JP2003012906A - Polyester elastomer resin composition for blow molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester elastomer resin composition excellently stable in melt viscosity retention and capable of providing a blow-molded product which is uniform in thickness, contains less foreign matters, and has an excellent external appearance. SOLUTION: The resin composition is prepared by adding 0.01-10 pts.wt. of (B) a bifunctional or higher epoxy compound or 0.01-10 pts.wt. of (C) a bifunctional or higher isocyanate compound to (X) a polyether ester block copolymer formed by solid phase polycondensation to have a specific MFR, and has a specific MFR and a specific carboxyl terminal group amount.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can provide a blow-molded article having excellent melt viscosity retention stability, uniform wall thickness, few foreign substances, and excellent appearance and performance, particularly flexible boots and the like. Of the polyester elastomer resin composition for blow molding, which is suitable for blow molding applications.

[0002]

Polyether ester 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. Extrudability,
It has excellent injection moldability, high mechanical strength, rubber properties such as impact resistance, elastic recovery, flexibility, low temperature and high temperature properties, and water resistance. Furthermore, it is thermoplastic and easy to process. Therefore, its applications are expanding to automobile parts, electric / electronic parts, textiles, films, etc.

However, when an attempt is made to use a polyetherester block copolymer as a blow molding resin, in the production by the melt polycondensation method, a polymer having a sufficiently high melt viscosity applicable to blow molding is obtained. It is difficult to get. When the polyetherester block copolymer is produced by the melt polycondensation method for a long time, the physical properties of the obtained polymer are often inferior.

In view of such circumstances, many attempts have hitherto been made to increase the melt viscosity of the polyether ester block copolymer, for example, JP-A-49-1329.
Japanese Unexamined Patent Publication 7 discloses a solid phase polycondensation method in which a polyether ester block copolymer obtained by melt polycondensation is finely divided and then the degree of polymerization is increased by solid phase polycondensation.

Further, attempts have been made to increase the melt viscosity such that blow molding is possible by adding a cross-linking agent and a thickening agent. For example, JP-A-11-323110 discloses a polyether ester block copolymer. And 2
A resin composition containing an epoxy compound having a functionality or higher is disclosed in JP-A-52-121699 and JP-A-57-7841.
No. 3, a resin composition obtained by reacting a polyether ester block copolymer with polyisocyanate is disclosed in JP-A-61-111318, and liquid diphenylmethane diisocyanate is mixed with the polyether ester block copolymer. Each resin composition is disclosed.

However, according to the solid phase polycondensation method disclosed in Japanese Patent Laid-Open No. 49-13297, a polyester elastomer resin having a high melt viscosity can be obtained, but the obtained polyester elastomer resin has a melt viscosity of There is a problem that there is a large dependence on residence time, and if molding is restarted after molding has been interrupted for a certain period of time, the molding conditions will change significantly, and adjustment will be required each time. .

Further, the above-mentioned JP-A-52-121699, JP-A-11-323110, and JP-A-52-1.
The polyester elastomer resin compositions disclosed in JP-A-21699, JP-A-57-78413, JP-A-61-111318 and the like are certainly polyester elastomer resin compositions having a high melt viscosity. In order to react with a polyether ester block copolymer having a relatively low melt viscosity obtained by the melt polymerization method by adding a thickener or a crosslinking agent, it is necessary to add a large amount of these compounds. Then, in this case, the reaction is difficult to control, it is difficult to stably obtain a resin composition having a desired melt viscosity, that the melt viscosity is variable even within the same lot, and stable blow molding cannot be performed.
Also, there is a problem that foreign matter is generated in the molded product due to easy formation of gelled product, resulting in poor appearance of the molded product and deterioration of performance of the molded product. Further, there is a problem that the flexural fatigue resistance and the tear strength at high temperature are not sufficiently high due to the structural change of the polymer chain due to branching or crosslinking. In particular, the polyether ester block copolymer obtained by melt polycondensation contains low-molecular weight monomers and oligomers, and therefore, even when it is reacted with a thickener or a cross-linking agent, flex fatigue resistance at high temperatures and The fact is that a polyester elastomer resin composition having a sufficiently high tear strength cannot be obtained.

On the other hand, many attempts have been made to improve the heat aging resistance, oil resistance, grease resistance and the like of polyester elastomers. For example, JP-A-2-173059 discloses a polyether ester block copolymer, A resin composition containing a copolyamide and a hindered phenol-based antioxidant, a sulfur-based antioxidant and / or a phosphorus-based antioxidant is disclosed in JP-A-11-323.
No. 109 discloses a polyether ester block copolymer containing an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant and / or a phosphorus-based antioxidant, if desired. Each discloses a resin composition containing a polyamide resin.

However, the polyester elastomer resin compositions disclosed in JP-A Nos. 2-173059 and 11-323109 all have excellent heat aging resistance, oil resistance, grease resistance and injection moldability. Although it is certainly excellent, it has problems that it is not enough as a material for blow molding in terms of melt viscosity, and that flexural fatigue resistance and tear strength at high temperatures are not sufficiently high. It was

Many attempts have been made to improve the sliding characteristics of polyester elastomers, for example, JP-A-6-
No. 329888 discloses a resin composition obtained by blending a polyester block copolymer with an aliphatic polyether compound, an aliphatic polylactone compound, an aliphatic polyester, an unmodified polyolefin, and the like, and JP-A-11-1812.
In Japanese Patent Laid-Open No. 59 and Japanese Patent Laid-Open No. 5-279557, resin compositions in which a fatty acid amide compound is mixed with a polyester block copolymer are disclosed.

However, the resin composition disclosed in JP-A-6-329888 has a high melt viscosity to some extent,
Although it has improved slidability, when it is tried to be used in blow molding applications such as flexible boots, it has heat aging resistance, grease resistance, oil resistance, and bending fatigue resistance at high temperatures. The properties and tear strength are still insufficient. Further, although the resin compositions disclosed in JP-A-11-181259 and JP-A-5-279557 have improved slidability, they are not suitable for blow molding in terms of melt viscosity, In terms of heat aging resistance, grease resistance, oil resistance, bending fatigue resistance at high temperature, and tear strength, it was insufficient for blow molding applications such as flexible boot applications.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of studying how to solve the above-mentioned problems in the prior art.

Therefore, an object of the present invention is to provide a blow-molded article having excellent melt viscosity retention stability, uniform wall thickness, little foreign matter, and excellent appearance and performance, especially flexible boots. Another object of the present invention is to provide a polyester elastomer resin composition for blow molding, which is suitable for blow molding applications. Furthermore, polyester elastomer resin composition for blow molding with improved heat aging resistance, grease resistance, bending fatigue resistance and tear strength at high temperatures, and improved sliding characteristics centering on stick-slip suppressing effect. To provide things.

[0014]

In order to achieve the above object, the polyester elastomer resin composition for blow molding of the present invention comprises a high melting point crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit. And a polyether ester block copolymer (A) mainly composed of a low melting point polymer segment (b) mainly composed of an aliphatic polyether unit, which is obtained by finely granulating and then solid-phase polycondensing From the melting point of the polyether ester block copolymer (A), the formula To = R (T
m) +20 ... (1) (where Tm is the melting point of the polyetherester block copolymer (A), and R (x) is x = 1.
It is defined as the value rounded up to the nearest zero. ), The melt flow rate measured at a load of 2160 g is 5 according to ASTM D-1238.
With respect to 100 parts by weight of the polyether ester block copolymer (X) whose viscosity has been increased to g / 10 minutes or less,
0.01 to 10 parts by weight of the bifunctional or higher functional epoxy compound (B) or the bifunctional or higher functional isocyanate compound (C) 0.
Melt flow measured at a load of 2160 g according to ASTM D-1238 at a temperature To determined by the above formula (1) from the melting point of the polyether ester block copolymer (A). It is characterized in that the rate is 5 g / 10 minutes or less and the amount of carboxyl end groups is 50 equivalents / ton or less.

In the blow-molded polyester elastomer resin composition of the present invention, 100 parts by weight of the polyether ester block copolymer (X) is used.
Further, the aromatic amine antioxidant (D), the hindered phenol antioxidant (E), the sulfur antioxidant (F), and the phosphorus antioxidant (G) are each 0.01 to.
5 parts by weight of (D) alone, a combination of (E) and (F),
Combination of (E) and (G), combination of (E) + (F) + (G), combination of (D) + (E) + (F), (D) +
Combination of (E) + (G), (D) + (E) + (F) +
(G) is added in any one of the combinations, and the polyamide resin (H) is added in an amount of 0.1 to 2 with respect to 100 parts by weight of the polyether ester block copolymer (X).
0 parts by weight of the polyether ester block copolymer (X), 100 parts by weight of the polyether ester block copolymer (X), an aliphatic polyether compound (I), an aliphatic polyester compound (J), and an aliphatic polylactone. Compound (K),
0.01 to 10 parts by weight of at least one compound selected from fatty acid amide compounds (L) is blended, and 100 parts by weight of the polyether ester block copolymer (X) is used. Further, 0.1 to 20 parts by weight of polyamide resin (H) and aliphatic polyether compound (I), aliphatic polyester compound (J), aliphatic polylactone compound (K), fatty acid amide compound (L), unmodified 0.01 to 10 parts by weight of at least one compound selected from the polyolefin (M) is mixed, and 100 parts by weight of the polyether ester block copolymer (X) is further added. And 0.01 to 10 parts by weight of the colorant (N).
The polyether ester block copolymer (X) is
From the melting point of the polyether ester block copolymer (A) at the temperature To determined by the above formula (1), A
According to STM D-1238, the melt flow rate measured under a load of 2160 g is 2 g / 10 minutes or less, preferably 1 g / 10 minutes or less, and the viscosity of the polyester elastomer resin composition is increased. From the melting point of the polyetherester block copolymer (A) to the temperature To determined by the above formula (1), A
According to STM D-1238, the melt flow rate measured with a load of 2160 g is 3 g / 10 minutes or less, preferably 2 g / 10 minutes or less, more preferably 1 g / 10.
Or less, and from the melting point of the polyether ester block copolymer (A) before the solid-phase polycondensation, the formula (1)
At temperature To determined by ASTM D-123
8, the melt flow rate measured at a load of 2160 g is 100 g / 10 minutes or less, 10 g / 10 minutes or more, the amount of carboxyl end groups of the polyester elastomer resin composition is 40 equivalents / ton or less, preferably 30 equivalents. It is a preferable condition that it is less than 1 ton / ton and that it is a molding composition for a flexible boot, and when these conditions are applied, it is possible to expect to obtain a more excellent effect.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The high melting point crystalline polymer segment (a) of the polyether ester block copolymer (A) used in the present invention is formed from an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol. A unit composed of crystalline aromatic polyester, preferably terephthalic acid and / or dimethyl terephthalate and 1,4
A polybutylene terephthalate unit derived from butanediol, and other than this, 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, and a molecular weight of 3
00 or less diol, for example, 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 quarterphenyl, or a copolyester 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, etc. within a range of 5 mol% or less.

The low melting point polymer segment (b) of the polyester block copolymer (A) used in the present invention is a unit containing an aliphatic polyether as a main constituent.
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 ethylene oxide addition polymers of propylene oxide) glycol and copolymers of ethylene oxide and tetrahydrofuran. Among these aliphatic polyethers, the use of ethylene oxide adducts of poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol is preferred because the polyester block copolymer obtained has excellent elastic properties. Further, the number average molecular weight of these low melting point polymer segments is 300 in the copolymerized state.
It is preferably about 6000.

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

The polyetherester block copolymer (A) used in the present invention is obtained by melt polycondensation. Melt polycondensation can be carried out by a known method.
For example, a method of subjecting a lower alcohol diester of dicarboxylic acid, an excess amount of a low molecular weight glycol, and a low melting point polymer segment component to transesterification in the presence of a catalyst, and polycondensing a reaction product obtained, a dicarboxylic acid and an excess amount. Of polyglycol and low melting point polymer segment components are subjected to an esterification reaction in the presence of a catalyst, and the resulting reaction product is polycondensed, and a high melting point crystalline segment is prepared in advance, and the low melting point segment component is added thereto. Then, any method such as a method of randomizing by a transesterification reaction may be used. The polymerization degree of the polyetherester block copolymer (A) is not particularly limited, but the polyetherester block copolymer (A) is not limited.
From the melting point of the formula To = R (Tm) +20 (1) (where Tm is defined as the melting point of the polyetherester block copolymer (A), and R (x) is defined as the value obtained by rounding up x to the 10th place. .) At a temperature To determined by AS
According to TMD-1238, the melt flow rate measured with a load of 2160 g is 100 g / 10 minutes or less, 10
It is preferable to perform melt polycondensation until it becomes g / 10 minutes or more.

The polyether ester block copolymer (A) obtained by melt polycondensation is then finely divided. Fine graining may be performed by a cold cut method in which the polyether ester block copolymer (A) taken out in a gut shape or a sheet shape is pelletized with a cutter, or by a hot cut method in which pelletization is performed without forming a gut shape or a sheet shape. Good. Alternatively, the polyether ester block copolymer (A) taken out in a lump form may be obtained by pulverization.

The solid phase polycondensation is carried out at a temperature at which the polyether ester block copolymer (A), which has been finely pulverized after melt polycondensation, does not fuse, but is usually about 140 ° C to about 220 ° C.
Perform in a temperature range of about. Prior to the solid phase polycondensation, a pre-crystallization and a drying step may be performed. Further, the solid phase polycondensation is carried out under a high vacuum or an inert gas stream. Under high vacuum,
Preferably 665 Pa or less, more preferably 133 P
It is performed under reduced pressure of a or less. In the case of an inert gas flow, it is typically preferable to carry out under a nitrogen gas 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 or a tower dryer capable of flowing an inert gas. By performing solid-phase polycondensation using such conditions and equipment, at the temperature To determined by the above formula (1) from the melting point of the polyetherester block copolymer (A), the ASTM
According to D-1238, the melt flow rate measured with a load of 2160 g is 5 g / 10 minutes or less, preferably 2
A polyether ester block copolymer (X) having a viscosity increased to g / 10 minutes or less, more preferably 1 g / 10 minutes or less is obtained.

Specific examples of the bifunctional or higher functional epoxy compound (B), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, include bisphenol A-diglycidyl ether and bisphenol F-.
Diglycidyl ether, bisphenol S-diglycidyl ether, isocyanuric acid triglycidyl ether,
Cresol novolac type glycidyl ether, phenol novolac type glycidyl ether, bisphenol A type epoxy resin produced by condensation reaction of bisphenol A and epichlorohydrin, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether,
Diglycidyl ether compounds of glycols such as dibromoneopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether Polyglycidyl ether compounds of polyols such as ether and sorbitol polyglycidyl ether, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid Acid diglycidyl ester, methyl terephthalic acid dig Sidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecane dicarboxylic acid diglycidyl ester, octadecane dicarboxylic acid diglycidyl ester, dimer Examples thereof include diglycidyl ester compounds of dicarboxylic acids such as acid diglycidyl ester, and polyglycidyl ester compounds of polycarboxylic acids such as trimellitic acid triglycidyl ester and pyromellitic acid tetraglycidyl ester. It may be an epoxidized diene block copolymer. Among these, bifunctional epoxy compounds having two glycidyl groups in the compound are preferable. Further, a glycidyl ester compound is particularly preferable.

Examples of the difunctional or higher functional isocyanate compound (C) which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and isophorone. Diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Examples thereof include xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Of these, 4,4'-diphenylmethane diisocyanate is preferably used.

In the blow-molding polyester elastomer resin composition of the present invention, a bifunctional or higher functional epoxy compound (B) or a bifunctional or higher functional isocyanate compound (C) is added to 100 parts by weight of a polyetherester block copolymer (A). 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, and more preferably 0.1 to 10 parts by weight.
Add 5 parts by weight. If the blending amount is less than the above range, the effect is small, and if the blending amount exceeds the above range, gelation occurs due to melt retention during molding and molding is not possible, which is not preferable.

In the blow-molding polyester elastomer resin composition of the present invention, when a antioxidant is further added, a polyether ester elastomer resin composition having excellent oil resistance, grease resistance and heat aging resistance can be obtained.

Specific examples of the aromatic amine antioxidant (D), which is one of the components used in the blow-molding polyester elastomer 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 of these, use of diphenylamine compounds is preferable.

Specific examples of the hindered phenolic antioxidant (E), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, include:
2,4-dimethyl-6-t-butylphenol, 2,6
-Di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-di-t
-Butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-
Ethylphenol, 4,4'-bis (2,6-di-t
-Butylphenol), 2,2'-methylene-bis-4
-Methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), 4,4'-methylene-bis (6-t-butyl-o)
-Cresol), 4,4'-methylene-bis (2,6-
Di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol),
4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), bis (3-methyl-4-)
Hydroxy-5-t-butylbenzyl) sulfide,
4,4'-thiobis (6-t-butyl-o-cresol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-bis (2'-hydroxy-)
3'-t-butyl-5'-methylbenzyl) -4-methylphenol, 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-t-butyl-4-hydroxyphenol) propionate],
N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-
Thio [diethyl-bis-3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionate], 3,5-
Di-t-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis [methylene-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2
-Methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, and tris [β- (3,5-di- t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like. Among them, especially those having a molecular weight of 50 such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.
Use of 0 or more is preferable.

The sulfur antioxidant (F), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, is a thioether type, a dithioate type such as nickel dithiocarbamate, or a mercaptobenzimidazole. And sulfur-containing compounds such as thiocarbanilide and thiodipropion ester.
Among these, it is particularly preferable to use a thiodipropion ester compound.

The phosphorus-based antioxidant (G), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, is phosphoric acid, phosphorous acid, a hypophosphorous acid derivative, or phenylphosphonic acid. , Phosphorus compounds such as polyphosphonates, dialkylpentaerythritol diphosphites, and dialkylbisphenol A diphosphites. Among these, compounds having a sulfur atom as well as a phosphorus atom in the molecule, or 2 in the molecule
Preference is given to using compounds with one or more phosphorus atoms.

The blending amount of these antioxidants (D) to (G) is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of the polyether ester block copolymer (X). Is 0.05 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight. Antioxidant (D)
When the compounding amount of (G) is less than the above range, the degree of obtaining the desired improvement effect is small, and when it exceeds the above range, blooming occurs or the mechanical strength of the polyether ester block copolymer decreases. It is not preferable because

The above antioxidants (D) to (G) are
(D) alone, (E) and (F) or (G) in combination with each other, or (D) to (F) or (D), (E), (G) in each of three types And further, four types of (D) to (G) are combined and blended.

When the polyamide resin (H) is further added to the blow-molding polyester elastomer resin composition of the present invention, a polyether ester elastomer resin composition having excellent oil resistance, grease resistance and heat aging resistance can be obtained.

The polyamide resin (H), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, is a polymer compound having an amide bond in the molecular chain, and is a polymer derived from lactam. Or a polymer of a salt obtained by the reaction of adipic acid, sebacic acid, dodecanedioic acid, etc. with ethylenediamine, hexamethylenediamine, metaxylenediamine, or ω
Polymers such as aminocarboxylic acids. These polyamide resins may be copolymers, or two or more different polymers may be used in combination. Among these polyamide resins, when a binary or ternary or more copolymerized polyamide resin is used, a higher effect can be obtained.

The amount of the polyamide resin (H) compounded is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the polyether ester block copolymer (X). It is more preferably 0.5 to 5 parts by weight. If the blending amount of the polyamide resin (H) exceeds the above range, the inherent flexibility and rubber-like properties of the polyetherester block copolymer will be impaired, which is not preferable.

In addition to the aliphatic polyester compound (I), the aliphatic polyester compound (J), the aliphatic polylactone compound (K) and the fatty acid amide compound (L), the blow molding polyester elastomer resin composition of the present invention is further prepared. When blending at least one selected compound,
Sliding characteristics are improved, contributing to improved wear resistance and reduced sliding noise when using flexible boots.

The aliphatic polyether compound (I), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, includes poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetraoxide). Methylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymer of ethylene oxide and propylene oxide, ethylene oxide addition polymer of poly (propylene oxide) glycol, copolymer of ethylene oxide and tetrahydrofuran, copolymer of propylene oxide and tetrahydrofuran , Ethylene oxide addition polymer of propylene oxide and tetrahydrofuran copolymer, ethylene oxide addition polymer of poly (tetramethylene oxide) glycol, neopentyloxy Copolymer of ethylene oxide and ethylene oxide, copolymer of neopentyl oxide and propylene oxide, ethylene oxide addition copolymer of copolymer of neopentyl oxide and propylene oxide, copolymer of neopentyl oxide and tetrahydrofuran, neopentyl oxide Examples thereof include an ethylene oxide addition polymer of a tetrahydrofuran copolymer and an ethylene oxide addition polymer of poly (neopentyl oxide) glycol.

Examples of the aliphatic polyester compound (J) which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention include polyethylene adipate and polybutylene adipate.

Examples of the aliphatic polylactone compound (K), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, include poly (ε-caprolactone), polyenanthlactone and polycaprylolactone. Can be mentioned.

The fatty acid amide compound (L), which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention, is a monoamide compound such as oleyl oleic acid amide, oleyl stearic acid amide, or stearyl stearic acid amide. , Bisamide compounds such as methylenebisstearic acid amide, ethylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisoleic acid amide, methylenediaminestearic acid oleic acid mixed bisamide, ethylenediaminestearic acid oleic acid mixed bisamide, and higher aliphatic compounds Examples thereof include a carboxylic acid amide wax obtained by reacting a mixture of a monocarboxylic acid and a polybasic acid with a diamine.

Examples of the unmodified polyolefin (M) which is one of the components used in the blow-molding polyester elastomer resin composition of the present invention include polyethylene, polypropylene and ethylene-propylene copolymer.

At least one or more selected from the aliphatic polyether compound (I), the aliphatic polyester compound (J), the aliphatic polylactone compound (K), the fatty acid amide compound (L) and the unmodified polyolefin (M). The compounding amount of each compound is preferably 0.01 to 1 with respect to 100 parts by weight of the polyether ester block copolymer (X).
The amount is 0 parts by weight, more preferably 0.05 to 7 parts by weight, still more preferably 0.1 to 4 parts by weight. Compounding amount of at least one compound selected from aliphatic polyether compound (I), aliphatic polyester compound (J), aliphatic polylactone compound (K), fatty acid amide compound (L), and unmodified polyolefin (M) Is more than the above range, blooming may occur, or the mechanical strength of the polyether ester block copolymer may decrease, which is not preferable.

The blow molding polyester elastomer resin composition of the present invention may further contain a coloring agent (N). As the colorant, carbon black, titanium oxide, red iron oxide, inorganic pigments such as ultramarine, azo pigments, phthalocyanine pigments, quinacridone pigments, organic pigments such as dioxazine pigments, anthraquinone pigments,
Examples include indigoid-based dyes and azo-based dyes.

The amount of the colorant (N) compounded is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyetherester block resin composition.
7 parts by weight, more preferably 0.1 to 4 parts by weight.
The colorant (N) may be in the form of powder or paste, or may be in the form of masterbatch.

In the production of the blow-molding polyester elastomer resin composition of the present invention, the polyetherester block copolymer (A) obtained by melt polycondensation is pulverized and then solid-phase polycondensed to give a predetermined composition. Additives (B) to (N) are added to the polyether ester block copolymer (X) obtained by increasing the viscosity until reaching the melt flow rate.

The method of blending the additives (B) to (N) is not particularly limited. For example, a raw material obtained by blending the polyether ester block copolymer (X) with a predetermined additive, or a polyether. Raw material in which the ester block copolymer (X) is blended with a prescribed additive and a polyamide resin, or polyether ester block copolymer (X) is blended with a prescribed additive, a polyamide resin and a compound for improving slidability. A method in which the raw material is supplied to a screw type extruder and melt-kneaded, and a polyether type ester block copolymer (X) is first supplied and melted in the screw type extruder, and an antioxidant or a sliding agent is further supplied from another supply port. A method of supplying a compound for improving mobility or other compounds and kneading them, and then supplying and kneading a polyamide resin from another port can be appropriately adopted.

The blow-molding polyester elastomer resin composition of the present invention can be obtained, for example, by the above-mentioned method. The obtained blow-molding polyester elastomer resin composition is a polyether ester block copolymer (A). From the melting point of the formula To = R (Tm) +20 (1)
(However, Tm is defined as the melting point of the polyether ester block copolymer (A), and R (x) is defined as a value obtained by rounding up x to the nearest ten.)
According to STM D-1238, the melt flow rate measured at a load of 2160 g is 5 g / 10 minutes or less, preferably 3 g / 10 minutes or less, more preferably 2 g / 10 minutes or less, still more preferably 1 g / 10 minutes or less.

When the melt flow rate of the polyester elastomer resin composition for blow molding measured by the above method exceeds the above range, the blow moldability is poor and the bending fatigue resistance and tear strength at high temperature are insufficient. Is.

Therefore, when the blow molding polyester elastomer resin composition of the present invention is produced, the cylinder of the screw extruder is adjusted so that the melt flow rate of the obtained resin composition measured by the above method is within the above range. It is necessary to appropriately set conditions such as temperature and screw rotation speed.

The blow-molded polyester elastomer resin composition of the present invention has a carboxyl end group concentration of 5
It is desirable that the amount is 0 equivalent / ton or less, preferably 40 equivalent / ton or less, and more preferably 30 equivalent / ton or less. When the carboxyl terminal group concentration of the blow-molding polyester elastomer resin composition exceeds the above range, the blow-molding property is inferior, and the bending fatigue resistance and tear strength at high temperature are insufficient.

Various additives may be added to the blow-molding polyester elastomer resin composition of the present invention, in addition to the above-mentioned additives (B) to (N), within a range not impairing the object of the present invention. For example, a diene-based copolymer or a liquid olefin-based polymer containing a liquid material such as liquid polybutadiene for improving friction / wear characteristics, a molding aid such as a known crystal nucleating agent or lubricant, an ultraviolet absorber or a hindered amine. A light-proofing agent, a hydrolysis resistance improving agent, an antistatic agent, a conductive agent, a flame retardant, a reinforcing agent, a filler, a plasticizer, a release agent, and the like, which are system compounds, can be optionally contained.

By applying the polyester elastomer resin composition for blow molding of the present invention, a blow molded article having excellent melt viscosity retention stability, uniform wall thickness, less foreign matter, and excellent appearance and performance is obtained. Automotive parts that can be obtained, especially flexible boots such as constant velocity joint boots and rack and pinion boots,
It can be suitably used for blow molding applications such as electric and electronic parts.

[0053]

EXAMPLES The constitution and effects of the present invention will be further described below with reference to examples. In the examples,% and parts are by weight unless otherwise specified. In addition, the physical properties shown in the examples were measured as follows.

[Melting Point] Differential Scanning Calorimeter (Du Pont
(Manufactured by DSC-910 model) was used to measure the peak temperature of the melting peak when heated at a temperature rising rate of 10 ° C./min in a nitrogen gas atmosphere.

[Hardness (Shore D Scale)] JIS K
It was measured according to -7215.

[Melt Viscosity Index (MFR)] ASTM D-1238 at a temperature To determined by the formula (1) from the melting point of the polyether ester block copolymer (A).
According to the above, the load was measured at 2160 g.

To = R (Tm) +20 (1) Tm is defined as the melting point R (x) of the polyetherester block copolymer (A), which is the value obtained by rounding up x to the nearest 10.

[Amount of carboxyl end group] Sample 1.5
g was dissolved by heating in 50 ml of a mixed solvent of o-cresol / chloroform and titrated with a 0.04N ethanolic sodium hydroxide solution.

[Stability of Melt Viscosity] From the melting point of the polyether ester block copolymer (A) to the above formula (1)
At temperature To determined by ASTM D-123
8, the melt viscosity index (MF) at a load of 2160 g
In measuring R), in addition to the case where the melt residence time was 5 minutes, it was extended to 30 minutes and 60 minutes and its change was examined.

[Heat-resistant aging resistance] After the pellets were dried at 80 ° C. for 5 hours, the molding temperature was 240 ° C. and the mold temperature was 60 ° C.
A JIS No. 2 type dumbbell is injection-molded, and this dumbbell is aged in a hot air oven at 160 ° C., and the time at which the tensile elongation at break falls to half of the initial value, or the dumbbell is set to 1
The time until it was broken when it was bent at 80 degrees was measured.

[Grease resistance] After the pellets were dried at 80 ° C. for 5 hours, the molding temperature was 240 ° C. and the mold temperature was 60 ° C.
Injection-molded into a No. S type 2 dumbbell.
Showa Sekiyu KK "Shoishi Sunlight Grease SW at 0 ℃"
-2 "(high grade lithium soap grease), and the time at which the tensile elongation at break decreased to half of the initial value was measured in the same manner.

[Flexural fatigue resistance] Each pellet dried at 80 ° C. for 5 hours was press-molded at a temperature of 250 ° C. to give a thickness of 2 m.
A test piece of m and 20 mm in width was prepared. Using this test piece, the flex fatigue resistance was tested under the following conditions, and the crack length after 300,000 flex cycles was measured. In this test, the shorter the length of the generated crack, the better the durability.

Test conditions: Tester: De-Matcher bending fatigue tester Test temperature: 100 ° C. Distance between chucks: 25 mm ← → 5.6 mm Bending cycle: 300 times / min [Tear strength] It was measured according to ASTM D-624. The die was type C, and a test piece having a thickness of 2 mm was used, and measurement was performed at 120 ° C.

[Stick Slip] Pellets at 80 ° C.
After drying for 5 hours, molding temperature 240 ℃, mold temperature 60 ℃
Then, a disc test piece having a diameter of 100 mm and a thickness of 3 mm was injection molded. A small-diameter disc test piece with a diameter of 50 mm was set from a set of disc test pieces that had been left to stand in an atmosphere of 23 ° C. for 3 days after molding, to the wear wheel rotary shaft of the Taber abrasion tester, and a diameter of 50 mm
The disk test piece of No. 1 was set on the wear wheel rotating shaft of the wear tester. A Taber abrasion test is conducted with a load of 2631 g applied to the abrasion wheel rotating shaft, and noise is measured during 100 revolutions of the tester. It is determined that stick-slip occurs when noise increases with respect to background noise (about 60 dB). The measurement was carried out on the surface of a disk test piece having a diameter of 100 mm in a dry state and in a state of being wet with water.

[Uniformity of wall thickness] Pellets dried with hot air at 80 ° C for 5 hours were heated at a cylinder temperature of 23 using a press blow molding machine (SBE50 / 140 manufactured by Osberger).
Using a mold having a diameter of 6 cm and a height of 19 cm under a molding condition of 0 ° C., a nozzle temperature of 230 ° C., and a mold temperature of 30 ° C., a thickness of 1
mm straight bottles were molded, and the thicknesses of the upper part, the central part and the lower part of the molded product were measured.

[Blow Moldability] Pellets dried with hot air at 80 ° C. for 5 hours were heated at a cylinder temperature of 2 using a press blow molding machine (SBE50 / 140 manufactured by Osberger).
Under a molding condition of 30 ° C., nozzle temperature of 230 ° C., and mold temperature of 30 ° C., a large diameter portion and a small diameter portion are connected by a bellows portion having a thickness of 0.5 mm and having five peaks and five valleys. Blow moldability was evaluated by attempting to mold into a flexible boot for constant velocity joints weighing 60 g.

[Bifunctional or higher functional epoxy compound] The bifunctional or higher functional epoxy compound used in the examples is as follows.

B-1: Hexahydrophthalic acid diglycidyl ester [difunctional or higher functional isocyanate compound] The bifunctional or higher functional isocyanate compounds used in the examples are as follows.

C-1: Diphenylmethane diisocyanate [antioxidant] The antioxidant used in the examples is as follows.

D-1: Diphenylamine type antioxidant "Nowguard" 445 manufactured by Uniroyal Co., Ltd. E-1: Hindered phenol type antioxidant "Irganox" 1010 (molecular weight: 117 manufactured by Ciba Geigy)
7.7) F-1: Sulfur type antioxidant "Rasmit" (dilauryl thiodipropionate) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. G-1: Phosphorus type antioxidant "Adeka Stub" manufactured by Asahi Denka Co., Ltd. "PEP-8 (containing two phosphorus atoms in the molecule) G-2: Johoku Chemical Co., Ltd. phosphorus antioxidant JPS31
2 (trilauryl trithiophosphite, containing phosphorus atom and sulfur atom in the molecule) [Production of polyamide resin] The composition ratio of polycaprolactam, polyhexamethylene adipamide and polyhexamethylene sebacamide is about 45/35 / A terpolymer of 20 (polyamide resin (H-1)) was produced.

[Sliding property improver] The sliding property improvers used in the examples are as follows.

I-1: poly (tetramethylene oxide) glycol having a number average molecular weight of about 2000 J-1: polybutylene adipate having a number average molecular weight of about 2000 K-1: polycaprolactone L-1 having a number average molecular weight of about 2000: ethylene Bisoleic acid amide M-1: low density polyethylene having a number average molecular weight of 100,000 [Examples 1 and 2] 419 parts of terephthalic acid, 409 parts of 1,4-butanediol and a molecular weight distribution represented by the following formula (2). The dispersity α is 1.95 and the number average molecular weight is about 1400.
476 parts of poly (tetramethylene oxide) glycol (“Terratan” 1400 manufactured by DuPont) together with 2 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 190 to 225 ° C. for 3 hours. The esterification reaction was carried out while distilling the water of reaction out of the system.

Molecular weight distribution dispersion value α = Mv / Mn (2) (where Mn is the number average molecular weight, Mv is the viscosity average molecular weight defined by the following formula (3), and μ in the following formula is 40 ° C. Melt viscosity in Poise.) Mv = antilog (0.494 log μ + 3.0646) (3) “Irganox” 1010 (Hindered phenol type antioxidant manufactured by Ciba Geigy) was added to the reaction mixture. .7
After adding 5 parts, the temperature was raised to 245 ° C., and then the pressure inside the system was reduced to 27 Pa over 40 minutes.
Polymerization was carried out for 40 minutes to obtain a polyetherester block copolymer (A-1). The obtained polymer was discharged into water in a strand form, cut and pelletized. The melting point of the pellets was 198 ° C. and the melt viscosity index (MFR) measured at 220 ° C. was 18 g / 10 minutes. The pellets were charged into a rotatable reaction vessel, the pressure inside the system was reduced to 27 Pa, and the temperature was raised to 170 to 180 ° C. for 2 hours.
Solid phase polymerization was performed by heating while rotating for 0 hours.

The MFR of the obtained polyetherester block copolymer (X-1) measured at 220 ° C. was 4.5.
It was g / 10 minutes. Using the obtained polyetherester block copolymer (X-1), the raw materials were dry-blended in a compounding ratio as shown in Table 1, and the cylinder temperature was set to 220 ° C. by a twin-screw extruder having a screw of 45 mmφ. After melt-kneading with, pelletized. Using these pellets, the hardness and the amount of carboxyl terminal groups were measured, and the retention stability of melt viscosity and the wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 1.

[Example 3] The pellets of the polyether ester block copolymer (A-1) obtained in Example 1 were charged into a rotatable reaction vessel, and the pressure inside the system was reduced to 27 Pa to 170 to 180. Solid phase polymerization was performed by heating while rotating at 36 ° C. for 36 hours.

The MFR of the obtained polyetherester block copolymer (X-2) measured at 220 ° C. was 2.4.
It was g / 10 minutes. The polyether ester block copolymer (X-2) was used to dry-blend the raw materials at a compounding ratio as shown in Table 1, and a cylinder set temperature of 220 was set by a twin-screw extruder having a screw of 45 mmφ.
The mixture was melt-kneaded at a temperature of 150 rpm and pelletized. The pellets were used to measure the hardness and the amount of carboxyl end groups, and to evaluate the retention stability of melt viscosity and the wall thickness uniformity of blow-molded products. The results are shown in Table 1.

[Comparative Examples 1 and 2] With respect to the polyether ester block copolymers (X-1) and (X-2), the hardness and the amount of carboxyl terminal groups were measured, and the retention stability of melt viscosity and blow molding were measured. The thickness uniformity of the product was evaluated.
The results are shown in Table 1.

[0078]

[Table 1]

As is clear from the results shown in Table 1, the polyester elastomer resin compositions of Examples 1 to 3 produced by the method of the present invention have excellent melt viscosity retention stability and can be retained in the molten state for a long time. However, the change in melt viscosity index (MFR) is small. Furthermore, by using these polyester elastomer resin compositions, blow-molded articles having a uniform wall thickness can be obtained.

On the other hand, the solid-state polymerized polyetherester block copolymers of Comparative Example 1 and Comparative Example 2 which do not contain the bifunctional or higher functional epoxy compound or the bifunctional or higher functional isocyanate compound used in the present invention are The melt viscosity was largely changed due to the retention, and the thickness of the blow-molded product was not uniform.

[Examples 4 to 7] The pellets of the polyetherester block copolymer (A-1) obtained in Example 1 were charged into a rotatable reaction vessel, and the pressure inside the system was reduced to 27 Pa, and 170 Solid phase polymerization was carried out by heating while rotating at ˜180 ° C. for 48 hours.

The MFR of the obtained polyetherester block copolymer (X-3) measured at 220 ° C. was 1.5.
It was g / 10 minutes. The polyether ester block copolymer (X-3) was used to dry-blend the raw materials at a compounding ratio as shown in Table 2, and a cylinder set temperature of 220 was set by a twin-screw extruder having a screw of 45 mmφ.
The mixture was melt-kneaded at a temperature of 150 rpm and pelletized. The hardness and the amount of carboxyl end groups were measured using this pellet, and the retention stability of melt viscosity, heat aging resistance, and wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 3.

[Comparative Example 3] The pellets of the polyether ester block copolymer (A-1) obtained in Example 1 were charged in a rotatable reaction vessel and the pressure in the system was adjusted to 27P.
Solid pressure polymerization was carried out by heating at 170 to 180 ° C. for 15 hours while rotating under reduced pressure of a.

The MFR of the obtained polyetherester block copolymer (S) measured at 220 ° C. was 6.8 g /
It was 10 minutes. Using the obtained polyetherester block copolymer (S), the raw materials were dry-blended in a compounding ratio as shown in Table 2, and a cylinder set temperature of 220 was set by a twin-screw extruder having a screw of 45 mmφ.
The mixture was melt-kneaded at ℃ and screw rotation speed of 150 rpm, and then pelletized. Using these pellets, the hardness and the amount of carboxyl end groups were measured, and the heat aging resistance, melt viscosity retention stability, and wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 3.

[Comparative Example 4] Using the polyetherester block copolymer (X-3) obtained in Example 4, raw materials were dry-blended at the compounding ratios shown in Table 2 and 4
With a twin-screw extruder having a screw of 5 mmφ, the cylinder set temperature is 220 ° C and the screw rotation speed is 150 rp.
The mixture was melt-kneaded at m and pelletized. Using these pellets, the hardness and the amount of carboxyl end groups were measured, and the heat aging resistance, melt viscosity retention stability, and wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 3.

[Comparative Example 5] Using the polyetherester block copolymer (A-1) obtained in Example 1, raw materials were dry-blended at the compounding ratios shown in Table 2 and 4
With a twin-screw extruder having a screw of 5 mmφ, the cylinder set temperature is 220 ° C and the screw rotation speed is 150 rp.
The mixture was melt-kneaded at m and pelletized. Using these pellets, the hardness and the amount of carboxyl end groups were measured, and the heat aging resistance, melt viscosity retention stability, and wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 3.

[Comparative Example 6] Using the polyetherester block copolymer (X-2) obtained in Example 3, raw materials were dry-blended at the compounding ratios shown in Table 2 and 4
With a twin-screw extruder having a screw of 5 mmφ, the cylinder set temperature is 250 ° C and the screw rotation speed is 200 rp.
The mixture was melt-kneaded at m and pelletized. Using these pellets, the hardness and the amount of carboxyl end groups were measured, and the heat aging resistance, melt viscosity retention stability, and wall thickness uniformity of blow-molded products were evaluated. The results are shown in Table 3.

[Comparative Example 7] With respect to the polyetherester block copolymer (X-3), the hardness was measured, and the retention stability of melt viscosity, heat aging resistance, and wall thickness uniformity of blow-molded products were evaluated. . The results are shown in Table 3.

[0089]

[Table 2]

[0090]

[Table 3]

As is clear from the results of Tables 2 and 3, the blow molding polyester elastomer resin compositions of Examples 4 to 7 of the present invention are excellent in melt viscosity retention stability and retained for a long time in a molten state. Melt viscosity index (MF
The change in R) is small. Further, the heat aging resistance is good and the elongation at break is slow to decrease. Furthermore, by using these polyester elastomer resin compositions, blow-molded articles having a uniform wall thickness can be obtained.

On the other hand, the resin composition of Comparative Example 3 in which the melt viscosity index (MFR) of the solid-state polymerized polyether ester is larger than the definition of the present invention, the bifunctional or higher functional epoxy compound used in the present invention, or the bifunctional or higher functional compound. Of the resin composition of Comparative Example 4 prepared without blending the isocyanate compound described above, a low-viscosity melt polymer before solid-state polymerization, and a bifunctional or higher functional epoxy compound used in the present invention and an antioxidant used in the present invention Manufactured by Comparative Example 5, the resin composition of Comparative Example 6 having a larger amount of carboxyl end groups than the resin composition of the present invention, the bifunctional or higher functional epoxy compound used in the present invention, and the bifunctional or higher functional isocyanate. The solid-state polymerized polyetherester block copolymer of Comparative Example 7 in which the compound and the antioxidant were not mixed had a large change in melt viscosity due to retention, and thus had a high heat resistance. Ring resistance insufficient, also, the wall thickness of the blow molded article is not uniform.

[Example 8] Using the polyetherester block copolymer (X-3) obtained in Example 4, raw materials were dry blended at a compounding ratio as shown in Table 4 to obtain 45 m.
Using a twin-screw extruder having a mφ screw, the mixture was melt-kneaded at a cylinder setting temperature of 220 ° C. and a rotation speed of 150 rpm, and then pelletized. The hardness of the pellets was measured, and the retention stability of melt viscosity, heat aging resistance, grease resistance, flex fatigue resistance, and tear strength were evaluated. The results are shown in Table 5.

[Comparative Example 8] 419 parts of terephthalic acid, 1,
409 parts of 4-butanediol and poly (tetramethylene oxide) glycol (“Terratan” 1400 manufactured by DuPont) having a molecular weight distribution dispersity α represented by the following formula (1) of 1.95 and a number average molecular weight of about 1400: 476 Part was charged together with 2 parts of titanium tetrabutoxide in a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system.

Molecular weight distribution dispersion value α = Mv / Mn (2) (where Mn is the number average molecular weight and Mv is the viscosity average molecular weight defined by the following formula (3). Μ in the following formula is 40 ° C.) Melt viscosity in Poise.) Mv = antilog (0.494 log μ + 3.0646) (3) “Irganox” 1010 (Hindered phenol type antioxidant manufactured by Ciba Geigy) was added to the reaction mixture. .7
After adding 5 parts, the temperature was raised to 245 ° C., and then the pressure inside the system was reduced to 27 Pa over 40 minutes.
Polymerization was carried out for 20 minutes, but it reached the ceiling and the stirring torque no longer increased. When the polymerization was further continued, the stirring torque decreased, so the polymer obtained after the completion of melt polymerization was discharged into water in a strand form, cut and pelletized to obtain a polyetherester block copolymer (R). It was The melting point of this pellet is 198 ° C, and it is 22
Melt viscosity index (MFR) measured at 0 ° C was 4.2 g / 1
It was 0 minutes.

Using the obtained polyetherester block copolymer (R), raw materials were dry-blended in a compounding ratio as shown in Table 4, and a cylinder was set using a twin-screw extruder having a screw of 45 mmφ. The mixture was melt-kneaded at a temperature of 220 ° C. and then pelletized. The pellets were used to measure the hardness and the amount of carboxyl end groups, and to evaluate the retention stability of melt viscosity, heat aging resistance, and thickness uniformity of blow moldability. The results are shown in Table 5.

[Comparative Example 9] Using the polyetherester block copolymer (A-1) obtained in Example 1, raw materials were dry blended at a compounding ratio as shown in Table 4 to obtain 45 m.
Using a twin-screw extruder having a mφ screw, the mixture was melt-kneaded at a cylinder setting temperature of 220 ° C. and a rotation speed of 150 rpm, and then pelletized. The hardness of the pellets was measured, and the retention stability of melt viscosity, heat aging resistance, grease resistance, flex fatigue resistance, and tear strength were evaluated. The results are shown in Table 5.

[0098]

[Table 4]

[0099]

[Table 5]

As is clear from the results shown in Tables 4 and 5, the polyester elastomer resin composition of the present invention has excellent melt viscosity retention stability and has a melt viscosity index (MFR) even when retained in a molten state for a long time. Change is small. Further, the heat aging resistance is good and the elongation at break is slow to decrease. Furthermore, it has excellent grease resistance and flex fatigue resistance, and high tear strength.

On the other hand, in Comparative Example 8 in which the viscosity was made as high as possible by melt polymerization and the bifunctional or higher functional epoxy compound of the present invention and the additive of the present invention were mixed, the retention stability of melt viscosity was poor, The viscosity increased with the passage of time, and gelation occurred after 60 minutes. Further, in Comparative Example 9 in which the bifunctional or higher functional epoxy compound of the present invention and the additive of the present invention were blended with the melt-polymerized polymer before solid-phase polymerization, the retention stability of melt viscosity was poor, and with the passage of time. I lost viscosity. Further, in these comparative examples, heat aging resistance, grease resistance, flex fatigue resistance, and tear strength were lower than those of the examples.

[Examples 9 to 11] A polyester master resin composition 100 containing a black masterbatch containing 15% by weight of carbon black was added to the polyester elastomer resin compositions of the compositions of Examples 1, 6 and 8.
Add 2.5 parts by weight to 4 parts by weight.
Using a twin-screw extruder having a 5 mmφ screw, the mixture was melt-kneaded at a cylinder setting temperature of 220 ° C. and then pelletized. The melt viscosity index (MFR) of the pellets measured at 220 ° C. was 2.6 g / 10 min and 0.9 g, respectively.
/ 10 minutes, 1.1 g / 10 minutes, hardness is 47
D and the amount of carboxyl end groups are 31.8 equivalents /
Ton, 22.5 equivalent / ton, 24.6 equivalent / ton.

When the blow moldability was evaluated using these pellets, all the obtained flexible boot molded articles for constant velocity joints had the desired wall thickness at each site. The good dimensional stability was maintained without the need to make adjustments such as making large changes in molding conditions during an attempt of continuous molding for 3 hours. Further, not only immediately after the start of molding, but also in the molded product obtained after continuous molding for 3 hours, no visually observable foreign matter was generated, and a good appearance was maintained.

[Comparative Example 10] 15% by weight of carbon black was added to the polyester elastomer resin composition of Comparative Example 8.
The black masterbatch contained was added to 2.5 parts by weight with respect to 100 parts by weight of the polyester elastomer resin composition, and melted at a cylinder set temperature of 220 ° C. using a twin-screw extruder having a screw of 45 mmφ. After kneading, pelletized. The melt viscosity index (MFR) of the pellets measured at 220 ° C. was 1.5 g /
In 10 minutes, the hardness is 47D and the amount of carboxyl end groups is 5
It was 1.8 equivalents / ton. When blow moldability was evaluated using these pellets, the obtained flexible boot molded product for constant velocity joints had several parts that did not have the desired wall thickness, and the dimensional accuracy was not good. It was In addition, 10 to 20 foreign matters that were visible to the molded product were generated per molded product.

[Examples 12 to 17] terephthalic acid 403
Parts, 393 parts of 1,4-butanediol, and poly (tetramethylene oxide) glycol having a molecular weight distribution dispersity α represented by the following formula (2) of 1.80 and a number average molecular weight of about 2000 (Hodogaya Chemical Industry ( Ltd. PTG-20
00SN) 488 parts together with 2 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. .

Molecular weight distribution dispersion value α = Mv / Mn (2) (where Mn is the number average molecular weight and Mv is the viscosity average molecular weight defined by the following formula (3). Μ in the following formula is 40 ° C.) Melt viscosity in Poise.) Mv = antilog (0.494 log μ + 3.0646) (3) “Irganox” 1010 (Hindered phenol type antioxidant manufactured by Ciba Geigy) was added to the reaction mixture. .7
After adding 5 parts, the temperature was raised to 245 ° C., and then the pressure inside the system was reduced to 27 Pa over 40 minutes.
Polymerization was carried out for 50 minutes to obtain a polyetherester block copolymer (A-2). The obtained polymer was discharged into water in a strand form, cut and pelletized. The melting point of the pellets was 205 ° C. and the melt viscosity index (MFR) measured at 230 ° C. was 48 g / 10 minutes. The pellet was charged into a rotatable reaction vessel, the pressure inside the system was reduced to 27 Pa, and the temperature was raised to 170 to 180 ° C. for 3 hours.
Solid phase polymerization was performed by heating while rotating for 6 hours.

The MFR of the obtained polyetherester block copolymer (X-4) measured at 230 ° C. was 1.5.
It was g / 10 minutes.

Further, the pellets of the polyether ester block copolymer (A-2) were charged in a rotatable reaction vessel, the pressure inside the system was reduced to 27 Pa, and 170 to 18
Solid phase polymerization was carried out by heating while rotating at 0 ° C. for 42 hours. The MFR of the obtained polyetherester block copolymer (X-5) measured at 230 ° C. was 0.8 g / 1.
It was 0 minutes.

Further, pellets of the polyetherester block copolymer (A-2) were charged into a rotatable reaction vessel, and the pressure inside the system was reduced to 27 Pa to 170 to 1
Solid phase polymerization was carried out by heating while rotating at 80 ° C. for 50 hours. The MFR of the obtained polyetherester block copolymer (X-6) measured at 230 ° C. was 0.3 g /
It was 10 minutes.

The polyether ester block copolymers (X-4), (X-5) and (X-6) obtained above.
The raw materials were dry-blended in a blending ratio as shown in Table 6 by using, and melt-kneaded at a cylinder set temperature of 230 ° C. and a screw rotation speed of 150 rpm by a twin-screw extruder having a screw of 45 mmφ, and then pelletized. Using these pellets, the hardness and the amount of carboxyl end groups were measured, and the melt viscosity retention stability, grease resistance, flex fatigue resistance, tear strength, and stick-slip were evaluated. The results are shown in Table 7.

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

As described above, the polyester elastomer resin composition for blow molding of the present invention has excellent melt viscosity retention stability, uniform wall thickness, little foreign matter, and excellent appearance and performance. A blow-molded product can be provided, and it can be suitably used for blow-molding applications such as a constant velocity joint boot and a flexible boot represented by a rack and pinion boot. Furthermore, the polyester elastomer resin composition for blow molding of the present invention has heat aging resistance, grease resistance, bending fatigue resistance and tear strength at high temperatures sufficiently high, and sliding centering on the effect of suppressing stick-slip. It is possible to give a blow-molded product having improved properties.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/20 C08K 5/20 5/36 5/36 5/49 5/49 C08L 75/04 C08L 75 / 04 101/00 101/00 // C08G 59/40 C08G 59/40 (72) Inventor Kazuki Akiha 19 Toray DuPont Co., Ltd. Nagoya Office, 3804 North, Motoboshizaki-cho, Minato-ku, Nagoya, Aichi Prefecture (72) Inventor Mamoru Horiuchi 19 Toray DuPont Co., Ltd.Nagoya Plant F-term at 3804 North, Honboshizaki-cho, Minato-ku, Nagoya, Aichi Prefecture (Reference) 4J002 BB034 BB054 BB124 BB144 BB154 CD002 CD012 CD052 CD062 CD102 CD122 CD142 CD182 CF034 CF101 CF194 CH024 CK022 CL013 CL033 DA038 DE118 DE138 EE058 EJ026 EJ036 EN056 EP017 EP026 EP027 EQ018 EU028 EU038 EU186 EU196 EV046 EV056 EV076 EV096 EV136 EV346 EW046 EW066 EW126 FD076 FD098 GG0 1 4J029 AA03 AC03 AD01 AD06 AE01 BA02 BA03 BA04 BA05 BA10 BB03B BB10A BB11A BB13A BB15A BB18 BD04A BD08 BD10 BDH03 CB06A KD10 KD10 KD10 KD04 KD10 KD10 KD04 KD10 K02 K04 K04 K04 K04 K04 K04 K04 K04 K04 K04 K04 K04 K04 K02 HA01 HA06 HA07 HA08 HB05 HC03 HC12 HC13 HC17 JA06 QB19 QC10 QD04 RA06 SA08 SC03 SC04 SD10 4J036 AA01 AB01 AB02 AB03 AB08 AB10 AB17 AD08 AD21 AF06 AG04 AG06 AG07 AG13 AJ05 AJ06 DA01 DB14 DB17 FB11 HA12 JA15

Claims (15)

[Claims] 1. A polymer mainly composed of 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. It is obtained by finely granulating the ether ester block copolymer (A) and then subjecting it to solid phase polycondensation. From the melting point of the polyether ester block copolymer (A), the formula To = R (Tm) +20 ... ( 1) (where Tm is defined as the melting point of the polyetherester block copolymer (A), and R (x) is defined as the value obtained by rounding up x to the nearest 10).
According to STM D-1238, a bifunctional or higher epoxy with respect to 100 parts by weight of the polyether ester block copolymer (X) whose viscosity is increased to a melt flow rate measured at a load of 2160 g of 5 g / 10 minutes or less. Compound (B) 0.01 to 10 parts by weight or difunctional or higher functional isocyanate compound (C) 0.01 to 10 parts by weight is blended, and the above formula (from the melting point of the polyether ester block copolymer (A) Load 2 according to ASTM D-1238 at the temperature To determined in 1).
A blow-molding polyester elastomer resin composition having a melt flow rate measured at 160 g of 5 g / 10 minutes or less and a carboxyl end group amount of 50 equivalents / ton or less. 2. An aromatic amine-based antioxidant (D), a hindered phenol-based antioxidant (E), and a sulfur-based oxidation based on 100 parts by weight of the polyether ester block copolymer (X). 0.01 to 5 parts by weight of the antioxidant (F) and the phosphorus-based antioxidant (G), respectively, (D) alone, a combination of (E) and (F), a combination of (E) and (G), Combination of (E) + (F) + (G), (D) + (E)
+ (F) combination, (D) + (E) + (G) combination,
The polyester elastomer resin composition for blow molding according to claim 1, wherein the polyester elastomer resin composition is blended in any one of a combination of (D) + (E) + (F) + (G). 3. The polyamide resin (H) in an amount of 0.1 to 20 parts by weight is further mixed with 100 parts by weight of the polyether ester block copolymer (X). Alternatively, the polyester elastomer resin composition for blow molding according to 2). 4. An aliphatic polyether compound (I), an aliphatic polyester compound (J), an aliphatic polylactone compound (K), relative to 100 parts by weight of the polyether ester block copolymer (X). 0.01 or more of at least one compound selected from fatty acid amide compound (L) and unmodified polyolefin (M)
The blended polyester elastomer resin composition for blow molding according to claim 1 or 2, wherein the blended amount is 10 to 10 parts by weight. 5. A polyamide resin (H) in an amount of 0.1 to 20 parts by weight, an aliphatic polyether compound (I), and an aliphatic polyester relative to 100 parts by weight of the polyether ester block copolymer (X). 0.01 to 10 parts by weight of at least one compound selected from the compound (J), the aliphatic polylactone compound (K), the fatty acid amide compound (L), and the unmodified polyolefin (M) is mixed. The polyester elastomer resin composition for blow molding according to claim 1 or 2, wherein 6. The coloring agent (N) is further mixed in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyether ester block copolymer (X). The polyester elastomer resin composition for blow molding according to claim 1. 7. The temperature T determined by the formula (1) from the melting point of the polyetherester block copolymer (A), the polyetherester block copolymer (X).
melt flow rate measured at a load of 2160 g according to ASTM D-1238 of 2 g / 1.
The blow-molded polyester elastomer resin composition according to any one of claims 1 to 6, wherein the polyester elastomer resin composition has a viscosity increased to 0 minutes or less. 8. The temperature T determined by the formula (1) from the melting point of the polyether ester block copolymer (A),
melt flow rate measured at a load of 2160 g according to ASTM D-1238 of 1 g / 1.
The polyester elastomer resin composition for blow molding according to any one of claims 1 to 7, wherein the polyester elastomer resin composition has a viscosity increased to 0 minutes or less. 9. The temperature To determined by the formula (1) from the melting point of the polyether ester block copolymer (A) of the polyester elastomer resin composition,
Load 2160g according to ASTM D-1238
9. The blow molding polyester elastomer resin composition according to any one of claims 1 to 8, wherein the melt flow rate measured by the method is 3 g / 10 minutes or less. 10. The polyetherester block copolymer (A) of the polyester elastomer resin composition.
At the temperature To determined by the equation (1) from the melting point of No. 1, load 216 in accordance with ASTM D-1238.
The blow-molded polyester elastomer resin composition according to any one of claims 1 to 9, wherein a melt flow rate measured at 0 g is 2 g / 10 minutes or less. 11. The polyetherester block copolymer (A) of the polyester elastomer resin composition.
At the temperature To determined by the equation (1) from the melting point of No. 1, load 216 in accordance with ASTM D-1238.
The blow-molded polyester elastomer resin composition according to any one of claims 1 to 10, wherein the melt flow rate measured at 0 g is 1 g / 10 minutes or less. 12. ASTM D-1238 at a temperature To determined by the above formula (1) from the melting point of the polyether ester block copolymer (A) before solid phase polycondensation.
The blow-molding polyester elastomer resin composition according to any one of claims 1 to 11, wherein the melt flow rate measured with a load of 2160 g is 100 g / 10 minutes or less and 10 g / 10 minutes or more. object. 13. The blow-molding polyester elastomer resin composition according to claim 1, wherein the amount of carboxyl terminal groups of the polyester elastomer resin composition is 40 equivalents / ton or less. . 14. The blow-molding polyester elastomer resin composition according to claim 1, wherein the amount of carboxyl end groups of the polyester elastomer resin composition is 30 equivalents / ton or less. . 15. The polyester elastomer resin composition for blow molding according to claim 1, wherein the blow molded product is a flexible boot.