JP5413162B2 - Heat resistant thermoplastic elastomer resin composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer that is flexible and has excellent heat resistance and is suitable for extrusion molding, blow molding, and injection molding.

  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 obtained by dynamically crosslinking a carboxy group-containing (meth) acrylate copolymer rubber by melt kneading (see, for example, Patent Document 3), 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 investigations to solve the above-mentioned problems of the prior art, and has the strength, rigidity and flexibility necessary for applications requiring heat resistance, excellent heat resistance, and extrusion. An object of the present invention is to provide a heat-resistant thermoplastic elastomer resin composition suitable for molding and blow molding.

That is, the present invention refers to a high-melting-point crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester units and a low-melting-point polymer segment (a2) mainly composed of aliphatic polyether units and / or aliphatic polyester units. And a flexible polyester block copolymer (A1) having a melting point of less than 205 ° C. (51 to 95% by weight), a high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit, 49 to 5 weights of a high-hardness polyester block copolymer (A2) having a melting point of 205 ° C. or higher mainly comprising a low-melting polymer segment (a2) mainly composed of aliphatic polyether units and / or aliphatic polyester units. 10% to 35% by weight of a polyester elastomer resin composition (A) Polyacrylate, polymethacrylate, acrylate / methacrylate copolymer, polyethylene / acrylate copolymer, polyethylene / methacrylate copolymer crosslinkable with 10 to 50% by weight of polyalkylene phthalate polyester polymer and / or copolymer (b1) When melt-mixing a mixture of at least one (co) polymer (b2) 50 to 90% by weight selected from a polymer and a polyethylene / acrylate / methacrylate copolymer in an extruder in the presence of a radical generator An aromatic amine-based antioxidant and a hindered phenol-based antioxidant with respect to 100 parts by weight of a thermoplastic elastomer composition obtained by mixing 10 to 35% by weight of a dynamically crosslinked thermoplastic elastomer (B) , Comprising a sulfur-based antioxidant and a phosphorus-based antioxidant It is one or more consisting of heat stabilizers (C) heat thermoplastic elastomer resin composition characterized by comprising blending 0.01 to 5 parts by weight was further selected.

The heat-resistant thermoplastic elastomer resin composition of the present invention is
In addition to the components (A1), (A2), (B), and (C), the polyamide resin (D) is further blended in an amount of 0.5 to 10 parts by weight,
The polyalkylene phthalate polyester polymer and / or copolymer (b1) is selected from polyalkylene terephthalate, polyalkylene terephthalate copolymer, polyalkylene isophthalate polyether ester and polyalkylene terephthalate copolymer polyether ester. At least one selected,
At least one selected from the dynamically cross-linked polyacrylates, polymethacrylates, acrylate / methacrylate copolymers, polyethylene / acrylate copolymers, polyethylene / methacrylate copolymers and polyethylene / acrylate / methacrylate copolymers ( co) polymer (b2) are, that it is a polyacrylate elastomer and / or polyethylene acrylate elastomers are preferred.

  According to the present invention, as described below, 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.

  Hereinafter, the present invention will be described in detail.

  The high-melting crystalline polymer segment (a1) of the polyester block copolymer (A1) (A2) used in the present invention is mainly composed of an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative. Specific examples of aromatic dicarboxylic acids that are formed are terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl- Examples include 4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. 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.

  Specific examples of the diol include diols having a molecular weight of 400 or less, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, , 1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, alicyclic diols such as tricyclodecane dimethanol, 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 Aromatic diols such as 4,4′-dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl are preferred, and such diols are ester-forming derivatives such as acetyl compounds and alkali metal salts. It can also be used in the form.

  Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination. An example of a preferable high-melting crystalline polymer segment (a1) is a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Also preferred are those composed of polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate, and polybutylene isophthalate units derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol. .

  The low-melting point polymer segment (a2) of the polyester block copolymers (A1) and (A2) 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 (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) Examples thereof include ethylene oxide addition polymers of glycol and copolymer glycols of ethylene oxide and tetrahydrofuran. 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 flexible polyester block copolymer (A1) having a melting point of less than 205 ° C. used in the present invention means that the melting point measured by a differential scanning calorimeter (DSC) is less than 205 ° C., preferably a high melting point. The crystalline polymer segment (a1) is 1 to 55% by weight, and the low melting point polymer segment (a2) is 99 to 45% by weight.

  Further, the high hardness polyester block copolymer (A2) having a melting point of 205 ° C. or higher used in the present invention means that the melting point measured by a differential scanning calorimeter (DSC) is 205 ° C. or higher. The high melting point crystalline polymer segment (a1) is 55 to 99% by weight, and the low melting point polymer segment (a2) is 45 to 1% by weight.

  The polyester block copolymers (A1) and (A2) 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.

  In the polyester elastomer resin composition (A) of the present invention, the flexible polyester block copolymer (A1) is 51 to 95% by weight, the high hardness polyester block copolymer (A2) is 49 to 5% by weight, preferably the flexible polyester. The block copolymer (A1) is 55 to 90% by weight, the high hardness polyester block copolymer (A2) is 45 to 10% by weight, and the flexible polyester block copolymer (A1) is less than 51% by weight and high hardness. When the polyester block copolymer (A2) is 49% by weight or more, the resulting heat-resistant thermoplastic elastomer resin composition has insufficient flexibility and toughness, and the flexible polyester block copolymer (A1) is 95% by weight or more. Heat-resistant thermoplastic elastomer tree obtained when the high-hardness polyester block copolymer (A2) is less than 5% by weight It is not preferable because the moldability of the composition is poor.

  The dynamically crosslinked thermoplastic elastomer composition (B) used in the present invention comprises 10 to 50% by weight of the polyalkylene phthalate polyester polymer and / or copolymer (b1) and 50 to 90% by weight of the crosslinked polymer. At least one (co) polymer selected from possible polyacrylates, polymethacrylates, acrylate / methacrylate copolymers, polyethylene / acrylate copolymers, polyethylene / methacrylate copolymers and polyethylene / acrylate / methacrylate copolymers When the mixture with (b2) is melt-mixed in an extruder in the presence of a radical generator, it is dynamically crosslinked.

  In this case, when the polyalkylene phthalate polyester (co) polymer (b1) is 10% by weight or less, the polyalkylene phthalate polyester (co) polymer does not become a continuous phase, and the heat processability such as injection molding or extrusion molding is improved. This is not preferable because it is significantly reduced. Further, if the polyalkylene phthalate polyester (co) polymer (b1) exceeds 50% by weight, the balance of hot water resistance, weather resistance, heat resistance and flexibility is unfavorable.

  A known method can be used for dynamic crosslinking of the polyalkylene phthalate polyester (co) polymer (b1) and the (co) polymer (b2). Examples of the method for forming this dynamically crosslinked thermoplastic elastomer (B) include polyalkylene phthalate polyester (co) polymer (b1), (co) polymer (b2), and radicals as an appropriate amount of a crosslinking agent. Generators such as 2,5-dimethyl-2,5- (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, t-butylperoxybenzo And crosslinking aids such as diethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, N, N′-m-phenylene dimaleimide, triallyl isocyanate, and the like Antioxidants such as n-octadecyl-3- (3 ′, 5′- -T-butyl-4'-hydroxyphenyl) -propionate, n-octadecyl-3- (3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate ], 1,4-butanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], triethylene glycol-bis- [3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di-t-butyl) -4'-hydroxyphenyl) propionylhexamethylenediamine, N, N'-tetramethylene-bis-3- (3'-methyl-5'-t-butyl-4'-hydroxyphenol) propionyldiamine, N, N ' -Bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) Particularly preferred are mino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Are triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4'-Hydroxyphenyl) propionate] A method of dynamically cross-linking hindered phenolic antioxidants such as methane and the like with an extruder or an injection molding machine can be used.

  The polyalkylene phthalate polyester or copolymer (b1) used in the dynamically crosslinked thermoplastic elastomer composition (B) used in the present invention is composed of a high-melting crystalline polymer segment (a1) and mainly a fat. Is a polyester block copolymer mainly composed of a low melting point polymer segment (a2) composed of an aromatic polyether unit and / or an aliphatic polyester unit, and the high melting point crystalline polymer segment (a1) is an aromatic Polyesters formed from dicarboxylic acids or their ester-forming derivatives and aliphatic diols, preferably polybutylene terephthalates derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. And isophthalic acid, phthalic acid, naphthalene-2,6 Dicarboxylic acid components such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and molecular weight Diols of 300 or less, such as aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethylol, etc. Alicyclic diol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2 − Fragrances such as droxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quarterphenyl It may be a polyester derived from a group diol or the like, or a copolyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component, and the like in a range of 5 mol% or less.

  Two or more of these dicarboxylic acids and their derivatives or diol components may be used in combination. Examples of preferred high melting crystalline polymer segments are polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Further, polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and polybutylene derived from isophthalic acid and / or dimethylisophthalate and 1,4-butanediol. Those composed of isophthalate units are also preferably used.

  The low melting point polymer segment of the polyester block copolymer is an aliphatic polyether and / or an aliphatic polyester. Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) Examples thereof include ethylene oxide addition polymers of glycol and copolymer glycols of ethylene oxide and tetrahydrofuran. 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 Preferred are the use of copolymer glycols, poly (ε-caprolactone), polybutylene adipate, and polyethylene adipate, among which poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adducts, 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 copolymerization amount of the low melting point polymer segment in the polyester block copolymer used in the dynamically crosslinked thermoplastic elastomer composition (B) used in the present invention is preferably 15 to 90% by weight, more preferably It is in the range of 30 to 85% by weight.

  The (co) polymer (b2) used in the dynamically crosslinked thermoplastic elastomer (B) used in the present invention is an acrylic rubber, and the crosslinked product is one or more acrylic esters or methacrylic esters. Acid esters, and also copolymers of mixtures thereof, or linear copolymers formed from copolymers of ethylene and one or more acrylic or methacrylic esters or mixtures thereof. The acrylic rubber contains ethylene as a main component, and the acrylate can be cross-linked even at 6.5 mol%, but the acrylate is preferably 20 mol% or more from the viewpoint of compression set. In addition, poly (meth) acrylate and polyethylene / (meth) acrylate are linear copolymers that are inherently crosslinkable with organic peroxides and organic diene-based crosslinking aids, and especially require a third monomer necessary for crosslinking. However, a crosslinking site monomer can be added as long as it does not affect the degree of crosslinking reached by dynamic crosslinking with a free radical initiator.

  The uncrosslinked acrylic rubber used in the dynamically crosslinked thermoplastic elastomer (B) used in the present invention is ethylene and one or more alkyl esters of acrylic acid, methacrylic acid or a mixture thereof, for example, alkyl acrylate. A copolymer of ˜60% by weight is preferred.

  The production method of the dynamically crosslinked thermoplastic elastomer (B) used in the present invention can be produced by a known method. For example, a thermoplastic resin component containing a polyalkylene phthalate polyester polymer and / or copolymer (b1) and a rubber component made of uncrosslinked acrylic rubber are melt-kneaded with a twin-screw kneading extruder or the like to obtain a continuous phase. The rubber component is dispersed as a dispersed phase (domain) in the thermoplastic resin forming the (matrix phase). Next, in order to cross-link the rubber component, a cross-linking agent (free radical generator) and an organic diene-based cross-linking aid are added under kneading to dynamically cross-link the rubber component. Further, various compounding agents for the thermoplastic resin or the rubber component may be added during the kneading, but it is preferable to premix them before kneading. At this time, a crosslinking agent may be mixed in advance in the rubber component, and vulcanization may be simultaneously performed while kneading the thermoplastic resin and the rubber component. The kneading machine used for kneading the thermoplastic resin and the rubber component is not particularly limited, and a screw extruder, a kneader, a Banbury mixer, a biaxial kneading extruder, or the like can be used. Among these, it is preferable to use a twin-screw kneading extruder for kneading the thermoplastic resin and the rubber component and for dynamic vulcanization of the rubber component. Further, two or more types of kneaders may be used and kneaded sequentially.

  The dynamically crosslinked thermoplastic elastomer (B) thus obtained is finely dispersed in a vulcanized rubber phase in which at least a part is a discontinuous phase in a thermoplastic resin phase in which at least a part is a continuous phase. Therefore, the dynamically crosslinked thermoplastic elastomer (B) exhibits the same behavior as the crosslinked rubber, and at least the continuous phase is a thermoplastic resin phase. Processing according to plastic resin is possible. Commercially available products of such dynamically crosslinked thermoplastic elastomer (B) include “Du Pont ™ ETPV” manufactured by Du Pont.

In the heat-resistant thermoplastic elastomer resin composition of the present invention, the polyester elastomer resin composition (A) is 90 to 65% by weight, and the dynamically crosslinked thermoplastic elastomer (B) is 10 to 35% by weight. Become .

The heat-resistant agent (C 1 ) used in the present invention is one selected from the group consisting of an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant, or Ru der 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 with respect to 100 parts by weight of the thermoplastic elastomer obtained by mixing the polyester elastomer resin composition (A) and the dynamically crosslinked thermoplastic elastomer composition (B). 0.01 to 5 parts by weight, preferably 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 machine of the heat-resistant thermoplastic elastomer resin composition It is not preferable because the mechanical strength is lowered.

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

  The polyamide resin (D) 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 blending amount of the polyamide resin (D) is 0. 0 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer obtained by mixing the polyester elastomer resin composition (A) and the dynamically crosslinked thermoplastic elastomer composition (B). 5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 1 to 5 parts by weight. When the blending amount of the polyamide resin (D) 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 heat resistant thermoplastic elastomer resin composition originally has. Since flexibility and rubber-like properties are impaired, it is not preferable.

  Furthermore, in addition to the additives (C) to (D), 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.

  The method for producing the heat-resistant thermoplastic elastomer resin composition of the present invention is not particularly limited. For example, the flexible polyester block copolymer (A1), the high-hardness polyester elastomer block copolymer (A2), A method of supplying a raw material in which a predetermined heat-resistant agent (C) is blended with a thermoplastic elastomer composition (B) that has been cross-linked, and a raw material in which a predetermined polyamide resin is blended, to a screw-type extruder and melt-kneading, or screw First, a flexible polyester block copolymer (A1) and a high-hardness polyester elastomer block copolymer (A2) are supplied to a mold extruder to produce a polyester elastomer resin composition (A). A polyester elastomer resin composition (A) is prepared separately. A screw containing a dynamically crosslinked thermoplastic elastomer composition (B) and a heat-resistant agent (C) It can be appropriately employed a method of melt kneading and fed into the extruder.

  The heat-resistant thermoplastic elastomer resin composition of the present invention can be molded by various methods such as injection molding, blow molding, extrusion molding, and compression molding.

  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, “parts” and “%” indicate weight units unless otherwise specified.

  In addition, the hardness, tensile breaking strength, tensile breaking elongation, heat aging resistance, blow moldability, and extrusion moldability of the heat resistant thermoplastic elastomer resin compositions in the following 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 K7215.

[Tensile breaking strength, tensile breaking elongation]
JIS K7113 No. 2 dumbbell specimens are molded from pellets that have been hot-air dried at 90 ° C for 3 hours or longer using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries) under the molding conditions of the specified cylinder temperature and mold temperature. And measured according to JIS K7113.

[Heat-resistant]
JIS K 7113 No. 2 type test, in which pellets dried with hot air at 90 ° C. for 3 hours or more were molded under the molding conditions of a predetermined cylinder temperature and mold temperature using an injection molding machine (NEX-1000 manufactured by Nissei Plastic Industries) The piece was left in a hot air oven at a predetermined temperature for 1000 hours and then taken out and measured according to JIS K 7113.

[Blow moldability]
Pellets dried with hot air at 90 ° C. for 3 hours or more using a press blow molding machine (SBE50 / 140 model manufactured by Osberger) under the molding conditions of a predetermined cylinder temperature, nozzle temperature, mold temperature, diameter 60 mm, high A straight bottle having a thickness of 1 mm was molded using a 190 mm-thick mold, and the thicknesses of the upper, middle and lower portions of the bottle molded product were measured. The evaluation was evaluated with a rank where ○: the uneven thickness of the bottle was 1 mm or less, and X: the uneven thickness of the bottle was over 1 mm.

[Extrudability]
Pellets dried in hot air at 90 ° C. for 3 hours or more using a φ30 single screw extruder under the predetermined cylinder temperature, adapter temperature, and die temperature molding conditions using water-cooled vacuum sizing, outer diameter φ8 mm, inner diameter φ6 mm The tube was molded, and the thickness of the tube molded product was measured. The evaluation was evaluated with a rank of ◯: tube thickness deviation of 0.5 mm or less and x: tube thickness deviation of more than 0.5 mm.

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

[Melting point measurement]
DSC Q100 manufactured by TA Instruments Inc. was used, and the melting point was measured by heating from room temperature to 240 ° C. at a rate of temperature increase of 10 ° C./min.
[Flexible polyester block copolymer (A-1-1)]
Made by Toray DuPont Co., Ltd. Hytrel 3046 Melting point 160 ° C
[Flexible polyester block copolymer (A-1-2)]
Made by Toray DuPont Co., Ltd. Hytrel 5077 Melting point 202 ° C
[Flexible polyester block copolymer (A-1-3)]
Made by Toray DuPont Co., Ltd. Hytrel 4057 Melting point 163 ° C

[Production of High Hardness Polyester Block Copolymer (A-2-1)]
302 parts of terephthalic acid, 327 parts of 1,4-butanediol and 216 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 are placed in a reaction vessel equipped with a helical ribbon stirring blade together with 0.15 part of titanium tetrabutoxide. The esterification reaction was performed while charging and heating the reaction water at 190 to 225 ° C for 3 hours to distill the reaction water out of the system. After adding 0.75 part of “Irganox” 1010 (a hindered phenol antioxidant manufactured by Ciba Geigy Co., Ltd.) to the reaction mixture, the temperature was raised to 245 ° C. The pressure was reduced to 2 mmHg, and polymerization was performed for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged in the form of strands into water, and cutting was performed to obtain pellets. The resulting pellet had a melting point of 208 ° C.

[Production of high hardness polyester block copolymer (A-2-2)]
384 parts of terephthalic acid, 416 parts of 1,4-butanediol, and 101 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1000 are placed in a reaction vessel equipped with a helical ribbon type stirring blade together with 0.15 part of titanium tetrabutoxide. The esterification reaction was performed while charging and heating the reaction water at 190 to 230 ° C. for 3 hours to distill the reaction water out of the system. After adding 0.75 part of “Irganox” 1010 (a hindered phenol antioxidant manufactured by Ciba Geigy Co., Ltd.) to the reaction mixture, the temperature was raised to 245 ° C. The pressure was reduced to 2 mmHg, and polymerization was performed for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged in the form of strands into water, and cutting was performed to obtain pellets. The melting point of the obtained pellet was 218 ° C.

[Production of Dynamically Crosslinked Thermoplastic Elastomer (B-1)]
100 parts of a polyethylene / acrylate elastomer (for example, Baymac manufactured by DuPont) obtained by copolymerizing ethylene and 63% by weight of methyl acrylate is quantitatively fed to the front stage of a twin screw extruder having a 45 mmφ screw, It knead | mixed under the temperature of 100-130 degreeC. Thereafter, 2.9 parts of a crosslinking agent (peroxide crosslinking agent: for example, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3) and an auxiliary agent (organic diene-based crosslinking auxiliary agent: For example, 4.3 parts of dimethylene glycol dimethacrylate) was quantitatively added to a twin screw extruder by a pump. Next, 33 parts of a polyester block copolymer (A-2-1) and "Irganox" 1010 (Ciba Geigy's hindered phenol) were added to the middle part of the twin-screw extruder whose temperature was raised to 240 to 250 ° C. System antioxidant) 0.5 parts of the dry blended blend is quantitatively fed to the twin screw extruder with a feeder, mixed with the polyethylene / acrylate elastomer melt kneaded in the previous stage, and kneaded. The polyethylene / acrylate elastomer was crosslinked and simultaneously kneaded and dispersed strongly at the subsequent stage. Further, after the devolatilization treatment at the last step part, it was discharged from the extruder through a three-hole strand die, cut with water and then cut into pellets. The dynamically crosslinked thermoplastic elastomer composition thus obtained had a melting point of 207 ° C. and a hardness of 60A.

[Production of Dynamically Crosslinked Thermoplastic Elastomer (B-2)]
100 parts of a polyethylene / acrylate elastomer (for example, Baymac manufactured by DuPont) obtained by copolymerizing ethylene and 63% by weight of methyl acrylate is quantitatively fed to the front stage of a twin screw extruder having a 45 mmφ screw, It knead | mixed under the temperature of 100-130 degreeC. Thereafter, 2.9 parts of a crosslinking agent (peroxide crosslinking agent: for example, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3) and an auxiliary agent (organic diene-based crosslinking auxiliary agent: For example, 4.3 parts of dimethylene glycol dimethacrylate) was quantitatively added to a twin screw extruder by a pump. Next, 100 parts of a polyester block copolymer (A-2-2) and "Irganox" 1010 (Ciba Geigy's hindered phenol) were added to the middle part of the twin-screw extruder whose temperature was raised to 240 to 250 ° C. System antioxidant) 0.5 parts of the dry blended blend is quantitatively fed to the twin screw extruder with a feeder, mixed with the polyethylene / acrylate elastomer melt kneaded in the previous stage, and kneaded. The polyethylene / acrylate elastomer was crosslinked and simultaneously kneaded and dispersed strongly at the subsequent stage. Further, after the devolatilization treatment at the last step part, it was discharged from the extruder through a three-hole strand die, cut with water and then cut into pellets. The dynamically crosslinked thermoplastic elastomer composition thus obtained had a melting point of 215 ° C. and a hardness of 95A.

[Heat-resistant agent]
Table 1 shows the abbreviations and structural formulas of the antioxidants (C-1), (C-2) and (C-5) used in the following Examples.

[Production of polyamide resin]
As the polyamide resin (D-1), “Amilan CM4000” (polycaprolactam / polyhexamethylene adipamide / polyhexamethylene sebamide ternary copolymer) manufactured by Toray Industries, Inc. was used.

[Examples 1 to 4, Reference Example 1 , Comparative Examples 1 to 8]
Polyether ester block copolymers (A1-2), (A2-1), (A2-1) and (A2-2) obtained in Reference Examples, and dynamically crosslinked thermoplastic elastomer compositions (B -2), heat-resistant agents (C-1), (C-2), (C-3) and polyamide resin (D-1) were all dry blended at a blending ratio as shown in Table 2, and 45 mmφ The mixture was melt-kneaded at a temperature setting of 220 ° C. to 240 ° C. using a twin-screw extruder having a screw, and pelletized. The pellets were dried at 80 ° C. for 5 hours, and then injection-molded under conditions of a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to obtain test pieces for hardness, tensile breaking strength, tensile breaking elongation, and heat aging test. It was. Various tests were carried out on the obtained molded product. For heat aging, a tensile fracture test was performed after 1000 hours of treatment in an oven at 150 ° C. For blow moldability, a press blower molding machine (SBE50 / 140 model manufactured by Osberger) was used, and the cylinder, accumulator, nozzle temperature was 230 ° C., and the mold temperature was 30 ° C., and the diameter was 60 mm and the height was 190 mm. A straight bottle having a thickness of 1 mm was molded using a mold, and the thickness of the upper part, the center part, and Co., Ltd. of the bottle molded product was measured. For extrusion moldability, a tube with an outer diameter of φ8 mm and an inner diameter of φ6 mm was formed using a water-cooled vacuum sizing using a φ30 mm single screw extruder under the molding conditions of a cylinder, an adapter, and a die temperature of 230 ° C. The wall thickness was measured. The surface appearance of the molded product was determined by visual inspection of the injection molded product. The test results are shown in Table 2.

[Examples 5 to 10 , Comparative Examples 9 to 14]
Polyether ester block copolymers (A1-1), (A1-3), (A2-1) and (A2-2) obtained in Reference Examples, and dynamically crosslinked thermoplastic elastomer composition (B -1) is dry blended with the heat-resistant agents (C-1), (C-2), (C-3) and the polyamide resin (D-1) at a blending ratio as shown in Table 3, and a 45 mmφ screw Was melt-kneaded at a temperature setting of 210 ° C. to 220 ° C. using a twin-screw extruder having The pellets were dried at 80 ° C. for 5 hours and then injection molded under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. to obtain test pieces for hardness, tensile breaking strength, tensile breaking elongation, and heat aging test. It was. Various tests were carried out on the obtained molded product. The heat aging property was subjected to a tensile break test after being treated in an oven at 130 ° C. for 1000 hours. For blow moldability, a press blower molding machine (SBE50 / 140 model manufactured by Osberger) was used, and the cylinder, accumulator, nozzle temperature was 210 ° C., and the mold temperature was 30 ° C., and the diameter was 60 mm and the height was 190 mm. A straight bottle having a thickness of 1 mm was molded using a mold, and the thickness of the upper part, the center part, and Co., Ltd. of the bottle molded product was measured. For extrusion moldability, a tube with an outer diameter of φ8 mm and an inner diameter of φ6 mm was formed using a water-cooled vacuum sizing under a molding condition of a cylinder, adapter, and a die temperature of 210 ° C. using a φ30 mm single screw extruder. The wall thickness was measured. The appearance of the molded product surface was determined by visual inspection of the injection molded product. The test results are shown in Table 3.

  As is clear from the results in Tables 2 and 3, a thermoplastic elastomer formed by mixing a polyester elastomer resin composition and a dynamically crosslinked thermoplastic elastomer composition is combined with a heat resistant agent (aromatic amine antioxidant, hinder). The heat-resistant thermoplastic elastomer resin composition of the present invention containing at least one of a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant) and, if necessary, a polyamide resin, has a hardness, a tensile strength at break. In addition, it has excellent tensile elongation at break and heat aging properties, as well as blow moldability and extrusion moldability. However, in Example 5 in which 60% by weight of the dynamically crosslinked thermoplastic elastomer composition was blended, the blow moldability and extrusion moldability were inferior and the thickness unevenness was relatively large.

  On the other hand, the resin compositions of Comparative Examples 1 to 14 that do not satisfy the conditions of the present invention are compared with the resin compositions of the present invention in terms of hardness, tensile breaking strength, tensile breaking elongation, thermal aging property, blow moldability, Either or all of extrusion moldability and molded product surface appearance are poor. Comparative Example 14 has relatively good moldability but poor heat aging properties.

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

Claims (4)

Main components are a high-melting-point crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester units and a low-melting-point polymer segment (a2) mainly composed of aliphatic polyether units and / or aliphatic polyester units. , Flexible polyester block copolymer (A1) having a melting point of less than 205 ° C. (A1) 51 to 95% by weight, a high-melting-point crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit, and an aliphatic polyether unit And / or polyester elastomer comprising 49 to 5% by weight of a high-hardness polyester block copolymer (A2) having a melting point of at least 205 ° C. Resin composition (A) 90-65% by weight Polyacrylate, polymethacrylate, acrylate / methacrylate copolymer, polyethylene / acrylate copolymer, polyethylene / methacrylate copolymer and polyethylene crosslinkable with 10 to 50% by weight of the rate polyester polymer and / or copolymer (b1) Dynamically when a mixture of at least one (co) polymer (b2) 50 to 90% by weight selected from / acrylate / methacrylate copolymer is melt-mixed in an extruder in the presence of a radical generator For 100 parts by weight of the thermoplastic elastomer composition obtained by mixing 10 to 35% by weight of the crosslinked thermoplastic elastomer (B), an aromatic amine antioxidant, a hindered phenol antioxidant, and a sulfur type One selected from the group consisting of antioxidants and phosphorus antioxidants Heat thermoplastic elastomer resin composition characterized by being obtained by blending a refractory material (C) 0.01 to 5 parts by weight of two or more kinds. The heat-resistant thermoplastic elastomer resin composition according to claim 1, wherein 0.5 to 10 parts by weight of a polyamide resin (D) is further blended with 100 parts by weight of the thermoplastic elastomer composition. The polyalkylene phthalate polyester polymer and / or copolymer (b1) is selected from polyalkylene terephthalate, polyalkylene terephthalate copolymer, polyalkylene isophthalate polyether ester and polyalkylene terephthalate copolymer polyether ester. The heat-resistant thermoplastic elastomer resin composition according to claim 1, wherein the heat-resistant thermoplastic elastomer resin composition is at least one kind. At least one selected from the dynamically cross-linked polyacrylates, polymethacrylates, acrylate / methacrylate copolymers, polyethylene / acrylate copolymers, polyethylene / methacrylate copolymers and polyethylene / acrylate / methacrylate copolymers ( The heat-resistant thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein the (co) polymer (b2) is a polyacrylate elastomer and / or a polyethylene acrylate elastomer.