant, and a polyamide resin is supplied to a screw type extruder and melt-kneaded,
In addition, a method in which a polyetherester block copolymer is first supplied to a screw-type extruder and melted, and then another compound is supplied from another supply port and kneaded, may be appropriately employed.

The polyester elastomer resin or resin composition of the present invention has a melt viscosity index (M) measured at a temperature of 250 ° C. under a load of 2160 g according to ASTM D1238.
FR value) is 10 g / 10 min or less, more preferably 8 g / 10 min or less, and particularly preferably 5 g / 10 min.
Minutes or less. Melt viscosity index (MFR value) is 10 g / 1
If the time exceeds 0 minutes, the blow moldability decreases, the tear strength at high temperatures decreases, and the abrasion resistance, bending fatigue resistance, and the like become insufficient.

The polyester elastomer resin of the present invention thus constituted has high tear strength at high temperatures, excellent wear resistance and bending fatigue resistance, high melt viscosity, and good blow moldability. . Further, the polyester elastomer resin composition of the present invention thus configured,
High tear strength at high temperature, excellent wear resistance, bending fatigue resistance, low temperature and high temperature properties, excellent heat aging resistance, oil resistance, grease resistance, high melt viscosity, good blow moldability, especially It is suitable for molding applications such as flexible boots such as constant velocity joint boots and rack and pinion boots.

[0042]

EXAMPLES The structure and effect of the present invention will be further described below with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified. The physical properties shown in the examples were measured as follows. [Melt viscosity index (MFR value)] Measured at a temperature of 250 ° C and a load of 2160 g in accordance with ASTM D1238. [Melting Point] Differential Scanning Calorimeter (Du Pont DSC-
910) was measured at the top of the melting peak when heated at a rate of 10 ° C./min in a nitrogen gas atmosphere. [Hardness (Shore D scale)] Measured according to JIS K7215. [Tear strength] Measured according to ASTM D-624. The die was type C and measured on a test piece having a thickness of 2 mm. [Abrasion resistance] Each pellet dried at 80 ° C for 5 hours was injection molded at a temperature of 250 ° C to produce a disk having a thickness of 3 mm and a diameter of 10 mm. Using this disk, abrasion resistance was tested under the following conditions, and the amount of abrasion was measured. In this test, the smaller the wear amount, the better the wear resistance.

Test conditions: Test machine: Suzuki-type thrust wear tester Surface pressure: 2.76 kg / cm ² (pressurized load 5.52 k
g) Peripheral speed: 5 m / min Test time: 1 hour Test temperature: 23 ° C., 100 ° C. Counterpart material: Same material [Bending fatigue resistance] Each pellet dried at 80 ° C. for 5 hours is press-formed at a temperature of 250 ° C. , Thickness 2mm, width 20m
m test pieces were prepared. Using this test piece, the bending fatigue resistance was tested under the following conditions, and the crack length after 300,000 bending cycles was measured. In this test, the shorter the length of the generated crack, the better the durability.

Test conditions: Testing machine: Dematcher bending fatigue tester Test temperature: 100 ° C. Distance between chucks: 25 mm → 5.6 mm Flexing cycle: 300 times / minute [Blow moldability] Pellets dried by hot air at 80 ° C. for 5 hours Using a press blow molding machine (SBE50 manufactured by Osberger)
/ 140 type) with a cylinder temperature of 230 ° C., a nozzle temperature of 250 ° C., and a mold temperature of 30 ° C. under a molding condition of a large diameter portion and a small diameter portion having five peaks and five valleys.
Weight 60 having a shape connected by 5 mm bellows
g was evaluated for blow moldability by attempting to mold it into a flexible boot for constant velocity joints. [Grease resistance] The pellets dried with hot air at 80 ° C for 5 hours were subjected to JIS 2 at a molding temperature of 250 ° C and a mold temperature of 60 ° C.
No. dumbbell injection molding. This dumbbell, 120
Showa Oil Co., Ltd.'s “Showa Sunlight Grease SW-
2 "(high-grade lithium soap grease), and the time required for the tensile elongation at break to drop to half the initial value was measured. [Reference Example] [Production of polyetherester block copolymer (A-1)] 403 parts of terephthalic acid, 371 parts of 1,4-butanediol and a molecular weight distribution dispersity α of 1.65 and a number average molecular weight of about 2,000 Poly (tetramethylene oxide)
Glycol (PTMG2000 manufactured by Sanyo Kasei Co., Ltd.) 48
8 parts together with 2 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and
The esterification reaction was performed while heating at 5 ° C. for 3 hours to distill the reaction water out of the system. To the reaction mixture was added 0.75 parts of "Irganox" 1010 (a hindered phenol-based antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C, and the pressure in the system was raised to 27 Pa over 40 minutes. The pressure was reduced, and polymerization was carried out under the conditions for 2 hours and 45 minutes. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. The molten polymer when discharged in the form of a strand was transparent. [Production of polyetherester block copolymer (A-2)] 403 parts of terephthalic acid, 371 parts of 1,4-butanediol and poly (tetra) having a molecular weight distribution dispersity α of 1.97 and a number average molecular weight of about 2000 Methylene oxide)
Glycol (Dupont "Terratan" 2000) 48
8 parts together with 2 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and
The esterification reaction was performed while heating at 5 ° C. for 3 hours to distill the reaction water out of the system. To the reaction mixture was added 0.75 parts of "Irganox" 1010 (a hindered phenol-based antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C, and the pressure in the system was raised to 27 Pa over 40 minutes. The pressure was reduced, and polymerization was carried out for 2 hours and 30 minutes under the reduced pressure. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. The molten polymer when discharged in a strand form was cloudy and had a pearly luster. [Production of polyetherester block copolymer (A-3)] 436 parts of dimethyl terephthalate, 344 parts of 1,4-butanediol and a molecular weight distribution dispersity α of 1.8.
Poly (tetramethylene oxide) glycol having a number average molecular weight of about 1800 (PTG manufactured by Hodogaya Chemical Industry Co., Ltd.)
-1800SN) 531 parts together with 2 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade and heated at 210 ° C. for 2 hours to remove 95% of the theoretical methanol amount of methanol out of the system. Distilled. After adding 0.75 parts of “Irganox” 1010 to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 40 minutes, and polymerization was carried out under these conditions for 2 hours and 20 minutes. I let you. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. The molten polymer when discharged in the form of a strand was transparent. Table 1 shows the composition and physical properties of A-1, A-2, and A-3.

[0045]

[Table 1] [Epoxy Compound] The bifunctional or higher functional epoxy compounds used in the examples are as follows. B-1: Hexahydrophthalic acid diglycidyl ester [Isocyanate compound] The bifunctional or higher functional isocyanate compound used in the examples is as follows. C-1: Diphenylmethane diisocyanate [Metal salt] The alkali or alkaline earth metal salts of fatty acids used in the examples are as follows. D-1: Sodium stearate [Ionomer resin] The ionomer resin used in the examples is as follows. E-1: "Himilan" 1707 (an ionic copolymer obtained by neutralizing an ethylene-methacrylic acid copolymer with sodium) manufactured by DuPont-Mitsui Polychemicals Co., Ltd. [Olefin-based copolymer] Olefin used in Examples The system copolymer is as follows. F-1: "Bond First" 2C manufactured by Sumitomo Chemical Co., Ltd.
(Ethylene-glycidyl methacrylate copolymer) [Antioxidant] The antioxidants used in the examples are as follows. G-1: Uniroyal diphenylamine antioxidant "Nowgard" 445 H-1: Ciba-Geigy hindered phenol antioxidant "Irganox" 1010 (molecular weight: 1177.
7) I-1: Daiichi Kogyo Seiyaku Co., Ltd. sulfur antioxidant "Rasmit" (dilauryl thiodipropionate) J-1: Asahi Denka Kogyo Co., Ltd. phosphorus antioxidant "ADEKA STAB" PEP -8 (contains two phosphorus atoms in the molecule) J-2: Johoku Kagaku Co., Ltd. phosphorus antioxidant JPS31
2 (trilauryl trithiophosphite, containing phosphorus and sulfur atoms in the molecule) [Production of polyamide resin] The composition ratio of polycaprolactam, polyhexamethylene adipamide and polyhexamethylene sebacamide is about 45/35 / A terpolymer (polyamide resin (K-1)) consisting of 20 was produced. [Example 1] 445 parts of terephthalic acid, 241 parts of 1,4-butanediol and poly (tetramethylene oxide) glycol having a molecular weight distribution dispersity α of 1.74 and a number average molecular weight of about 1400 (Hodogaya Chemical Industry Co., Ltd. ) PTG-1
439 parts were charged together with 2 parts of titanium tetrabutoxide into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. . To the reaction mixture was added 0.75 parts of "Irganox" 1010 (a hindered phenol-based antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C, and the pressure in the system was raised to 27 Pa over 40 minutes. Under reduced pressure, polymerization was carried out for 3 hours and 50 minutes under the reduced pressure. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. The polyetherester block copolymer (A-4) thus obtained had a transparent molten polymer when discharged in a strand form. Table 2 shows the composition and physical properties of A-4. Using the pellets of the polyetherester block copolymer (A-4), tear strength, abrasion resistance, flex fatigue resistance, and blow moldability were evaluated. Table 3 shows the results.

[0046]

[Table 2]

[0047]

[Table 3] [Comparative Example 1] Poly (tetramethylene oxide) glycol having a molecular weight distribution dispersity α of 1.74 and a number average molecular weight of about 1400 (PTG manufactured by Hodogaya Chemical Industry Co., Ltd.) used in Example 1
-1400SN) in the same manner as in Example 1 except that poly (tetramethylene oxide) glycol having a molecular weight distribution dispersity α of 1.95 and a number average molecular weight of about 1400 (“Terratan” 1400 manufactured by DuPont) is used instead of -1400SN). Melt polymerization was performed. In the obtained polyetherester block copolymer (A-5), the molten polymer when discharged in the form of a strand was cloudy. Table 2 shows the composition and physical properties of A-5. This polyetherester block copolymer (A
Using the pellets of -5), tear strength, wear resistance, bending fatigue resistance, and blow moldability were evaluated. Table 3 shows the results. Example 2 Pellets of the polyetherester block copolymer (A-1) obtained in Reference Example were charged into a rotatable reaction vessel, and the pressure in the system was reduced to 27 Pa,
Solid-state polymerization was performed by heating at 70 to 180 ° C. while rotating for 72 hours. Table 2 shows the composition and physical properties of the obtained polyetherester block copolymer (A-6). Using pellets of this polyetherester block copolymer (A-6), tear strength, wear resistance, flex fatigue resistance,
The blow moldability was evaluated. Table 3 shows the results. [Comparative Example 2] The pellets of the polyetherester block copolymer (A-2) obtained in Reference Example were charged into a rotatable reaction vessel, and the pressure in the system was reduced to 27 Pa.
Solid-state polymerization was performed by heating at 70 to 180 ° C. while rotating for 72 hours. Table 2 shows the composition and physical properties of the obtained polyetherester block copolymer (A-7). Using the pellets of the polyetherester block copolymer (A-7), tear strength, abrasion resistance, flex fatigue resistance,
The blow moldability was evaluated. Table 3 shows the results. Comparative Example 3 The tear strength, abrasion resistance and flex fatigue resistance were evaluated using the pellets of the polyetherester block copolymer (A-1) obtained in the reference example. Table 3 shows the results.

As is evident from Table 3, the polyester elastomer resin of the present invention is particularly excellent in tear strength, abrasion resistance and bending fatigue resistance at high temperatures, and is suitable for blow molding. On the other hand, the polyester elastomer resin of the comparative example lacking the conditions of the present invention has a low tear strength at a high temperature, a large amount of wear, is inferior in bending fatigue resistance, and cannot be blow-molded. [Examples 3 to 6] Using the polyetherester block copolymer (A-3) obtained in the reference example, the raw materials were dry-blended at the compounding ratios shown in Table 4 to obtain a mixture having a screw of 45 mmφ. Using a screw extruder, the mixture was melt-kneaded at a cylinder set temperature of 240 ° C. and then pelletized. Using these pellets, the melt viscosity index (MFR) was measured, and the tear strength, wear resistance, flex fatigue resistance,
The grease resistance and blow moldability were evaluated. Table 5 shows the results.

[0049]

[Table 4]

[0050]

[Table 5] [Comparative Example 4] Using the pellets of the polyetherester block copolymer (A-3) itself obtained in Reference Example, tear strength, abrasion resistance, bending fatigue resistance, grease resistance, blow moldability. Was evaluated. Table 5 shows the results.

As is clear from Table 5, the polyester elastomer resin composition of the present invention is particularly excellent in tear strength, abrasion resistance, flex fatigue resistance and grease resistance at high temperatures, and is suitable for blow molding. .

[0052]

As described above, the polyester elastomer resin of the present invention has high tear strength at high temperatures, excellent wear resistance and bending fatigue resistance, high melt viscosity, and good blow moldability. To provide a suitable resin. Further, the polyester elastomer resin composition of the present invention has high tear strength at high temperatures, excellent wear resistance, bending fatigue resistance, low temperature and high temperature properties, excellent heat aging resistance, oil resistance, grease resistance, and high melt viscosity. And a resin composition having good blow moldability and particularly suitable for molding applications such as flexible boots represented by constant velocity joint boots, rack and pinion boots and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/49 C08K 5/49 C08L 63/00 C08L 63/00 A 67/00 67/00 75/06 75 / 06 77/00 77/00 // F16J 3/04 F16J 3/04 A (C08L 67/00 23:26 23:02) (72) Inventor Mamoru Horiuchi 3804 Honhoshizakicho, Minato-ku, Nagoya-shi, Aichi No. 19 Toray Dupont Co., Ltd. Nagoya Office

Claims (19)

[Claims] 1. A high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit, and an aliphatic polyether unit having a molecular weight distribution dispersion value α in a range represented by the following formula (I). It is composed of a polyetherester block copolymer (A) composed of a low melting polymer segment (b), and has a melt viscosity index (MFR value) of 10 g / 10 minutes measured at a temperature of 250 ° C. under a load of 2160 g according to ASTM D1238. The following polyester elastomer resin. Molecular weight distribution dispersion value α = Mv / Mn ≦ 1.9 (I) (where Mn is a number average molecular weight, Mv is a viscosity average molecular weight defined by the following formula (II), and μ in the following formula is 40) The melt viscosity at 0 ° C. is indicated by poise.) Mv = antilog (0.494 log μ + 3.0646) (II) 2. A high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and an aliphatic polyether unit having a molecular weight distribution dispersion value α in the range represented by the following formula (I). It is composed of a polyetherester resin composition (X) having a polyetherester block copolymer (A) as a main component composed of a low-melting polymer segment (b) at a temperature of 250 ° C. and a load of 2160 g according to ASTM D1238. A polyester elastomer resin composition having a measured melt viscosity index (MFR value) of 10 g / 10 minutes or less. Molecular weight distribution dispersion value α = Mv / Mn ≦ 1.9 (I) (where Mn is a number average molecular weight, Mv is a viscosity average molecular weight defined by the following formula (II), and μ in the following formula is 40) The melt viscosity at 0 ° C. is indicated by poise.) Mv = antilog (0.494 log μ + 3.0646) (II) 3. The polyetherester block copolymer composition (X) is based on 100 parts by weight of the polyetherester block copolymer (A). At least one selected from isocyanate compounds (C) and alkali or alkaline earth metal salts of fatty acids (D) of 0.01 to 1
The polyester elastomer resin composition according to claim 2, wherein the polyester elastomer resin composition is blended with 0 parts by weight. 4. The polyetherester block copolymer composition (X) is based on 100 parts by weight of the polyetherester block copolymer (A) and α-olefin and α, 3 to 8 carbon atoms. An ionomer resin (E) in which a copolymer of β-unsaturated carboxylic acid is added with a metal ion having 1 to 3 valences, and an olefin copolymer (F) comprising an α-olefin and a glycidyl ester of α, β-unsaturated acid The polyester elastomer resin composition according to claim 2, wherein 1) to 25 parts by weight of each) are blended. 5. A polyester elastomer resin composition 100.
The aromatic amine-based antioxidant (G), hindered phenol-based antioxidant (H), sulfur-based antioxidant (I), and phosphorus-based antioxidant (J) were each added to 0.1 part by weight based on the weight. 5. The polyester elastomer resin composition according to claim 3, wherein the polyester elastomer resin composition is blended with any of the following combinations in an amount of from 0.01 to 5 parts by weight. [(G) alone, (H) + (I) combination, (H) +
(J) combination, (H) + (I) + (J) combination,
(G) + (H) + (I) combination, (G) + (H) +
Combination of (J), combination of (G) + (H) + (I) + (J)] 6. A polyester elastomer resin composition 100.
The polyamide resin (K) 0.1
The polyester elastomer resin composition according to claim 5, wherein the polyester elastomer resin composition is blended in an amount of from 20 to 20 parts by weight. 7. The high-melting crystalline polymer segment (a), which is a component of the polyetherester block copolymer (A), comprises a polybutylene terephthalate unit and / or
Or the polyester elastomer resin composition according to any one of claims 2 to 6, which is composed of polybutylene naphthalate units. 8. The aliphatic polyether constituting the low-melting polymer segment (b) which is a component of the polyetherester block copolymer (A) is a poly (tetramethylene oxide) glycol unit. 2-7
The polyester elastomer resin composition according to any one of the above. 9. The aliphatic polyether constituting the low-melting polymer segment (b), which is a component of the polyetherester block copolymer (A), has a number average molecular weight of 1300 to 3500. The polyester elastomer resin composition according to any one of items 1 to 8, above. 10. The molecular weight distribution dispersion value α of the aliphatic polyether constituting the low melting point polymer segment (b), which is a constituent of the polyetherester block copolymer (A), is 1.85 or less. Item 10. The polyester elastomer resin composition according to any one of Items 2 to 9. 11. The molecular weight distribution dispersion α of the aliphatic polyether constituting the low-melting polymer segment (b), which is a constituent of the polyetherester block copolymer (A), is 1.8 or less. Item 11. The polyester elastomer resin composition according to any one of Items 2 to 10. 12. The polyetherester block copolymer (A) according to claim 2, wherein the copolymerization amount of the low melting point polymer segment (b) is 10 to 80% by weight. Polyester elastomer resin composition. 13. The polyetherester block copolymer (A) according to claim 2, wherein the copolymerization amount of the low melting point polymer segment (b) in the block copolymer (A) is 30 to 70% by weight. Polyester elastomer resin composition. 14. The method according to claim 1, wherein the temperature is 2
Melt viscosity index (MF) measured at 50 ° C. under a load of 2160 g
The polyester elastomer resin composition according to any one of claims 2 to 13, wherein the R value is 8 g / 10 minutes or less. 15. According to ASTM D1238, temperature 2
Melt viscosity index (MF) measured at 50 ° C. under a load of 2160 g
The polyester elastomer resin composition according to any one of claims 2 to 14, wherein R value) is 5 g / 10 minutes or less. 16. The bifunctional or higher functional epoxy compound (B)
Is a glycidyl ester compound, The polyester elastomer resin composition of Claim 3. 17. The polyester elastomer resin composition according to claim 6, wherein the polyamide resin (K) is a copolymer polyamide resin. 18. The method according to claim 2, wherein the composition is used for blow molding.
8. The polyester elastomer resin composition according to any one of items 7 to 7. 19. The polyester elastomer resin composition according to claim 2, which is a molding composition for a flexible boot.