JP2013189550A - Heat-resistant thermoplastic elastomer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant thermoplastic elastomer resin composition having strength, rigidity and flexibility necessary for a molded article and excellent also in heat resistance and moldability.SOLUTION: This heat-resistant thermoplastic elastomer resin composition is obtained by combining 100 pts.wt. of a thermoplastic elastomer composition, that is prepared by mixing 60-98 wt.% of a polyester block copolymer (A), having as constituents a high-melting crystalline polymer segment (a3) in which a dicarboxylic acid component comprises terephthalic acid or its ester forming derivative (a1) and at least one dicarboxylic acid other than terephthalic acid or its ester forming derivative (a2) and a low-melting polymer segment (a4) comprising an aliphatic polyether unit and/or an aliphatic polyester unit, and 2-40 wt.% of a polyester resin (B), with 0.1-15 pts.wt. of a glycidyl group-modified polyolefin resin (C) and 0.01-5 pts.wt. of an antioxidant (D).

Description

  The present invention relates to a heat-resistant thermoplastic elastomer composition that is flexible and has excellent heat resistance and excellent moldability.

  A polyester block copolymer having a crystalline aromatic polyester unit as a hard segment and an aliphatic polyether unit such as poly (alkylene oxide) glycol and / or an aliphatic polyester unit such as polylactone as a soft segment has a strength, It is widely used in automotive parts and industrial materials because it has excellent mechanical properties such as impact resistance, elastic recovery, and flexibility, as well as low and high temperature properties, and is thermoplastic and easy to mold.

  However, the flexibility of the above-mentioned polyester block copolymer generally becomes more flexible as the soft segment ratio is larger, while its heat resistance has a property of becoming better as the hard segment ratio is higher. Due to this property, high-hardness polyester block copolymers are used in applications that require heat resistance, and cross-linked rubber is still used in applications that require more flexibility and heat resistance. is there. Therefore, the actual condition is that the flexible polyester block copolymer is only applied to a portion having a low heat resistance requirement.

  However, in recent years, it has been required to provide thermoplastic elastomers that have both heat resistance and flexibility in consideration of environmental issues in automobile parts and industrial materials. Therefore, polyester block copolymers also have heat resistance. Various improvements have been reported and development of thermoplastic elastomers having both heat resistance and flexibility has been reported.

  For example, a block polyether ester copolymer composition obtained by adding a polyamide resin and a hindered phenol-based antioxidant, a sulfur-based antioxidant and / or a phosphorus-based antioxidant to a polyether ester block copolymer (for example, Patent Document 1), and polyester elastomer resin in which aromatic amine antioxidant, hindered phenol antioxidant, sulfur antioxidant, phosphorus antioxidant and / or polyamide resin are added to polyester elastomer A composition (see, for example, Patent Document 2) has been proposed, but in such a configuration, as long as it is basically a polyetherester block copolymer, it can be improved to some extent but has flexibility and flexibility. It was difficult to satisfy heat resistance at a high level.

  Further, a thermoplastic elastomer composition obtained by dynamically crosslinking a covalently crosslinked acrylic rubber with a polyfunctional compound to a thermoplastic polyester resin (see, for example, Patent Document 3), a thermoplastic copolyester elastomer and an epoxy group-containing and / or Alternatively, a thermoplastic elastomer composition (for example, see Patent Document 4) obtained by dynamically crosslinking a carboxy group-containing (meth) acrylate copolymer rubber by melt kneading, and a thermoplastic copolyester elastomer having a specific hard / soft ratio There has been proposed a thermoplastic elastomer composition (for example, see Patent Document 5) in which an acrylic rubber or an ethylene component-containing rubber containing acrylic acid and an alkyl ester moiety is dynamically crosslinked in the presence of a known crosslinking agent. However, with such a configuration, the strength, rigidity and flexibility required for hoses, tubes and ducts To obtain both the cause composition and heat resistance has been difficult. Furthermore, a heat resistant thermoplastic elastomer resin composition (see, for example, Patent Document 6) obtained by blending a polyester block copolymer, a dynamically crosslinked thermoplastic elastomer composition, and a heat resistant material in a specific ratio has been proposed. However, in this configuration, the ductile deformation region is small and the surface appearance of the molded product is inferior.

JP-A-2-173059 (pages 1 and 2) JP-A-11-323109 (pages 2 and 3) JP-A-1-306447 (pages 1 and 2) Japanese Patent Laid-Open No. 5-25376 (2nd page) JP 2000-351889 A (2nd page) JP 2009-29990 A (pages 1 and 2)

  The present invention has been achieved as a result of studies to solve the above-mentioned problems of the prior art, has the strength, rigidity and flexibility necessary for applications requiring heat resistance, and has excellent heat resistance, molding. An object of the present invention is to provide a heat-resistant thermoplastic elastomer resin composition excellent in processability.

In order to achieve the above object, according to the present invention,
The dicarboxylic acid component is composed of terephthalic acid or its ester-forming derivative (a1) and at least one dicarboxylic acid other than terephthalic acid or its ester-forming derivative (a2), and the molar ratio of (a2) to (a1) (( a1) / (a2)) from a high-melting-point crystalline polymer segment (a3) comprising a crystalline aromatic polyester unit of 0.2 to 7.0, an aliphatic polyether unit and / or an aliphatic polyester unit A thermoplastic elastomer composition comprising a polyester block copolymer (A) 60 to 98% by weight and a polyester resin (B) 2 to 40% by weight comprising a low melting point polymer segment (a4) as a constituent component. 0.1 to 15 parts by weight of a glycidyl group-modified polyolefin resin (C), 0.1 parts by weight of an antioxidant (D) with respect to 100 parts by weight. Heat thermoplastic elastomer resin composition obtained by blending 1 to 5 parts by weight is provided.

  According to the present invention, a heat-resistant thermoplastic elastomer resin composition having excellent heat resistance, particularly long-term heat aging resistance, and excellent mechanical properties such as strength and flexibility can be obtained.

  The heat-resistant thermoplastic elastomer resin composition of the present invention has sufficient strength, rigidity and flexibility as a molded body, and also has high heat resistance, so that it is particularly flexible for automobile parts, electrical equipment, industrial products, etc. In addition, it is suitable for products that require heat resistance, and can be widely applied particularly in applications that have both flexibility and a heat resistance life longer than that of conventional products.

  Hereinafter, the present invention will be described in detail.

  The high melting point crystalline polymer segment (a3) of the polyester block copolymer (A) used in the present invention is a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4 ′. -Dicarboxylic acid, diphenoxyethane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate and the like. Although aromatic dicarboxylic acid is mainly used, if necessary, a part of the aromatic dicarboxylic acid may be converted to alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, etc. Alternatively, it may be substituted with an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Of course, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can be used equally.

  The polyester block copolymer (A) used in the present invention comprises at least one dicarboxylic acid other than terephthalic acid or its ester formation in addition to terephthalic acid or its ester-forming derivative (a1) as a constituent dicarboxylic acid component. Including the derivative (a2), the molar ratio of (a2) to (a1) ((a1) / (a2)) is 0.2 to 7.0, preferably 0.3 to 6.0. If the molar ratio of (a2) to (a1) is less than 0.2, the moldability deteriorates, and if it exceeds 7.0, the heat resistance decreases.

  The diol or the ester-forming derivative thereof forming the high-melting crystalline polymer segment (a3) of the polyester block copolymer (A) includes diols having a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol , Trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol and other aliphatic diols, 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol, etc. Alicyclic diols, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2 Hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quaterphenyl, etc. Aromatic diols of the above are preferred, and such diols can also be used in the form of ester-forming derivatives such as acetyl compounds and alkali metal salts.

  The low melting point polymer segment (a4) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether and / or an aliphatic polyester. Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (trimethylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and a combination of ethylene oxide and propylene oxide. And a polymer, an ethylene oxide addition polymer of poly (propylene oxide) glycol, a copolymer glycol of ethylene oxide and tetrahydrofuran, and the like. Examples of the aliphatic polyester include poly (ε-caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. From the elastic properties of the polyester block copolymers obtained from these aliphatic polyethers and / or aliphatic polyesters, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adducts, ethylene oxide and tetrahydrofuran Are preferably used such as copolymer glycol, poly (ε-caprolactone), polybutylene adipate, and polyethylene adipate, among which poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, and The use of a copolymer glycol of ethylene oxide and tetrahydrofuran is preferred. The number average molecular weight of these low-melting polymer segments is preferably about 300 to 6000 in the copolymerized state.

  The amount of copolymerization of the high-melting crystalline polymer segment (a3) and the low-melting polymer segment (a4) of the polyester block copolymer (A) used in the present invention is the same as that of the high-melting crystalline polymer segment (a3). The weight ratio of the low-melting polymer segment (a4) is preferably 85/15 to 35/65, more preferably 85/15 to 40/60.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. Specific examples thereof include, for example, a method of transesterifying a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol and a low melting point polymer segment component in the presence of a catalyst, and polycondensing the resulting reaction product, and Any method such as a method in which a dicarboxylic acid, an excess amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst and the resulting reaction product is polycondensed may be used. Examples of such commercially available polyester elastomers include “Primalloy” manufactured by Mitsubishi Chemical Corporation, “Perprene” manufactured by Toyobo Co., Ltd., “Hytrel” manufactured by Toray DuPont Co., Ltd., and the like.

  The polyester resin (B) used in the present invention includes at least one acid component selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, and the like, ethylene glycol, propylene glycol, butylene glycol, hexylene. It is obtained by polycondensation with at least one diol component selected from glycol, polyethylene glycol, polyalkylene glycol such as polytetramethylene glycol, and the like. Specifically, polybutylene terephthalate (PBT), polypropylene terephthalate ( PPT), polyethylene terephthalate (PET), polyhexylene terephthalate (PHT), polyethylene naphthalate, polybutylene naphthalate (PBN), polycyclohexane-1,4-dimethylol In addition to such terephthalate, polyethylene isophthalate-terephthalate (PET / I), etc. copolymerized polyester such as polybutylene iso freight isophthalate (PBT / I) can be exemplified. Among these polyester resins, the most effective results are obtained when PET, PBT, PEN, and PBN are used.

  The heat-resistant thermoplastic elastomer resin composition of the present invention is obtained by mixing 60 to 98% by weight of the polyester block copolymer (A) and 2 to 40% by weight of the polyester resin (B). The polyester block copolymer (A) is preferably 65 to 98% by weight, more preferably 70 to 98% by weight, and the polyester resin (B) is preferably 2 to 35% by weight, more preferably 2 to 2% by weight. 30% by weight. When the blending amount of the polyester resin (B) is less than 2% and exceeds 40% by weight, the heat resistance is remarkably lowered.

  The heat resistant thermoplastic elastomer resin composition of the present invention comprises 100 parts by weight of a thermoplastic elastomer composition obtained by mixing 60 to 98% by weight of a polyester block copolymer (A) and 2 to 40% by weight of a polyester resin (B). In contrast, 0.1 to 15 parts by weight of a glycidyl group-modified polyolefin resin (C) and 0.01 to 5 parts by weight of an antioxidant (D) are blended.

  The glycidyl group-modified polyolefin resin (C) used in the present invention is preferably a terpolymer composed of α-olefin, α, β-unsaturated acid and glycidyl ester of α, β-unsaturated acid. Examples of the α-olefin include ethylene, propylene, and butene-1, and among these, ethylene is preferably used. Examples of the α, β-unsaturated acid include vinyl esters such as vinyl ethers, vinyl acetate, and vinyl propionate, esters of acrylic acid and methacrylic acid such as methyl, ethyl, propyl, and butyl, acrylonitrile, and styrene. Among them, butyl acrylate and methyl methacrylate are preferably used. Furthermore, examples of the glycidyl ester of α, β-unsaturated acid include acrylic acid glycidyl ester, methacrylic acid glycidyl ester, and ethacrylic acid glycidyl ester. Among them, methacrylic acid glycidyl ester is preferably used.

  The compounding quantity of glycidyl group modification | denaturation polyolefin resin (C) is 0.1-15 weight part with respect to 100 weight part of thermoplastic polyester elastomers (A), Preferably it is 0.1-12 weight part. If the amount is less than 0.1 part by weight, the degree of improvement of the intended effect is small, and if the blending amount exceeds 15 parts by weight, gelation occurs due to melt retention during molding, and the moldability deteriorates.

  The antioxidant (D) used in the present invention is one selected from the group consisting of aromatic amine antioxidants, hindered phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants. Or two or more.

  Specific examples of the aromatic amine antioxidant include phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, and 4-isopropoxydiphenylamine. However, among these, the use of diphenylamine compounds is preferred.

  Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy Methyl-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- Chlorylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-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, diethyl ester of 3,5-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-tert-butyl-4-hydroxyphenol) propionate], N, N′-hexamethylene-bis (3,5-di-tert-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-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris ( , 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, tris [β- (3,5-di-t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate, and the like. Among these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

  The sulfur-based antioxidant is a compound containing sulfur such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. Among these, the use of a thiodipropion ester-based compound is particularly preferable.

  The phosphorus-based antioxidant is a compound containing phosphorus such as phosphoric acid, phosphorous acid, hypophosphorous acid derivative, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite. Among these, it is preferable to use a compound having a sulfur atom in the molecule and a compound having two or more phosphorus atoms in the molecule.

  The total amount of these antioxidants is 0.01 to 5 parts by weight, preferably 100 parts by weight of the thermoplastic elastomer obtained by mixing the polyester block copolymer (A) and the polyester resin (B). Is 0.05 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight. When the total amount of antioxidants is less than 0.01 parts by weight, the degree of obtaining the desired improvement effect is small, and when it exceeds 5 parts by weight, blooming occurs or the mechanical strength of the polyester block copolymer Decreases.

  The heat resistance can be improved by further adding a polyamide resin (E) to the heat resistant thermoplastic elastomer composition of the present invention.

  The polyamide resin (E) used in the heat-resistant thermoplastic elastomer composition of the present invention is a polymer compound having an amide bond in the molecular chain, such as 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 polyamide resins may be copolymers, or two or more different polymers may be used in combination. Among these polyamide resins, when nylon 6 and / or binary or ternary or higher copolymer polyamide resin is used, even higher effects can be obtained.

  The compounding amount of the polyamide resin (E) is 0.5 to 10 parts by weight, preferably 100 parts by weight of the thermoplastic elastomer obtained by mixing the polyester block copolymer (A) and the polyester resin (B). 1 to 8 parts by weight, more preferably 1 to 5 parts by weight. When the blending amount of the polyamide resin (E) is less than 0.5 parts by weight, the degree of obtaining the intended improvement effect is small, and when it exceeds 10 parts by weight, the polyether ester block copolymer originally has. Since flexibility and rubber-like properties are impaired, it is not preferable.

  Furthermore, in addition to the additives (C) to (E), various additives can be added to the heat-resistant thermoplastic elastomer resin composition of the present invention as long as the object of the present invention is not impaired. For example, known molding auxiliaries such as crystal nucleating agents and lubricants, UV absorbers and light-resistant agents such as hindered amine compounds, hydrolysis resistance improvers, colorants such as pigments and dyes, antistatic agents, conductive agents, flame retardants, Reinforcing agents, fillers, plasticizers, release agents and the like can be optionally contained.

  Although the manufacturing method of the heat-resistant thermoplastic elastomer resin composition of this invention is not specifically limited, For example, a predetermined antioxidant (D) is added to a polyester block copolymer (A) and a polyester resin (B). Or a raw material blended with a polyester block copolymer (A) and a polyester resin (B) with a predetermined antioxidant (D) and a polyamide resin (E) is supplied to a screw extruder and melted. First, the polyester block copolymer (A) and the polyester resin (B) are supplied and melted in a kneading method or a screw type extruder, and then the antioxidant (D) or other compound is added from another supply port. A method of feeding and kneading the product and further feeding and kneading the polyamide resin (E) from another supply port can be appropriately employed.

  The heat-resistant thermoplastic elastomer resin composition of the present invention preferably has a Shore D hardness (JIS K 7215 (1986 edition)) of 40D or more and 75D or less, and is molded by injection molding, blow molding, extrusion molding, compression molding or the like. It is assumed to be a body.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples, and can be implemented with appropriate modifications within the scope of the gist of the present invention.

  In the following examples and comparative examples, “parts” and “%” indicate weight units unless otherwise specified.

  Moreover, the hardness, tensile breaking strength, tensile breaking elongation, heat aging resistance, and surface appearance of the heat resistant thermoplastic elastomer resin compositions in the following examples and comparative examples were evaluated by the following methods.

[hardness]
A pellet that has been hot-air dried at 90 ° C. for 3 hours or more is molded into a 120 × 75 × 2 mm thick square plate under molding conditions of a predetermined cylinder temperature and mold temperature using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries). Measured according to K 7215 (1986 edition).

[Tensile breaking strength, tensile breaking elongation]
JIS K7113 (1995 edition) No. 2 dumbbell, using pellets dried with hot air at 90 ° C. for 3 hours or more, using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries) under the molding conditions of a predetermined cylinder temperature and mold temperature A test piece was molded and measured according to JIS K7113 (1995 edition).

[Heat-resistant]
JIS K 7113 (1995 edition), pellets that had been hot-air dried at 90 ° C. for 3 hours or more were molded using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries) under molding conditions of a predetermined cylinder temperature and mold temperature. The No. 2 type test piece was left in a hot air oven at 170 ° C. for 500 hours and then taken out, measured according to JIS K 7113 (1995 edition), and evaluated from the value of tensile elongation at break in the following three stages.
A: Tensile elongation at break is 100% or more.
○: The tensile elongation at break is 50% or more and less than 100%.
X: The tensile elongation at break is less than 50%.

[Surface appearance]
JIS K 7113 (1995 edition), pellets that had been hot-air dried at 90 ° C. for 3 hours or more were molded using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries) under molding conditions of a predetermined cylinder temperature and mold temperature. The surface appearance of the No. 2 type test piece was visually observed, and a molded product having a uniform surface was evaluated as ◯, and a molded product in which unevenness or roughness was observed on the surface was evaluated as x.

[Production of polyester block copolymer (A-1)]
443 parts of terephthalic acid, 190 parts of isophthalic acid, 600 parts of 1,4-butanediol and 177 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1000, 0.4 parts of titanium tetrabutoxide and mono-n-butyl- An esterification reaction was carried out while distilling the reaction water out of the system by charging the reaction vessel equipped with 0.1 parts of monohydroxytin oxide and a helical ribbon type stirring blade and heating at 190 to 225 ° C. for 3 hours. After adding 2.0 parts of titanium tetrabutoxide to the reaction mixture and adding 0.5 parts of “Irganox” 1098 (Hindered Phenolic Antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C., Subsequently, the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was performed for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and cut into pellets.

[Production of polyester block copolymer (A-2)]
330 parts of terephthalic acid, 96 parts of isophthalic acid, 403 parts of 1,4-butanediol and 467 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.3 part of titanium tetrabutoxide and mono-n-butyl- An esterification reaction was carried out while distilling the reaction water out of the system by charging the reaction vessel equipped with 0.1 parts of monohydroxytin oxide and a helical ribbon type stirring blade and heating at 190 to 225 ° C. for 3 hours. After adding 2.0 parts of titanium tetrabutoxide to the reaction mixture and adding 0.5 parts of “Irganox” 1098 (Hindered Phenolic Antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C., Subsequently, the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was performed for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and cut into pellets.

[Production of Polyester Block Copolymer (A-3)]
504 parts of terephthalic acid, 438 parts of 1,4-butanediol and 354 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.3 parts of titanium tetrabutoxide and mono-n-butyl-monohydroxytin oxide 0 The mixture was charged in a reaction vessel equipped with a helical ribbon type stirring blade together with 2 parts, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling the reaction water out of the system. After adding 2.0 parts of titanium tetrabutoxide to the reaction mixture and adding 0.5 parts of “Irganox” 1098 (Hindered Phenolic Antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C., Subsequently, the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was performed for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and cut into pellets.

  Table 1 shows the compositions and physical properties of the polymers A-1, A-2, and A-3 thus obtained.

[Polyester resin]
Toraycon 1400S (polybutylene terephthalate resin) manufactured by Toray Industries, Inc. was used as the polyester resin (B-1). Toraycon 1100S (polybutylene terephthalate resin) manufactured by Toray Industries, Inc. was used as the polyester resin (B-2).

[Glycidyl group-modified polyolefin resin]
As the glycidyl group-modified polyolefin resin (C-1), Bond First 7M manufactured by Sumitomo Chemical Co., Ltd. was used.

[Antioxidant]
Table 2 shows the abbreviations and structural formulas of the antioxidants (D-1), (D-2) and (D-3) used in the following Examples.

[Polyamide resin]
As the polyamide resin (E-1), Amilan CM4000 manufactured by Toray Industries, Inc. was used.

[Examples 1 to 5, Comparative Examples 1 to 4]
Polyether ester block copolymers (A-1), (A-2), (A-3) obtained in Reference Examples and polyester resins (B-1), (B-2) were modified with glycidyl group. The polyolefin resin (C-1), the antioxidants (D-1), (D-2), (D-3), and the polyamide resin (E-1) are all dried at a blending ratio as shown in Table 3. The mixture was blended and melt kneaded at a temperature setting of 220 ° C. to 250 ° C. using a twin screw extruder having a 45 mmφ screw, and then pelletized. This pellet was dried at 80 ° C. for 5 hours, and then injection molded under conditions of a cylinder temperature of 230 ° C. to 250 ° C. and a mold temperature of 50 ° C., and tests for hardness, tensile breaking strength, tensile breaking elongation, and heat aging test. I got a piece. Various tests were carried out on the obtained molded product. For heat aging, a tensile test was conducted after treatment in an oven at 170 ° C. for 500 hours. The surface appearance of the molded product was determined by visual inspection of the injection molded product. The test results are shown in Table 3.

  As is apparent from the results in Table 3, a glycidyl group-modified polyolefin resin, an antioxidant (aromatic amine type) is added to a thermoplastic elastomer obtained by mixing the polyester block copolymer and polyester resin shown in Examples 1 to 5. One or more of an antioxidant, a hindered phenol antioxidant, and a sulfur antioxidant) and a polyamide resin are blended with the heat-resistant thermoplastic elastomer resin composition of the present invention, which has hardness, tensile rupture strength, and tensile rupture. It has excellent elongation and heat aging properties as well as a molded product surface appearance. On the other hand, the resin compositions of Comparative Examples 1 to 5 that do not satisfy the conditions of the present invention have hardness, tensile breaking strength, tensile breaking elongation, heat aging property, and molded article surface appearance as compared with the resin compositions of the present invention. Either is inferior.

  In Comparative Example 1 in which the compounding amount of the polyester resin is larger than the conditions of the present invention, the tensile elongation at break is small, and the tensile elongation at break in heat aging is less than 50%, which is inferior. In Comparative Example 2 using a polyester block copolymer composed only of terephthalic acid as the dicarboxylic acid component, the tensile elongation at break in heat aging is less than 50%, which is inferior. In Comparative Examples 3 and 4 in which no polyester resin was blended, the heat aging treatment conditions of 170 ° C. and 500 hours could not be endured, and the heat aging property was extremely inferior. In Comparative Example 5 in which the glycidyl group-modified polyolefin resin, the antioxidant, and the polyamide resin are not blended, the tensile elongation at break in heat aging is less than 50%, which is inferior.

Claims (6)

The dicarboxylic acid component is composed of terephthalic acid or its ester-forming derivative (a1) and at least one dicarboxylic acid other than terephthalic acid or its ester-forming derivative (a2), and the molar ratio of (a2) to (a1) (( a1) / (a2)) from a high-melting-point crystalline polymer segment (a3) comprising a crystalline aromatic polyester unit of 0.2 to 7.0, an aliphatic polyether unit and / or an aliphatic polyester unit A thermoplastic elastomer composition comprising a polyester block copolymer (A) 60 to 98% by weight and a polyester resin (B) 2 to 40% by weight comprising a low melting point polymer segment (a4) as a constituent component. 0.1 to 15 parts by weight of a glycidyl group-modified polyolefin resin (C), 0.1 parts by weight of an antioxidant (D) with respect to 100 parts by weight. Heat thermoplastic elastomer resin composition that by blending from 1 to 5 parts by weight. The heat-resistant thermoplastic elastomer resin composition according to claim 1, wherein 0.5 to 10 parts by weight of a polyamide resin (E) is further blended with 100 parts by weight of the thermoplastic elastomer composition. The heat-resistant thermoplastic elastomer according to claim 1 or 2, wherein a weight ratio of the high-melting crystalline polymer segment (a3) and the low-melting polymer segment (a4) of the polyester block copolymer is 85/15 to 35/65. Resin composition. The heat-resistant thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein the Shore D hardness is 40D or more and 75D or less. The glycidyl group-modified polyolefin resin (C) is a terpolymer composed of an α-olefin, an α, β-unsaturated acid and a glycidyl ester of an α, β-unsaturated acid. 2. A heat-resistant thermoplastic elastomer resin composition according to item 1. The antioxidant (D) is one or more selected from the group consisting of aromatic amine antioxidants, hindered phenol antioxidants, sulfur antioxidants and phosphorus antioxidants. The heat-resistant thermoplastic elastomer resin composition according to any one of claims 1 to 5.