JP2021105161A - Thermoplastic elastomer resin composition - Google Patents

Abstract

To provide a thermoplastic elastomer resin composition which has strength and flexibility required for a molding, achieves high heat resistance and excellent hydrolysis resistance and is also excellent in moldability, in applications such as automobile, electric machine and industrial applications.SOLUTION: A thermoplastic elastomer resin composition contains a thermoplastic polyester elastomer (A) composed of a polyester block copolymer which contains 40-80 wt.% of a high melting point crystalline polymer segment (a1) composed of a crystalline aromatic polyester unit and 20-60 wt.% of a low melting point polymer segment (a2) composed of an aliphatic polyether unit, and contains 0.05-10 pts.wt. of a novolac type epoxy resin (B1) or a polycarbodiimide compound (B2), 0-5 pts.wt. of a bifunctional epoxy resin (C), 0.1-20 pts.wt. of a glycidyl group-modified polyolefin resin (D), and 0.5-15 pts.wt. of a polyamide resin (E), with respect to 100 pts.wt. of the thermoplastic polyester elastomer (A).SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic elastomer composition that is flexible, has excellent heat resistance and hydrolysis resistance, and is also excellent in formability.

Polyesters in which the crystalline aromatic polyester unit is a high melting point crystalline polymer segment and the aliphatic polyether unit such as poly (alkylene oxide) glycol and / or the aliphatic polyester unit such as polylactone is a low melting point polymer segment. Block copolymers are excellent in mechanical properties such as strength, impact resistance, elastic recovery, flexibility, and bending fatigue, low temperature and high temperature characteristics, and are thermoplastic and easy to mold. Widely used for parts and industrial materials.

However, in general, the hydrolysis resistance of the polyester block copolymer becomes better as the ratio of low melting point crystalline polymer segments increases, but as the ratio of low melting point crystalline polymer segments increases at high temperatures, the higher the ratio of low melting point crystalline polymer segments. Since the heat resistance is lowered, it has been difficult to provide a highly flexible material having both hydrolysis resistance and heat resistance.

As a method for improving heat resistance, for example, a block polyether ester 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. Copolymer compositions (see, for example, Patent Document 1), polyester-based elastomers, aromatic amine-based antioxidants, hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants and / or A polyester elastomer resin composition to which a polyamide resin is added (see, for example, Patent Document 2) has been proposed.

Further, a block polyether ester copolymer composition (for example, a block polyether ester copolymer composition in which a glycidyl group-modified polyolefin resin and a polyamide resin are added to a mixture of a polyether ester block copolymer having two kinds of dicarboxylic acid components and a hard polyester resin). , Patent Document 3), or a mixture of a polyether ester block copolymer having two types of dicarboxylic acid components and a polyether ester block copolymer having a dicarboxylic acid component of terephthalic acid or an ester-forming derivative thereof. A block polyether ester copolymer composition (see, for example, Patent Document 4) in which a glycidyl-modified polyolefin resin and a polyamide resin are added has been proposed.

Further, the polyether ester block copolymer is liable to be deteriorated by hydrolysis, and as a method for improving the carbodiimide and a bifunctional or higher functional epoxy compound (see, for example, Patent Document 5) or a novolak type thermoplastic polyester resin. A method of blending an epoxy resin (see, for example, Patent Documents 6 and 7) and a method of blending a polyamide compound by using a carbodiimide compound and an epoxy compound in combination are known (for example, Patent Document 8).

Japanese Unexamined Patent Publication No. 2-173059 Japanese Unexamined Patent Publication No. 11-323109 Japanese Unexamined Patent Publication No. 2013-189550 Japanese Unexamined Patent Publication No. 2014-177566 International Publication No. 2007/029768 International Publication 2015/072216 International Publication No. 2017/001776 International release 2017/138548

However, in the compositions of Patent Document 1 and Patent Document 2, as long as they are basically polyether ester block copolymers, it is difficult to satisfy a high level of heat resistance even if the heat resistance can be improved to some extent. ..

Further, in the compositions of Patent Document 3 and Patent Document 4, although a high level of heat resistance can be obtained, there is a problem that the hydrolysis resistance is lowered.

Further, in the methods of Patent Document 5 and Patent Documents 6, 7 and 8, although the hydrolysis resistance is improved, it is a problem that sufficient heat resistance cannot be obtained.

The present invention has been achieved as a result of studies for solving the above-mentioned problems of the prior art, has strength and flexibility required for a molded product, has high heat resistance and hydrolysis resistance, and has molding processability. It is an object of the present invention to provide an excellent thermoplastic elastomer resin composition.

The present invention employs the following means in order to solve the above problems. That is, in the present invention, 40 to 80% by weight of a high melting point crystalline polymer segment (a1) composed of a crystalline aromatic polyester unit and 20 to 60% by weight of a low melting point polymer segment (a2) composed of an aliphatic polyether unit. Containing a thermoplastic polyester elastomer (A) composed of a polyester block copolymer containing and, with respect to 100 parts by weight of the thermoplastic polyester elastomer (A).
Novolac type epoxy resin (B1) or polycarbodiimide compound (B2) 0.05 to 10 parts by weight, bifunctional epoxy resin (C) 0 to 5 parts by weight, glycidyl group-modified polyolefin resin (D) 0.1 to 20 parts by weight It is a thermoplastic elastomer resin composition containing 0.5 to 15 parts by weight of the polyamide resin (E).

According to the present invention, as described below, a thermoplastic elastomer resin having the strength and flexibility required for a molded product, having high heat resistance, having excellent hydrolysis resistance, and having excellent molding processability. The composition can be obtained.

Hereinafter, the present invention will be described.

The thermoplastic polyester elastomer (A) used in the present invention has a high melting point crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low melting point polymer segment (a2) mainly composed of an aliphatic polyether unit. ) Is a polyester block copolymer composed of), and the refractory crystalline polymer segment is mainly composed of a crystalline aromatic polyester unit, that is, mainly an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a diol. Alternatively, it is a polyester formed from the ester-forming derivative thereof.

Examples of the aromatic dicarboxylic acid or an ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracenedicarboxylic acid, diphenyl-4,4. Included are'-dicarboxylic acid, diphenoxyetanedicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate and the like. In the present invention, the aromatic dicarboxylic acid is mainly used, and a part of the aromatic dicarboxylic acid is an alicyclic such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4′-dicyclohexyldicarboxylic acid. It may be replaced with a group dicarboxylic acid or an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecandioic acid, and dimer acid. Further, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonic acid esters, acid halides and the like can of course be used equally.

As the dicarboxylic acid component, the aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably terephthalic acid or dimethyl terephthalate, and more preferably terephthalic acid.

Examples of the diol or an ester-forming derivative thereof include diols having a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol. Alicyclic diols such as group diols, 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecanedimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy). ) Diphenyl propane, 2,2'-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) ethoxy) ) Phenyl] Aromatic diols such as cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quarterphenyl are preferred, such diols being ester-forming derivatives such as acetyls. It can also be used in the form of alkali metal salts and the like.

Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination.

Preferred examples of such a refractory crystalline polymer segment (a1) are polybutylene terephthalate units derived from terephthalic acid or dimethyl terephthalate and 1,4-butanediol, isophthalic acid or dimethyl isophthalate and 1,4-butane. Those consisting of polybutylene isophthalate units derived from diols are preferably used.

The copolymerization amount of the high melting point crystalline polymer segment (a1) is 40 to 80% by weight, preferably 50 to 70% by weight.

The copolymerization amount of the refractory crystalline polymer segment (a1) is, for example, terephthalic acid and 1,4-butanediol when the constituent component of the refractory crystalline polymer segment (a1) is a polybutylene terephthalate unit. It is the sum of each mass%.

The low melting point polymer segment (a2) used in the thermoplastic polyester elastomer (A) used in the present invention is mainly composed of an aliphatic polyether.

Specific examples of such aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (trymethylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and ethylene oxide. Examples include a copolymer of propylene oxide, an ethylene oxide adduct of poly (propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Among these, ethylene oxide adducts of poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol and / or copolymers of ethylene oxide and tetrahydrofuran are preferably used.

The copolymerization amount of the low melting point polymer segment (a2) of the (A) thermoplastic polyester elastomer used in the present invention is 20 to 60% by weight, preferably 30 to 50% by weight.

The amount of copolymerization of the low melting point crystalline polymer segment (a2) is, for example, poly (tetramethylene oxide) glycol when the constituent component of the low melting point crystalline polymer segment (a2) is a poly (tetramethylene oxide) glycol unit. Is the mass% of.

The thermoplastic polyester elastomer (A) used in the present invention can be produced by a known method. Specific examples thereof include a method in which a lower alcohol diester of a dicarboxylic acid, an excess amount of a low molecular weight glycol and a low melting point polymer segment component are subjected to a transesterification reaction in the presence of a catalyst, and the obtained reaction product is melt-polycondensed. Any method may be used, such as a method in which a dicarboxylic acid, an excess amount of glycol, and a low melting point polymer segment component are subjected to a transesterification reaction in the presence of a catalyst, and the obtained reaction product is melt-polycondensed.

The thermoplastic polyester elastomer (A) obtained by polycondensation may then be subjected to solid phase polycondensation. Solid phase polycondensation is carried out at a temperature at which the thermoplastic polyester elastomer (A) pelletized after melt polycondensation does not fuse, but is usually carried out in a temperature range of 140 ° C. to 220 ° C. Prior to solid phase polycondensation, it is desirable to go through a pre-crystallization and drying step. Further, the solid phase polycondensation is carried out under high vacuum or under an inert air flow. In the case of high vacuum, the pressure is preferably 665 Pa or less, more preferably 133 Pa or less. In the case of under an inert air flow, it is typically performed under a nitrogen air flow, and the pressure is not particularly limited, but atmospheric pressure is preferable. As the reaction vessel, it is preferable to use a rotatable vacuum dryer, a tower dryer capable of flowing an inert gas, or the like.

The novolak type epoxy resin (B1) used in the present invention is a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol novolac type epoxy resin, a naphthol novolac type epoxy resin, a naphthol-phenol co-condensed novolac type epoxy resin, a naphthol-cresol. Examples thereof include a co-shrink novolac type epoxy resin. Two or more of these may be blended.

The polycarbodiimide compound (B2) used in the present invention can be selected from aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and compounds obtained by polymerizing a mixture thereof. Specific examples of polycarbodiimides include poly (1,6-hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), and poly (1,4-cyclohexyl). Silencarbodiimide), poly (4,4'-dicyclohexylmethanecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide) ), Poly (p-phenylene carbodiimide), Poly (m-phenylene carbodiimide), Poly (trilcarbodiimide), Poly (diisopropylcarbodiimide), Poly (methyl-diisopropylphenylenecarbodiimide), Poly (1,3,5-triisopropylbenzene) ) Polycarbodiimide, poly (1,3,5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide, poly (triethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide) and other polycarbodiimides can be mentioned. .. Of these, an aromatic polycarbodiimide compound is preferable from the viewpoint of heat resistance.

The blending amount of the novolak type epoxy resin (B1) or the polycarbodiimide compound (B2) is 0.05 to 10 parts by weight, preferably 0.5 parts by weight, based on 100 parts by weight of the thermoplastic polyester elastomer composition (A). ~ 8 parts by weight. If it is less than 0.05 parts by weight, a sufficient effect cannot be obtained, and if it exceeds 10 parts by weight, the moldability is deteriorated due to a significant increase in viscosity.

The bifunctional epoxy resin (C) used in the present invention is a compound containing two epoxy groups in its molecule, and a liquid or solid compound can be used. For example, it is a polycondensate of epichlorohydrin and a phenol compound such as bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, bisphenol S, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol. Examples thereof include glycidyl ether-based epoxy compounds, glycidyl ester-based epoxy compounds such as phthalic acid glycidyl ester, and glycidyl amine-based epoxy compounds such as N, N'-methylenebis (N-glycidyl aniline). Two or more of these may be blended.

Among them, glycidyl ether-based epoxy compounds are preferable because they can suppress decomposition during melt processing, and by further improving the surface free energy of the resin composition and preventing permeation into chemicals such as industrial lubricating oils and greases. A bisphenol A type epoxy compound is preferable because it can improve chemical resistance, which is resistance to deterioration due to contact with high-temperature chemicals. Further, the component (C) used in the present invention does not contain a novolak type epoxy compound.

Further, among the bisphenol A type epoxy compounds, a bisphenol A type epoxy resin having an epoxy value of 300 to 3000 g / eq is preferable. When the epoxy value of the bisphenol A type epoxy resin is 300 g / eq or more, the amount of gas during melt processing can be suppressed. 500 g / eq or more is more preferable. Further, when the epoxy value of the bisphenol A type epoxy resin is 3000 g / eq or less, both long-term hydrolysis resistance and melt retention stability at high temperature can be achieved at a higher level. 2000 g / eq or less is more preferable.

The blending amount of the bifunctional epoxy resin (C) is 0 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester elastomer composition (A).

These novolak type epoxy resins (B1), polycarbodiimide compounds (B2), and bifunctional epoxy resins (C) can prevent hydrolysis of the polymer by blocking the carboxyl end groups of the polymer.

The glycidyl group-modified polyolefin resin (D) used in the present invention is a copolymer of α-olefin and glycidyl ester of α, β-unsaturated carboxylic acid, or α-olefin, α, β-unsaturated carboxylic acid alkyl ester. A ternary copolymer composed of glycidyl ester of α, β-unsaturated carboxylic acid and α-olefin, α, β-unsaturated carboxylic acid alkyl ester and glycidyl ester of α, β-unsaturated carboxylic acid are preferable. A ternary copolymer is particularly preferable. Examples of the α-olefin include ethylene, propylene and butene-1, but ethylene is most preferable.

Examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and glycidyl methacrylate is preferably used. As the α, β-unsaturated carboxylic acid alkyl ester, an ester of acrylic acid or methacrylic acid and a monovalent alcohol having 1 to 8 carbon atoms is preferable, and among them, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl. Methacrylate is preferable, and methyl acrylate, ethyl acrylate, and butyl acrylate are particularly preferable.

The blending amount of the glycidyl group-modified polyolefin resin (D) is 0.1 to 20 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the thermoplastic polyester elastomer composition (A). If it is less than 0.1 part by weight, the degree of improvement of the desired effect is small, and if it exceeds 20 parts by weight, gelation occurs due to melt retention during molding, and the moldability deteriorates.

The polyamide resin (E) used in the present invention is a polymer compound having an amide bond in the molecular chain, and is a polymer from lactam, adipic acid, sebacic acid, dodecandic acid, etc., ethylenediamine, hexamethylenediamine, etc. , A polymer of a salt obtained by reaction with 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, even higher effects can be obtained when nylon 6 and / or a copolymerized polyamide resin of 2 or 3 or more elements is used.

The blending amount of the polyamide resin (E) is 0.5 to 15 parts by weight, preferably 1 to 15 parts by weight, more preferably 1.5 to 15 parts by weight, based on 100 parts by weight of the thermoplastic polyester elastomer composition (A). It is a part by weight. If the blending amount of the polyamide resin (E) is less than 0.5 parts by weight, the degree of obtaining the desired improvement effect is small, and if it exceeds 15 parts by weight, the polyether ester block copolymer originally has. It is not preferable because the flexibility and rubbery properties are impaired.

The heat resistance can be improved by further adding the antioxidant (F) to the thermoplastic elastomer composition of the present invention.

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

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

Specific examples of hindered phenolic antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, and 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 (2,2-di-t-butylphenol) 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-di-t-butyl-4-hydroxybenzenesulfonic acid Dethyl ester, 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-hydroxyhydrosilicate 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, Tetrax [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-) Examples thereof include di-t-butyl-4-hydroxyphenyl) isocyanurate and tris [β- (3,5-di-t-butyl-4 hydroxyphenyl) propionyl-oxyethyl] isocyanurate. Among these, those having a molecular weight of 500 or more, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, are particularly preferable.

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

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

The total amount of these antioxidants (F) to be blended is 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.05 parts by weight, based on 100 parts by weight of the thermoplastic polyester elastomer composition (A). Is 0.10 to 5 parts by weight.

When the total amount of the antioxidant is 0.01 parts by weight or more, the degree of obtaining the desired improvement effect is increased, and when it is 5 parts by weight or less, blooming is less likely to occur, or polyester. This is preferable because the mechanical strength of the block copolymer is less likely to decrease.

Further, in addition to the above-mentioned additives (B1), (B2), (C) to (F), various additives are added to the thermoplastic elastomer resin composition of the present invention as long as the object of the present invention is not impaired. can do. For example, known molding aids such as crystal nucleating agents and lubricants, light-resistant agents such as ultraviolet absorbers and hindered amine compounds, hydrolysis-resistant improving agents, coloring agents such as pigments and dyes, antistatic agents, conductive agents, and flame retardants. Reinforcing agents, fillers, plasticizers, mold release agents and the like can be optionally contained.

The method for producing the thermoplastic elastomer resin composition of the present invention is not particularly limited, but for example, a novolak type epoxy resin (B1) or a polycarbodiimide compound (B2) is added to a polyester block copolymer. A method in which a raw material containing a resin (C), a glycidyl group-modified polyolefin resin (D), a polyamide resin (E), and an antioxidant (F) is supplied to a screw type extruder and melt-kneaded, or used in a screw type extruder. First, a polyester block copolymer, a novolak type epoxy resin (B1) or a polycarbodiimide compound (B2), and a bifunctional epoxy resin (C) are supplied and melted, and then a glycidyl group-modified polyolefin resin is further supplied from another supply port. A method of supplying (D) and kneading, and then supplying and kneading the polyamide resin (E) antioxidant (F) and other formulations from another supply port can be appropriately adopted.

The thermoplastic elastomer resin composition of the present invention is made into a molded product by injection molding, blow molding, extrusion molding, compression molding or the like.

The effects of the present invention will be described below by way of examples. The present invention can be appropriately modified and carried out within the scope of the gist of the present invention. In addition,% and part in an Example are all based on weight unless otherwise specified. The physical properties shown in the examples are measured by the following measuring methods.

[Melt flow rate (MFR)]
Measured according to ASTM D1238 at 240 ° C. and a load of 2160 g.

[Tensile breaking strength, tensile breaking elongation]
Pellets dried with hot air at 90 ° C. for 3 hours or more were molded using an injection molding machine (NEX-1000 manufactured by Nissei Resin Industry Co., Ltd.) under molding conditions of a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. It was molded and measured according to JIS K7113 (1995 edition).

[Heat aging]
JIS K 7113 No. 2 test in which pellets dried with hot air at 90 ° C. for 3 hours or more were molded using an injection molding machine (NEX-1000 manufactured by Nissei Resin Industry Co., Ltd.) under the molding conditions of a predetermined cylinder temperature and mold temperature. The pieces were left in a hot air oven at 160 ° C. for 400 hours, then taken out, measured according to JIS K 7113 (1995 version), and evaluated from the values of tensile elongation at break in the following three stages.
⊚: The tensile elongation at break is 80% or more.
◯: The tensile elongation at break is 40% or more and less than 80%.
X: The tensile elongation at break is less than 40%.

[Hydrolysis resistance]
JIS K 7113 No. 2 test in which pellets dried with hot air at 90 ° C. for 3 hours or more were molded using an injection molding machine (NEX-1000 manufactured by Nissei Resin Industry Co., Ltd.) under the molding conditions of a predetermined cylinder temperature and mold temperature. The piece was left in a constant temperature and humidity chamber at 80 ° C. and 95% RH for 2500 hours, then taken out, measured according to JIS K 7113 (1995 version), and evaluated from the value of tensile elongation at break in the following three stages.
⊚: The tensile elongation at break is 200% or more.
◯: The tensile elongation at break is 100% or more and less than 200%.
X: The tensile elongation at break is less than 100%.

[Manufacturing of polyester elastomer (A-1)]
505 parts of terephthalic acid and 251 parts of 1,4-butanediol as the high melting point crystalline polymer segment (a1), and 354 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 as the low melting point polymer segment (a2). Was charged into a reaction vessel equipped with a helical ribbon-type stirring blade together with 0.3 part of titanium tetrabutoxide and 0.2 part of mono-n-butyl-monohydroxytin oxide, and heated at 190 to 225 ° C. for 3 hours to react water. Was distilled out of the system while the esterification reaction was carried out. 2.0 parts of titanium tetrabutoxide was added to the reaction mixture, 0.5 part of "Irganox" 1098 (Hindered phenolic antioxidant manufactured by Ciba Geigy Co., Ltd.) was added, and then the temperature was raised to 245 ° C., and then 50. The pressure in the system was reduced to 0.2 mmHg over a minute, and under that condition, melt polycondensation was carried out for 2 hours and 45 minutes. The obtained polyester elastomer was discharged into water in the form of strands and cut into pellets.

The weight% of the high melting point crystalline polymer segment (a1) was 65, and the weight% of the low melting point polymer segment (a2) was 35.

[Manufacturing of polyester elastomer (A-2)]
420 parts of terephthalic acid and 196 parts of 1,4-butanediol as the high melting point crystalline polymer segment (a1), and 480 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 as the low melting point polymer segment (a2). Was charged into a reaction vessel equipped with a helical ribbon-type stirring blade together with 0.3 part of titanium tetrabutoxide and 0.2 part of mono-n-butyl-monohydroxytin oxide, and heated at 190 to 225 ° C. for 3 hours to react water. Was distilled out of the system while the esterification reaction was carried out. 2.0 parts of titanium tetrabutoxide was added to the reaction mixture, 0.5 part of "Irganox" 1098 (Hindered phenolic antioxidant manufactured by Ciba Geigy Co., Ltd.) was added, and then the temperature was raised to 245 ° C., and then 50. The pressure in the system was reduced to 0.2 mmHg over a minute, and under that condition, melt polycondensation was carried out for 2 hours and 45 minutes. The obtained polyester elastomer was discharged into water in the form of strands and cut into pellets.

The weight% of the high melting point crystalline polymer segment (a1) was 52, and the weight% of the low melting point polymer segment (a2) was 48.

[Manufacturing of polyester elastomer (A-3)]
593 parts of terephthalic acid and 307 parts of 1,4-butanediol as the high melting point crystalline polymer segment (a1), and 229 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 as the low melting point polymer segment (a2). Was charged into a reaction vessel equipped with a helical ribbon-type stirring blade together with 0.3 part of titanium tetrabutoxide and 0.2 part of mono-n-butyl-monohydroxytin oxide, and heated at 190 to 225 ° C. for 3 hours to react water. Was distilled out of the system while the esterification reaction was carried out. 2.0 parts of titanium tetrabutoxide was added to the reaction mixture, 0.5 part of "Irganox" 1098 (Hindered phenolic antioxidant manufactured by Ciba Geigy Co., Ltd.) was added, and then the temperature was raised to 245 ° C., and then 50. The pressure in the system was reduced to 0.2 mmHg over a minute, and under that condition, melt polycondensation was carried out for 2 hours and 45 minutes. The obtained polyester elastomer (A-3) was discharged into water in a strand shape and cut into pellets. The weight% of the high melting point crystalline polymer segment (a1) was 78, and the weight% of the low melting point polymer segment (a2) was 22.

[Novolak type epoxy resin (B1)]
NC-3000 manufactured by Nippon Kayaku Co., Ltd. was used as the novolak type epoxy resin (B1).

[Polycarbodiimide compound (B2)]
Lanxess Stabacsol P was used as the polycarbodiimide compound.

[Bifunctional epoxy resin (C)]
As the bifunctional epoxy resin (C), jER1007 manufactured by Mitsubishi Chemical Corporation was used.

[Glysidyl group-modified polyolefin resin (D)]
As the glycidyl group-modified polyolefin resin (D), Bond First 7M (a ternary copolymer of ethylene, methyl acrylate, and glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd. was used.

[Polyamide resin (E)]
As the polyamide resin (E), Amylan CM4000 (a ternary copolymer of polycaprolactam, polyhexamethylene adipamide, and polyhexamethylene sebacamide) manufactured by Toray Industries, Inc. was used.

[Antioxidant (F)]
Table 1 shows the abbreviations and structural formulas of the antioxidants F-1 (aromatic amine type), F-2 (hindered phenol type) and F-3 (sulfur type) used in the following examples.

[Examples 1 to 4]
Polyester elastomers (A-1), (A-2), (A-3) and novolak type epoxy resins (B1) or polycarbodiimide compounds shown in the reference examples using a twin-screw extruder having a screw with a diameter of 45 mm. (B2), glycidyl group-modified polyolefin resin (D) polyamide resin (E), antioxidant (F) and, if necessary, bifunctional epoxy resin (C) are mixed in the composition shown in Table 2 and charged. It was added from the part. A thermoplastic polyester elastomer resin composition pelletized by a strand cutter was obtained by melt-mixing the mixture under extrusion conditions of a heating temperature of 250 ° C. and a screw rotation of 150 rpm, discharging the mixture into strands, and passing the mixture through a cooling bath.

The obtained pellets are dried at 90 ° C. for 3 hours and then injection-molded under the conditions of a cylinder temperature of 230 ° C. to 250 ° C. and a mold temperature of 50 ° C., for tensile breaking strength, tensile breaking elongation, heat aging resistance test, and hydrolysis resistance. A test piece for a degradability test was obtained. Various tests were carried out using the obtained test pieces. The tensile breaking strength and the tensile breaking elongation were measured at 23 ° C. The heat aging property was determined by performing a tensile test (tensile breaking strength, tensile breaking elongation) at 23 ° C. after treating in an oven at 160 ° C. for 400 hours. The hydrolysis resistance was determined by performing a tensile test (tensile breaking strength, tensile breaking elongation) at 23 ° C. after treating for 2500 hours in a constant temperature and humidity chamber at 80 ° C. and 95% RH. The test results are shown in Table 2.

As is clear from the results in Table 2, the polyester elastomer (A) shown in Examples 1 to 5 is mixed with a novolak type epoxy resin (B1) or a polycarbodiimide compound (B2), a glycidyl group-modified polyolefin resin (D), and a polyamide. Resin (E) Further, an antioxidant (aromatic amine-based antioxidant, hindered phenol-based antioxidant, one or more of sulfur-based antioxidants) and, if necessary, a bifunctional epoxy resin (C) were blended. The thermoplastic elastomer resin composition of the present invention is excellent in tensile breaking strength and tensile breaking elongation. It also has excellent heat aging resistance and hydrolysis resistance. On the other hand, the resin compositions of Comparative Examples 1 to 4 that do not satisfy the conditions of the present invention have any of tensile breaking strength, tensile breaking elongation, heat aging resistance, and hydrolysis resistance as compared with the resin composition of the present invention. Is inferior.

As described above, the thermoplastic elastomer resin composition of the present invention has sufficient strength and rigidity as a molded product, and also has excellent heat aging resistance and hydrolysis resistance. Therefore, automobile parts, electrical equipment, and the like. It is particularly suitable for products that require flexibility, heat resistance, and quick hydrolyzability, such as industrial products.

Claims (6)

The constituent components are a high melting point crystalline polymer segment (a1) consisting of 40 to 80% by weight of a crystalline aromatic polyester unit and a low melting point polymer segment (a2) consisting of 20 to 60% by weight of an aliphatic polyether unit. A novolak type epoxy resin (B1) or a polycarbodiimide compound (B2) 0.05 to 10 with respect to 100 parts by weight of the thermoplastic polyester elastomer (A) containing a thermoplastic polyester elastomer (A) made of a polyester block copolymer. It is characterized by containing 0 to 5 parts by weight of a bifunctional epoxy resin (C), 0.1 to 20 parts by weight of a glycidyl group-modified polyolefin resin (D), and 0.5 to 15 parts by weight of a polyamide resin (E). The thermoplastic elastomer resin composition to be used. The thermoplastic elastomer resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of the antioxidant (F) with respect to 100 parts by weight of the thermoplastic polyester elastomer (A). The thermoplastic elastomer resin composition according to claim 1 or 2, wherein the bifunctional epoxy resin (C) is a bisphenol A type epoxy resin. The glycidyl group-modified polyolefin resin (D) is a copolymer of a glycidyl ester of α-olefin and α, β-unsaturated carboxylic acid, or an α-olefin, α, β-unsaturated carboxylic acid alkyl ester and α, β. The thermoplastic elastomer resin composition according to any one of claims 1 to 3, which is a ternary copolymer composed of a glycidyl ester of an unsaturated carboxylic acid. The thermoplastic elastomer resin composition according to any one of claims 1 to 4, wherein the polyamide resin (E) is made of nylon 6 and / or a copolymer resin of 2 or 3 or more elements. .. The antioxidant (F) is one or more selected from the group consisting of aromatic amine-based antioxidants, hindered phenol-based antioxidants, sulfur-based antioxidants and phosphorus-based antioxidants. The thermoplastic elastomer resin composition according to any one of claims 1 to 5, wherein the thermoplastic elastomer resin composition is obtained.