JPH11323109A - Polyester elastomer resin composition - Google Patents

Abstract

(57) [Problem] To provide a polyester elastomer resin composition excellent in oil resistance, grease resistance and heat aging resistance. A polyether having a high melting point crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a low melting point polymer segment (b) mainly composed of an aliphatic polyether unit as main components. 0.01 to 5 parts by weight of an aromatic amine-based antioxidant (B) based on 100 parts by weight of the ester block copolymer (A);
Hindered phenolic antioxidant (C) 0.01 to 5
Parts by weight, 0.01 to 5 parts by weight of a sulfur-based antioxidant (D) and / or 0.01 to 5 parts by weight of a phosphorus-based antioxidant (E)
A polyester elastomer resin composition which is blended with parts by weight. Further, if desired, a polyester elastomer resin composition further comprising 0.1 to 20 parts by weight of a polyamide resin (F).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetherester elastomer resin composition having excellent oil resistance, grease resistance and heat aging resistance.

[0002]

2. Description of the Related Art Polyetherester block copolymers having a crystalline aromatic polyester unit such as a polybutylene terephthalate unit as a hard segment and an aliphatic polyether unit such as a poly (alkylene oxide) glycol unit as a soft segment. Means extrudability,
Excellent injection moldability, high mechanical strength, excellent rubber properties such as impact resistance, elastic recovery, flexibility, low and high temperature properties, water resistance, etc. Further, it is thermoplastic and easy to mold For this reason, applications are expanding to automotive parts, electric / electronic parts, fibers, films, etc.

[0003] However, polyetherester block copolymers, although having the above-mentioned excellent properties, have poor oil resistance, and when immersed in high-temperature oil for a long period of time, the strength and elongation gradually decrease. In fact, the use of such a material is restricted, especially in applications where it comes into contact with hot oil.

Further, the polyetherester block copolymer has poor heat aging resistance due to its susceptibility to oxidative deterioration, and its strength and elongation are reduced in a relatively short time when used in a high-temperature atmosphere. Can no longer be used,
Since the molded article has a defect that a crack is generated on the surface and the appearance is deteriorated, the use of the molded article in a high-temperature oxidizing atmosphere is limited.

In view of such circumstances, many attempts have been made to improve the oil resistance and heat aging resistance of polyetherester block copolymers. For example, Japanese Patent Publication No. 46-38911 discloses a polyetherester block copolymer. By blending a hindered phenol-based antioxidant and a sulfur-based antioxidant and / or a phosphorus-based antioxidant with the block copolymer, a resin composition having improved heat aging resistance of the polyetherester block copolymer can be obtained. It has been disclosed. JP-A-48-89955 discloses a resin composition in which an arylamine-based antioxidant is blended with a polyetherester block copolymer to improve heat aging resistance.

Further, JP-A-58-23848 discloses a composition in which a mixture of a polyetherester block copolymer, a polyamide and an arylamine-based antioxidant has a remarkably enhanced resistance to oxidative deterioration at high temperatures. And ASTM No. No. 3 discloses that the resistance to oil at high temperatures is also good.
No. 73059 discloses that a polyether ester block copolymer is prepared by blending a polyamide resin with a hindered phenol-based antioxidant and a sulfur-based antioxidant and / or a phosphorus-based antioxidant. A resin composition having improved heat aging resistance of a polymer is disclosed.

The resin compositions disclosed in JP-B-46-38911 and JP-A-48-89955 are certainly resin compositions having improved heat aging resistance. It is hard to say enough, and it is hard to withstand aging under severe conditions. Also,
ASTM No. Resistance to lubricating oils represented by oil 3 is also insufficient.

Furthermore, the resin composition disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 58-23848 does have improved heat aging resistance. The resistance to lubricating oils represented by three oils is also improved. However, some uses of the polyetherester block copolymer include ASTM No. In some cases, not only oil resistance to low-viscosity lubricating oils such as Oil 3 but also resistance to grease, which is a semi-solid lubricant containing high-grade lithium soap and molybdenum disulfide, is required. The disclosed resin composition is not yet sufficiently resistant to grease.

The resin composition disclosed in Japanese Patent Application Laid-Open No. 2-173059 is a composition having no bleed-out or yellowing on the surface of a molded product, and has a time at which the tensile elongation at break becomes half of the initial value. The heat aging resistance evaluated in the above was certainly improved. However, the resin composition disclosed in the same publication still has insufficient heat aging resistance in a high-temperature oxidizing atmosphere when evaluated by the time until a test piece breaks in a 180-degree bending test, and furthermore has no oil resistance or grease resistance. Inferior in nature.

[0010]

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

Therefore, an object of the present invention is to provide an ASTM
No. Excellent in resistance to grease as well as lubricating oil typified by 3 oils, and also evaluated in a 180 ° bending test when evaluated by the retention of tensile elongation at break in a severe oxidizing atmosphere. Also in this case, it is to provide a resin composition having excellent heat aging resistance.

[0012]

In order to achieve the above object, the polyester elastomer resin composition of the present invention comprises:
A polyetherester block copolymer mainly composed of a high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (b) mainly composed of an aliphatic polyether unit. 0.01 to 5 parts by weight of an aromatic amine-based antioxidant (B), 0.01 to 5 parts by weight of a hindered phenol-based antioxidant (C), and 100 parts by weight of the combined (A) The composition is characterized by comprising 0.01 to 5 parts by weight of a system-based antioxidant (D) and / or 0.01 to 5 parts by weight of a phosphorus-based antioxidant (E).

Further, the polyester elastomer resin composition of the present invention comprises a high melting point crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low melting point polymer segment mainly composed of aliphatic polyether units ( b) with respect to 100 parts by weight of the polyetherester block copolymer (A) containing
0.01 to 5 parts by weight of an aromatic amine antioxidant (B) and 0.01 hindered phenol antioxidant (C)
-5 parts by weight, and sulfur-based antioxidant (D) 0.01-5
Parts by weight and / or phosphorus antioxidant (E) 0.01
-5 parts by weight and 0.1-20 parts by weight of the polyamide resin (F).

In the polyester elastomer resin composition of the present invention, the high-melting crystalline polymer segment (a), which is a component of the polyetherester block copolymer (A), is composed of polybutylene terephthalate units. Wherein the low-melting polymer segment (b), which is a component of the polyetherester block copolymer (A), is a poly (tetramethylene oxide) glycol unit and / or an ethylene oxide addition polymer of poly (propylene oxide) glycol The polyether ester block copolymer (A)
The copolymerization amount of the low melting polymer segment (b) is 1
0 to 80% by weight, the aromatic amine antioxidant (B) is a diphenylamine compound, and the hindered phenol antioxidant (C) has a molecular weight of 5
A hindered phenolic compound of at least 00,
The sulfur-based antioxidant (D) is a thiodipropionate compound, and the phosphorus-based antioxidant (E)
Is a compound having a sulfur atom together with a phosphorus atom in a molecule, and the phosphorus-based antioxidant (E) is a compound having two or more phosphorus atoms in a molecule, and the polyamide resin (F) is A copolymerized polyamide resin is a preferable condition in any case, and when these conditions are applied, it is possible to expect to obtain a more excellent effect.

[0015]

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

The high-melting crystalline polymer segment (a) of the polyetherester block copolymer (A) used in the present invention is formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. A unit composed of a crystalline aromatic polyester, preferably terephthalic acid and / or dimethyl terephthalate and 1,4
-Butanediol and polybutylene terephthalate units, and in addition, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-
A dicarboxylic acid component such as 4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof;
00 or less diol, such as 1,4-butanediol,
Aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol,
Alicyclic diols such as tricyclodecane dimethylol,
Xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,
2-bis [4- (2-hydroxyethoxy) phenyl]
Propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′- Dihydroxy-p-
It may be a polyester unit derived from an aromatic diol such as quarter phenyl, or a copolymerized polyester unit 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, a polyfunctional oxyacid component, a polyfunctional hydroxy component and the like in a range of 5 mol% or less.

The low-melting polymer segment (b) of the polyester block copolymer (A) used in the present invention is a unit mainly composed of an aliphatic polyether.
Specific examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, poly ( Examples include an ethylene oxide addition polymer of (propylene oxide) glycol and a copolymer of ethylene oxide and tetrahydrofuran. Among these aliphatic polyethers, it is preferable to use poly (tetramethylene oxide) glycol and an ethylene oxide adduct of poly (propylene oxide) glycol because the resulting polyester block copolymer has excellent elastic properties. The number average molecular weight of these low-melting polymer segments is 300 to 60 in the copolymerized state.
It is preferably about 00.

The copolymerization amount of the low melting polymer segment (b) in the polyetherester block copolymer (A) used in the present invention is preferably 10 to 80% by weight,
More preferably, the content is 15 to 75% by weight.

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

Specific examples of the aromatic amine antioxidant (B) which is one of the components used in the resin composition of the present invention include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'- Bis (α, α-dimethylbenzyl) diphenylamine, 4-isopropoxydiphenylamine and the like can be mentioned, and among these, use of a diphenylamine compound is preferable.

Specific examples of the hindered phenolic antioxidant (C) which is one of the components used in the resin composition of the present invention include 2,4-dimethyl-6-t-butylphenol and 2,6-dimethyl-6-t-butylphenol. Di-t-butylphenol, 2,6-
Di-t-butyl-p-cresol, hydroxymethyl-
2,6-di-t-butylphenol, 2,6-di-t-
α-dimethylamino-p-cresol, 2,5-di-t
-Butyl-4-ethylphenol, 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2 ' -Methylene-bis (4-ethyl-6-t-
Butylphenol), 4,4'-methylene-bis (6-
t-butyl-o-cresol), 4,4'-methylene-
Bis (2,6-di-t-butylphenol), 2,2 ′
-Methylene-bis (4-methyl-6-cyclohexylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-) Methylphenol), bis (3
-Methyl-4-hydroxy-5-t-butylbenzyl)
Sulfide, 4,4′-thiobis (6-t-butyl-o
-Cresol), 2,2′-thiobis (4-methyl-6
-T-butylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-
4-methylphenol, 3,5-di-t-butyl-4-
Hydroxybenzenesulfonic acid diethyl 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-tert-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-bis-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di Dioctadecyl ester of -t-butyl-4-hydroxybenzenephosphonic acid, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3
-Tris (2-methyl-4-hydroxy-5-di-t-
Butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate And the like. Among them, it is particularly preferable to use those having a molecular weight of 500 or more, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

The sulfur-based antioxidant (D), which is one of the components used in the resin composition of the present invention, includes thioether-based, dithioate-based, mercaptobenzimidazole-based,
It is a compound containing sulfur such as thiocarbanilide type and thiodipropion ester type. Among these,
Particularly, use of a thiodipropion ester-based compound is preferred.

The phosphorus antioxidant (E), which is one of the components used in the resin composition of the present invention, includes phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkyl Compounds containing phosphorus such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite. Among these, it is preferable to use a compound having a sulfur atom together with a phosphorus atom in the molecule, or a compound having two or more phosphorus atoms in the molecule.

The amount of each of these antioxidants (B) to (E) is 0.01 to 5 parts by weight, preferably 0.05 to 100 parts by weight, based on 100 parts by weight of the polyetherester block copolymer (A). To 3 parts by weight, more preferably 0.1 to
1.5 parts by weight. If the compounding amount of the antioxidants (B) to (E) is less than 0.01 part by weight, the degree of obtaining the intended improvement effect is small, and if the compounding amount is 5 parts by weight, blooming may occur or the polyetherester block may not be obtained. It is not preferable because the mechanical strength of the polymer is reduced.

The above antioxidants (B) to (E) are
It is essential that four types of (B) to (E) or three types of (B) to (D) or (B), (C) and (E) are combined and blended. If even one component is missing, the desired effect cannot be obtained.

When the polyester elastomer resin composition of the present invention is blended with a polyamide resin (F), it can be a polyetherester elastomer resin composition having further excellent oil resistance, grease resistance and heat aging resistance.
The polyamide resin (F) used in the polyester elastomer resin composition of the present invention is a polymer compound having an amide bond in a molecular chain, and a polymer from lactam,
Examples thereof include a salt polymer obtained by reacting adipic acid, sebacic acid, dodecanedioic acid and the like with ethylenediamine, hexamethylenediamine, metaxylenediamine, and the like, and a polymer from ω-aminocarboxylic acid. These polyamide resins may be copolymers,
Two or more different polymers may be used in combination. Among these polyamide resins, binary or 3
Even higher effects can be obtained when a copolymer polyamide resin of the original or higher is used.

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

In addition to the above-mentioned additives (B) to (E), various additives can be added to the polyester elastomer resin composition of the present invention as long as the object of the present invention is not impaired. For example, molding aids such as known crystal nucleating agents and lubricants, ultraviolet light absorbers and light-proofing agents that are hindered amine compounds,
It may optionally contain a hydrolysis resistance improver, a colorant such as a pigment or a dye, an antistatic agent, a conductive agent, a flame retardant, a reinforcing agent, a filler, a plasticizer, a release agent, and the like.

The method for producing the polyester elastomer resin composition of the present invention is not particularly limited. For example, a raw material in which a predetermined antioxidant is blended with a polyether ester block copolymer, or a polyether ester block A method in which a raw material in which a predetermined antioxidant and a polyamide resin are blended into a copolymer is supplied to a screw-type extruder and melt-kneaded, or a polyetherester block copolymer is first supplied to a screw-type extruder and melted. Then, an antioxidant or another compound may be supplied and kneaded from another supply port, and the polyamide resin may be supplied and kneaded from another supply port.

The polyester elastomer resin composition of the present invention constituted as described above is a product of ASTM No. Not only lubricating oils represented by 3 oils, but also excellent resistance to grease, and even when evaluated by the retention of tensile elongation at break in a severe oxidizing atmosphere, when evaluated by a 180-degree bending test, Exhibits excellent heat aging resistance.

Therefore, the polyester elastomer resin composition of the present invention is extremely excellent in grease resistance and heat aging resistance, and has rubber properties such as flexibility, resilience and elastic recovery, as well as extrudability and injection properties. It is a resin composition with excellent moldability, and is used for automobile parts, electric / electronic parts,
It is extremely useful in fields such as fibers and films.

[0032]

EXAMPLES The structure and effect of the present invention will be further described below with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified. The physical properties shown in Reference Examples were measured as follows.

[Relative Viscosity] A 0.5% polymer solution using o-chlorophenol as a solvent was measured at 25 ° C.

[Melting point] Differential scanning calorimeter (Du Pont)
Using a DSC-910 (manufactured by Sharp Corporation), the peak temperature of the melting peak when heated at a rate of 10 ° C./min in a nitrogen gas atmosphere was measured.

[Melt Viscosity Index (MFR Value)] ASTM
According to D-1238, temperature 240 ° C, load 2160g
Was measured.

[Hardness (Shore D scale)] JIS K
Measured according to -7215.

Reference Example Production of Polyester Block Copolymer (A-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 Was charged into a reaction vessel equipped with a helical ribbon type stirring blade together with 0.15 part of titanium tetrabutoxide, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. To the reaction mixture was added "Irganox" 1010 (a hindered antioxidant manufactured by Ciba Geigy) 0.7
After adding 5 parts, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out for 2 hours and 45 minutes under the conditions. The obtained polymer was discharged into water in the form of a strand, and cut into pellets.

[Production of polyetherester block copolymer (A-2)] 297 parts of dimethyl terephthalate,
243 parts of 1,4-butanediol and poly (tetramethylene oxide) glycol (number average molecular weight of about 200
0) 300 parts together with 0.15 part of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon-type stirring blade, and heated at 210 ° C. for 2 hours to obtain a theoretical methanol amount of 9 parts.
5% of methanol was distilled out of the system. To the reaction mixture
After adding 0.75 parts of Irganox "1010,
The temperature was raised to 245 ° C., and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 2 hours and 20 minutes. The obtained polymer was discharged into water in the form of a strand, and cut into pellets.

[Production of polyetherester block copolymer (A-3)] 189 parts of dimethyl terephthalate,
160 parts of 1,4-butanediol, poly (propylene oxide) end-capped with ethylene oxide
Glycol (number average molecular weight about 2200, EO content 26.
8%) 297 parts together with 0.15 part of titanium tetrabutoxide and 3 parts of trimellitic anhydride were placed in a reaction vessel equipped with a helical ribbon-type stirring blade, and heated at 210 ° C. for 2 hours 30 minutes to obtain theoretical methanol. 95% methanol
Was distilled out of the system. After adding 0.75 parts of “Irganox” 1010 to the reaction mixture, the temperature was raised to 245 ° C., and the pressure in the system was raised to 0.2 mmHg over 50 minutes.
The polymerization was carried out for 1 hour and 50 minutes under the reduced pressure. The obtained polymer was discharged into water in the form of a strand, and cut into pellets.

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

[0041]

[Table 1] [Antioxidant] The abbreviations and structural formulas of the antioxidants (B-1), (C-1), (D-1), (E-1) and (E-2) used in the following Examples are shown. It is shown in FIG.

[0042]

[Table 2] [Production of polyamide resin] A copolymer (polyamide resin (F-1)) having a composition ratio of polycaprolactam and polyhexamethylene adipamide of about 65/35, and polycaprolactam, polyhexamethylene adipamide and polyhexamethylene adipamide Hexamethylene sebacamide has a composition ratio of about 45/35
/ 20 terpolymer (polyamide resin (F-
2)) was manufactured.

Examples 1 to 5 The polyetherester block copolymers (A-1) and (A-
2) and (A-3), each antioxidant alone, or both the antioxidant and the polyamide resin were dry-blended at the compounding ratio shown in Table 3, and a twin-screw extruder having a 45 mmφ screw was used. After melt-kneading at 240 ° C., the mixture was pelletized. After drying the pellets at 80 ° C. for 5 hours, JIS 2 at a molding temperature of 240 ° C. and a mold temperature of 60 ° C.
No. dumbbell injection molding. 120 ° C
ASTM No. 3 The sample was immersed in oil, and the time required for the tensile elongation at break to fall to half of the initial value was measured. "Showa Sunlight Grease SW-2" manufactured by Showa Sekiyu KK at 120 ° C
(High-grade lithium soap grease) and “Molyrex No. 2” (combined with high-grade lithium soap grease and molybdenum disulfide) manufactured by Kyodo Yushi Co., Ltd. at 120 ° C., respectively. The time to drop in half was measured. Further, the injection-molded dumbbell is heated to 160 ° C.
Was measured in a hot air oven to reduce the tensile elongation at break to half of the initial value, and the time until the dumbbell was broken at 180 ° bending was measured. Table 4 shows the results.

[0044]

[Table 3]

[Table 4] [Comparative Examples 1 to 10] Raw materials of the resin composition were dry-blended at the respective mixing ratios shown in Table 3 and pelletized in the same manner as in Examples 1 to 5. These pellets and the polyester block copolymers (A-1), (A-
2) and (A-3) were themselves injection-molded to produce dumbbells in the same manner as in Examples 1 to 5, and evaluated similarly. The results are shown in Table 4.

As is evident from the results in Table 4, the polyether ester block copolymer was blended with an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, and a sulfur-based antioxidant. The polyester elastomer resin composition of the invention (Example 1) is excellent in oil resistance, grease resistance, and heat aging resistance. Further, an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant and / or a phosphorus-based antioxidant, and a polyamide resin were further added to the polyetherester block copolymer. The polyester elastomer resin composition of the present invention (Examples 2 to 5) is extremely excellent in oil resistance, grease resistance, and heat aging resistance. on the other hand,
The resin compositions of Comparative Examples 1 to 10 are inferior in oil resistance, grease resistance, and heat aging resistance as compared with the resin composition of the present invention.

[0046]

As described above, the polyester elastomer resin composition of the present invention comprises a polyetherester block copolymer, an aromatic amine antioxidant, a hindered phenol antioxidant, and a sulfur-based antioxidant. An antioxidant and / or a phosphorus-based antioxidant, or a polyetherester block copolymer, an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, and a sulfur-based antioxidant By mixing the agent and / or phosphorus-based antioxidant and polyamide resin,
Exhibits excellent oil resistance, grease resistance and heat aging resistance.

Claims (11)

[Claims] 1. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (b) mainly composed of an aliphatic polyether unit. 0.01 to 5 parts by weight of an aromatic amine-based antioxidant (B) based on 100 parts by weight of the ether ester block copolymer (A);
Hindered phenolic antioxidant (C) 0.01 to 5
Parts by weight, 0.01 to 5 parts by weight of a sulfur-based antioxidant (D) and / or 0.01 to 5 parts by weight of a phosphorus-based antioxidant (E)
A polyester elastomer resin composition which is blended with parts by weight. 2. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly composed of aliphatic polyether units. 0.01 to 5 parts by weight of an aromatic amine-based antioxidant (B) based on 100 parts by weight of the ether ester block copolymer (A);
Hindered phenolic antioxidant (C) 0.01 to 5
Parts by weight, 0.01 to 5 parts by weight of a sulfur-based antioxidant (D) and / or 0.01 to 5 parts by weight of a phosphorus-based antioxidant (E)
A polyester elastomer resin composition obtained by mixing parts by weight and 0.1 to 20 parts by weight of a polyamide resin (F). 3. The high-melting crystalline polymer segment (a) which is a component of the polyetherester block copolymer (A) is composed of polybutylene terephthalate units. Resin composition. 4. The low-melting polymer segment (b), which is a constituent component of the polyetherester block copolymer (A), comprises a poly (tetramethylene oxide) glycol unit and / or an ethylene oxide of poly (propylene oxide) glycol. The polyester elastomer resin composition according to any one of claims 1 to 3, which is composed of a polymer unit. 5. The polyetherester block copolymer (A) according to claim 1, wherein a copolymerization amount of the low melting point polymer segment (b) is 10 to 80% by weight. Polyester elastomer resin composition. 6. The polyester elastomer resin composition according to claim 1, wherein the aromatic amine antioxidant (B) is a diphenylamine compound. 7. The polyester elastomer resin composition according to claim 1, wherein the hindered phenolic antioxidant (C) is a hindered phenolic compound having a molecular weight of 500 or more. 8. The polyester elastomer resin composition according to claim 1, wherein the sulfur-based antioxidant (D) is a thiodipropionate compound. 9. The resin composition according to claim 1, wherein the phosphorus antioxidant (E) is a compound having a sulfur atom as well as a phosphorus atom in the molecule. 10. The phosphorus antioxidant (F) is a compound having two or more phosphorus atoms in a molecule.
The resin composition according to any one of the above. 11. The polyester elastomer resin composition according to claim 1, wherein the polyamide resin (G) is a copolymerized polyamide resin.