JP5549902B2 - Polyether ester block copolymer composition - Google Patents

Description

  The present invention relates to a polyetherester block copolymer resin composition that has excellent heat resistance, can prevent resin deterioration due to melt retention, suppress the amount of carbide generation, and has improved slidability.

  Polyether ester block copolymers with crystalline aromatic polyester units such as polybutylene terephthalate units as hard segments and aliphatic polyether units such as poly (alkylene oxide) glycol units as soft segments are injection moldable. In addition to excellent moldability such as extrusion moldability and blow moldability, it has high mechanical strength, rubber properties such as impact resistance, elastic recovery, flexibility, low and high temperature characteristics, and water resistance. Furthermore, since it is thermoplastic and can be easily molded, its application is expanded to fields such as automobile parts, electrical / electronic parts, fibers, and films.

  However, the polyether ester block copolymer has excellent characteristics as described above, but is susceptible to oxidative deterioration, and when used at high temperatures, the mechanical strength decreases in a short time and cannot be used. There is a problem that the surface of the molded product is cracked and the appearance is deteriorated.

  Therefore, for the purpose of improving the thermal stability of the polyetherester block copolymer, a method of blending various hindered phenolic antioxidants with a sulfurous antioxidant (for example, see Patent Document 1). , A method of blending a hindered phenol antioxidant and a phosphorus antioxidant (for example, see Patent Document 2), a method of blending a polyamide and an arylamine (for example, see Patent Document 3), a polyamide and a hindered phenol system A method of blending an antioxidant with a sulfur-based antioxidant and / or a phosphorus-based antioxidant (see, for example, Patent Document 4) has been proposed.

  However, in any of the above methods, although the thermal stability in a solid state such as a molded product is improved, the thermal stability in the molten state is not always sufficient, so that the molding machine and the extruder are in a molten state for a long time. If the resin stays in the molding machine for a long time, the viscosity decreases and deterioration proceeds, and in some cases, carbonization may proceed. In order to avoid such problems, it is conceivable to remove the deteriorated resin in the cylinder by purging when restarting molding or extrusion. However, if the purge is insufficient, the deteriorated resin or carbide is mixed into the product. It may cause poor appearance and reduced physical properties of the molded product. For this reason, it may be possible to replace the inside of the molding machine or extruder with another resin that is difficult to deteriorate. In this case, if the replacement resin cannot be completely removed even after returning to the original resin, it is replaced with a product. Not only does the resin enter and cause foreign matter, but even if the purge time is increased, the loss of the resin and the amount of energy consumption increase, which is not preferable.

  Moreover, in order to improve the thermal stability of a polyetherester block copolymer, a method of blending an epoxy compound is known (see, for example, Patent Documents 5, 6, 7, and 8). However, in this case, although the epoxy compound reacts with the end of the polyetherester block copolymer to improve heat resistance and hydrolysis resistance, the thermal stability in the molten state is still insufficient.

Furthermore, when the polyether ester block copolymer has tackiness on the surface of the molded product, the molded products adhere to each other, which may cause yield and reduce productivity. For this purpose, a method of blending a lubricant for the purpose of imparting slidability (for example, see Patent Documents 9 and 10) is known. In this case, the lubricant itself is thermally deteriorated, resulting in a polyether. In order to affect the thermal stability at the time of melting of the ester block copolymer resin composition, improvement of this point has been desired.
Japanese Patent Publication No.46-37422 JP 60-217257 A JP 58-23848 A Japanese Patent Laid-Open No. 2-173059 JP 2000-143949 A JP 2000-143950 A JP-A-61-111318 JP 2000-159985 A Japanese Patent Laid-Open No. 3-229752 JP 2003-3050 A

  The present invention has been made as a result of studying the solution of the above-described problems in the prior art as an issue.

  Accordingly, an object of the present invention is to provide a polyether ester block copolymer composition that has excellent heat resistance, can prevent resin deterioration due to melt retention and suppress the amount of carbide generation, and further imparts slidability. There is to do.

  As a result of diligent studies to achieve the above-mentioned object, the present inventors have combined the above-mentioned polyether ester block copolymer with a specific antioxidant, a specific glycidyl ether compound, and a specific lubricant, to thereby The inventors have found that the object can be achieved effectively and have arrived at the present invention.

That is, in order to achieve the above object, according to the present invention, 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) and 100 parts by weight of the polyether ester block copolymer (A) as a main constituent, 0.05 to 5 parts by weight of a hindered phenol-based antioxidant (B), a phosphorus-based antioxidant ( Polyether ester block copolymer resin composition comprising 0.05 to 5 parts by weight of C) and / or sulfur-based antioxidant (D) and 0.1 to 3 parts by weight of glycidyl ether compound (E) A glycidyl ether compound (E) having an ethylene glycol skeleton, a propylene glycol skeleton, a neopentyl glycol skeleton in the molecule 1,6-hexanediol skeleton or resorcinol skeleton, a polyether ester block copolymer resin composition is a diglycidyl ether compound having a hydroquinone skeleton, before heat treatment of the polyether ester block copolymer resin composition A polyether ester block copolymer resin composition having a relative viscosity of 0.02 to 0.04 lower than the relative viscosity of the polyether ester block copolymer (A) is provided.

In the polyetherester block copolymer resin composition of the present invention,
Furthermore, 0.01 to 5 parts by weight of a polyolefin-based lubricant (F) is blended,
After heat treatment in air at a temperature T ° C. satisfying melting point + 15 ≦ T ≦ melting point + 40 for 2 hours, the resin composition has a surface carbonized layer having a thickness of less than 1 mm and an inner layer that is not more brittle than the surface carbonized layer. The relative viscosity ηr (conforming to JIS standard K7367-1, temperature: 25 ° C., solvent: o-chlorophenol) of the resin composition having a depth of 1 to 3 mm from the surface is represented by the following formula (I) Be satisfied,
ηr0−ηr1 ≦ 0.6 (I)
ηr0: Relative viscosity of the resin composition before treatment ηr1: Relative viscosity of the resin composition at a depth of 1 to 3 mm from the surface after the heat treatment The high melting crystalline polymer segment (a) is made of polybutylene terephthalate. about,
The low melting polymer segment (b), poly (tetramethylene oxide) be formed of a glycol, that you and the polyolefin-based lubricant (F) is a modified polyethylene wax, a both preferred conditions, these conditions By applying, it can be expected to obtain even better effects.

  According to the present invention, as will be described below, a polyetherester block copolymer that has excellent heat resistance, can prevent resin degradation due to melt retention and can suppress the amount of carbide generation, and has improved slidability. A resin composition can be obtained.

  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 a crystalline fragrance formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. A polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, but also terephthalic acid, isophthalic acid, phthalic acid, naphthalene- Dicarboxylic acid components such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof And a diol having a molecular weight of 300 or less, such as 1, -Aliphatic diols such as butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, alicyclic such as 1,4-cyclohexanedimethanol, tricyclodecane dimethylol Diol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) Aromatic diols such as phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quaterphenyl Invite from Polyester units are, or may be a copolymer polyester unit obtained by combining these dicarboxylic acid components and diol components of two or more. 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 point polymer segment (b) of the polyether ester block copolymer (A) used in the present invention is a unit comprising an aliphatic polyether as a main constituent component. Specific examples of aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (trimethylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide and propylene. And poly (alkylene oxide) glycols such as copolymers of oxides, ethylene oxide addition polymers of poly (propylene oxide) glycol, and copolymers of ethylene oxide and tetrahydrofuran. Among these aliphatic polyethers, the resulting polyester block copolymer has excellent elastic properties, so poly (trimethylene oxide) glycol, poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol are added with ethylene oxide. Such as poly (trimethylene oxide) glycol is particularly preferred. The number average molecular weight of these low-melting polymer segments is preferably about 300 to 6000 in the copolymerized state.

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

  The polyether ester block copolymer (A) used in the present invention is obtained by melt polycondensation. The melt polycondensation can be carried out by a known method. For example, a method in which a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol, and a low melting point polymer segment component are transesterified in the presence of a catalyst and the resulting reaction product is polycondensed, an excess amount of the dicarboxylic acid A method in which the glycol and low-melting-point polymer segment components are esterified 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 a low-melting-point segment component is added to this. Then, any method such as a method of randomizing by transesterification may be used.

  The polyether ester block copolymer (A) obtained by melt polycondensation is then finely divided. Fine granulation 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 a hot cut method in which pelletization is performed without forming a gut shape or a sheet shape. It may be. Moreover, you may obtain by grind | pulverizing the polyetherester block copolymer (A) taken out in the lump shape.

  The polyetherester block copolymer (A) obtained by melt polycondensation may then be subjected to solid phase polycondensation. The solid phase polycondensation is carried out at a temperature at which the polyether ester block copolymer (A) finely divided after melt polycondensation is not fused, but is usually carried out in a temperature range of about 140 ° C. to about 220 ° C. Prior to solid phase polycondensation, it is desirable to go through a precrystallization and drying step. The solid phase polycondensation is carried out under high vacuum or under an inert air stream. In the case of high vacuum, it is preferably performed under a reduced pressure of 665 Pa or less, more preferably 133 Pa or less. In the case of an inert air stream, it is typically preferable to carry out under a nitrogen stream, and the pressure is not particularly limited, but atmospheric pressure is preferred. As the reaction vessel, it is preferable to use a rotatable vacuum dryer or a tower dryer capable of flowing an inert gas.

  Specific examples of the hindered phenol antioxidant (B) that is one of the components used in the polyether ester block copolymer 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-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4′-thiobis (6-t -Butyl-o-cresol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-bis (2'-hydroxy-3'-tert-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, '-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-t-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis [methylene-3 (3,5-di-t-butyl-4- Loxyphenyl) 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 these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

  The compounding quantity of the hindered phenolic antioxidant (B) used for the polyetherester block copolymer resin composition of this invention is 0.05-5 with respect to 100 weight part of polyetherester block copolymers. Part by weight is preferable, and 0.1 to 3 parts by weight is more preferable.

  Phosphorus antioxidant (C) which is one of the components used in the polyether ester block copolymer composition of the present invention is phosphoric acid, phosphorous acid, hypophosphorous acid derivative, phenylphosphonic acid, poly Compounds containing phosphorus such as phosphonates, dialkylpentaerythritol diphosphites, and dialkylbisphenol A diphosphites. Among these, it is preferable to use a compound having two or more phosphorus atoms in the molecule, or a compound having a sulfur atom together with a phosphorus atom in the molecule.

  The sulfur-based antioxidant (D) used in the polyether ester block copolymer resin composition of the present invention is a thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, or thiodipropion ester. And other sulfur-containing compounds. Among these, the use of a thiodipropion ester-based compound is particularly preferable.

  The amount of the phosphorus-based antioxidant (C) and / or the sulfur-based antioxidant (D) used in the polyether ester block copolymer composition of the present invention is 100 parts by weight of the polyether ester block copolymer. On the other hand, 0.05-5 weight part is preferable and 0.1-3 weight part is further more preferable.

The glycidyl ether compound (E 1) used in the polyether ester block copolymer resin composition of the present invention contains, in one molecule, an ethylene glycol skeleton, a propylene glycol skeleton, a neopentyl glycol skeleton, and 1,6-hexanediol. It is a diglycidyl ether having a skeleton, or a resorcinol skeleton or a hydroquinone skeleton.

The blending amount of the glycidyl ether compound (E) used in the polyether ester block copolymer resin composition of the present invention is 0 . Ru 1 to 3 parts by weight of Der.

  The polyolefin-based lubricant (F) used in the polyetherester block copolymer resin composition of the present invention is a polyolefin-based wax having a molecular weight of 5000 or less obtained from a high-pressure method or a low-pressure method, and preferably a polyethylene-based wax lubricant. used. Further, a modified polyethylene wax in which a carboxylic acid or a hydroxyl group is introduced into the molecule by a method such as oxidation or acid-modified with maleic anhydride is particularly preferably used.

The polyether ester block copolymer resin composition of the present invention is a surface carbonized layer having a thickness of 1 mm or less after heat treatment in air in a molten state at a temperature T ° C. satisfying a melting point + 15 ≦ T ≦ melting point + 40. And a relative viscosity ηr of the resin composition having a depth of 1 to 3 mm from the surface (in accordance with JIS standard K7367-1, temperature: 25 ° C.) , Solvent: o-chlorophenol) satisfies the following formula (I).
ηr0−ηr1 ≦ 0.6 (I)
ηr0: relative viscosity of the resin composition before treatment ηr1: relative viscosity of the resin composition at a depth of 1 to 3 mm from the surface after heat treatment

  Here, the heat treatment is performed at a temperature T ° C. satisfying a melting point + 15 ≦ T ≦ melting point +40 corresponding to a normal processing temperature using pellets or powder of the polyether ester block copolymer resin composition. If possible, the heat treatment apparatus is not particularly limited, and for example, a thermostatic bath or an electric furnace can be used. The heat treatment is carried out at a temperature T ° C. satisfying the melting point + 15 ≦ T ≦ melting point + 40. The heat treatment is carried out at a temperature at which the pellets and powders of the polyetherester block copolymer resin composition are melted and naturally flow and become intangible. It is preferable to do. When the melting point is lower than + 15 ° C., the fluidity is not sufficient, and it is not suitable for the heat treatment temperature of the polyetherester block copolymer resin composition. Moreover, when it exceeds melting | fusing point +40 degreeC, it becomes higher than normal processing temperature, and since it becomes easy to accelerate | stimulate heat deterioration and oxidation deterioration, it is not suitable.

  The method for producing the polyetherester block copolymer composition of the present invention is not particularly limited. For example, the polyetherester block copolymer (A), the hindered phenol antioxidant (B), The raw material which mix | blended phosphorus antioxidant (C) and / or sulfur type antioxidant (D), glycidyl ether compound (E), and olefin lubricant (F) together is supplied to a screw type extruder. In the melt-kneading method, a polyether-type block copolymer is first supplied to a screw type extruder and melted, and then the hindered phenol antioxidant (B), phosphorus antioxidant ( C) and / or a sulfur antioxidant (D), a glycidyl ether compound (E), and an olefin lubricant (F) are supplied and kneaded. It can be employed as appropriate.

  In addition, the polyether ester block copolymer resin composition of the present invention can be subjected to solid-phase polycondensation after the melt-kneading and production.

  Various additives can be added to the polyether ester block copolymer resin composition of the present invention as long as the object of the present invention is not impaired. For example, a coloring agent such as a known pigment, a light stabilizer, an ultraviolet absorber, an antistatic agent, a release agent, a crystallization nucleating agent, a lubricant, a conductive agent, and a reinforcing agent can be optionally contained.

  The polyether ester block copolymer resin composition of the present invention can give a molded article by various molding methods for injection molding, extrusion molding, blow molding and the like. In addition, the molded article comprising the polyetherester block copolymer resin composition of the present invention can be used for automobiles, electronic / electric equipment, precision equipment, various parts for general consumer goods, etc., such as tubes, sheets, Suitable for film, fiber, etc.

  The configuration and effects of the present invention will be further described below with reference to examples. In the examples, “%” and “parts” are based on weight unless otherwise specified. The physical properties shown in the examples were measured as follows.

[Melting point]
Using a differential scanning calorimeter (DSC Q100, manufactured by TA Instruments Inc.), the top temperature of the melting peak when heated at a heating rate of 10 ° C./min in a nitrogen gas atmosphere was measured.

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

[Relative viscosity ηr]
The relative viscosity ηr at a temperature of 25 ° C. was determined according to JIS K7367-1. O-Chlorophenol was used as a solvent, the concentration was 500 mg of resin, and the solvent was 100 mL.

[specific gravity]
Measured according to ASTM D-792.

[Heat treatment evaluation]
Put 20 g of polyether ester block copolymer or polyether ester block copolymer composition pellets dried in vacuum at 80 ° C. for 3 hours in an aluminum cup (circular bottom with a diameter of 5 cm, side surface in bowl) It was placed in an electric furnace heated to a temperature T ° C. satisfying melting point + 15 ≦ T ≦ melting point + 40. The pellets were melted in an electric furnace to become non-shaped, accumulated in a molten state having a depth of 4 to 6 mm from the bottom surface of the aluminum cup, and the surface was in a horizontal state. After leaving the surface in contact with the air for 2 hours in this way, the aluminum cup is taken out of the electric furnace and naturally cooled to solidify the resin, and (1) to (3) are evaluated. The melt heat stability was determined.
(1) Thickness of surface carbonized layer after heat treatment The heat-treated resin was cut perpendicularly to the standing state during heat treatment, and then the thickness of the surface carbonized layer was measured. The surface carbonized layer is oxidized and deteriorated due to contact with oxygen, and carbonized to dark brown. The thicker the carbonized layer, the greater the influence of oxidation deterioration and the poorer stability at the time of melting.
(2) State of inner layer after heat treatment The inner layer deeper than the surface carbonized layer was examined for the presence of embrittlement. Those in which embrittlement is observed are inferior in thermal stability in the molten state.
(3) Relative viscosity ηr
After the heat treatment, the resin composition of the inner layer at a depth of 1 to 3 mm from the surface was cut out, and the relative viscosity ηr (based on JIS standard K7367-1, 25 ° C., solvent: o-chlorophenol) was measured. When embrittlement was observed in the inner layer, a portion that was not embrittled was used.
(4) Determination of thermal stability during melting The stability during melting of the resin composition was determined as follows.
○: (1) The thickness of the surface carbonized layer is 1 mm or less (2) No embrittlement in the inner layer (3) Relative viscosity difference before and after heat treatment ηr0−ηr1 ≦ 0.6
When all of the above are satisfied ×: All items that do not meet the condition of ○

[Slidability evaluation]
A square plate having a length of 75 mm, a width of 125 mm, and a thickness of 2 mm was formed by injection molding (molding temperature: 230 ° C.), and two square plate molded products were stacked after one day had passed after the molding. Then, only the lower square plate was held, and the side of 125 mm was inclined so that the square plate was not warped, and the inclination angle at which the molded product placed on the upper side was evaluated was evaluated. As the determination of the slidability, the case where the inclination angle was less than 45 degrees was marked with ◯, and the case where the inclination angle was 45 degrees or more was marked with x.

[Reference example]
[Production of Polyether Ester Block Copolymer (A)]
Polyether ester block polymers (A-1), (A-2), and (A-3) were produced by polymerization as in Reference Examples 1 to 4.

[Reference Example 1]
50.5 parts of terephthalic acid, 43.8 parts of 1,4-butanediol and 35.4 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 part of titanium tetrabutoxide and mono-n-butyl -0.02 part of monohydroxytin oxide was charged into a reaction vessel equipped with a helical ribbon type stirring blade and heated at 190 to 225 ° C for 3 hours to conduct esterification while distilling the reaction water out of the system. After adding 0.2 parts of tetra-n-butyl titanate to the reaction mixture and adding 0.05 parts of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.), 245 ° C. The pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was performed for 2 hours and 50 minutes under the conditions to obtain a polyether ester block copolymer (A-1). It was. The physical properties were a relative viscosity of 2.05 measured at melting points of 207 ° C. and 230 ° C., a hardness of 55 Shore D, and a specific gravity of 1.19.

[Reference Example 2]
41.9 parts of terephthalic acid, 40.9 parts of 1,4-butanediol and 47.6 parts of poly (tetramethylene oxide) glycol (“Tertan” 1400, manufactured by DuPont) having a number average molecular weight of about 1400 are added to titanium tetrabutoxide. The reaction vessel equipped with 0.2 part of a helical ribbon type stirring blade was charged and heated at 190 to 225 ° C. for 3 hours to conduct esterification while distilling the reaction water out of the system. After adding 0.075 part of “Irganox” 1010 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.) to this reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system over 40 minutes. Was reduced to 27 Pa, and polymerization was performed for 2 hours and 40 minutes under the conditions to obtain a polyetherester block copolymer (A-2). The physical properties were a melting point of 195 ° C., a relative viscosity of 1.90, a hardness of 47 Shore D, and a specific gravity of 1.15.

[Reference Example 3]
75.5 parts of dimethyl terephthalate, 42.8 parts of 1,4-butanediol and 15.8 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1000, 0.3 parts of titanium tetrabutoxide and trimellitic anhydride Into a reaction vessel equipped with a helical ribbon type stirring blade together with 0.1 part of the product, it was heated at 210 ° C. for 2 hours and 30 minutes, and 95% of the theoretical methanol amount was distilled out of the system. After adding 0.5 part of “Irganox” 1330 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.) to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system over 50 minutes. Was reduced to 27 Pa, and polymerization was carried out for 1 hour and 50 minutes under the conditions to obtain a polyether ester block copolymer (A-3). The physical properties were mp 218 ° C., relative viscosity 1.67, hardness 72 Shore D, specific gravity 1.26.

[Hindered phenol antioxidant (B)]
Irganox 1010 manufactured by Ciba Japan Co., Ltd. was used.

[Phosphorus antioxidant (C)]
PEP-8 manufactured by ADEKA Corporation was used.

[Sulfur Antioxidant (D)]
Rasmit LG manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used.

[Glycidyl ether compound (E)]
(E-1) to (E-6) were used.
E-1: Nagase ChemteX Corp. Denacol EX-811 (diethylene glycol diglycidyl ether)
E-2: Denasel EX-920 (polypropylene glycol diglycidyl ether) manufactured by Nagase ChemteX Corporation
E-3: Nagase ChemteX Corp. Denacol EX-211 (Neopentylglycol diglycidyl ether)
E-4: Nagase ChemteX Corp. Denacol EX-212 (1,6-hexanediol diglycidyl ether)
E-5: Nagase ChemteX Corp. Denacol EX-201 (resorcinol diglycidyl ether)
E-6: Denacol EX-203 (hydroquinone diglycidyl ether) manufactured by Nagase ChemteX Corporation

[Olefin lubricant (F)]
High wax 1105A manufactured by Mitsui Chemicals, Inc. was used.

[Others]
G: Denasel EX-721 (diglycidyl o-phthalate) manufactured by Nagase ChemteX Corporation

[Example]
[Example 1]
After the polyether ester block copolymer (A-1) obtained in Reference Example 1 was dried at 80 ° C. for 3 hours with a hot air dryer, the hindered phenol antioxidant (B) and the phosphorous oxidation were used. The inhibitor (C) and the glycidyl ether compound (E-1) were dry blended so as to have a composition as shown in Table 1, and at 230 ° C. using a twin screw extruder having a cylinder diameter of 45 mmφ. A polyether ester block copolymer resin composition was obtained by melt-kneading. Table 1 shows the hardness and melting point as physical properties, and the results of heat treatment evaluation.

[Examples 2 to 8]
Except for the composition shown in Table 1, a polyether ester block copolymer resin composition was obtained in the same manner as in Example 1. Table 1 shows the hardness and melting point as physical properties, and the results of heat treatment evaluation.

[Example 9]
A polyether ester block copolymer resin composition was obtained in the same manner as in Example 1 except that the blending composition shown in Table 1 and the melt kneading temperature were changed to 240 ° C. Table 1 shows the hardness and melting point as physical properties, and the results of heat treatment evaluation.

[Example 10]
The polyether ester block copolymer (A-1) obtained in Reference Example 1 was dried at 80 ° C. for 3 hours with a hot air dryer, and then hindered phenol antioxidant (B) and phosphorus antioxidant. Agent (C), glycidyl ether compound (E-1), and olefin lubricant (F) were dry blended so as to have the composition shown in Table 3, and a twin screw extruder having a cylinder diameter of 45 mmφ was used. Then, it was melt-kneaded at 230 ° C. to obtain a polyetherester block copolymer resin composition. Table 1 shows the hardness and melting point as physical properties, and the results of heat treatment evaluation.

[Comparative Examples 1-6]
A polyether ester block copolymer resin composition was obtained by melt-kneading in the same manner as in Example 1 so as to obtain the blending composition shown in Table 2. Table 2 shows hardness and melting point as physical properties, and results of heat treatment evaluation.

  In the heat resistance evaluation of the polyetherester block copolymer compositions of Examples 1 to 10, the surface in contact with air is dark brown and a 0.5 mm carbonized layer is formed, but the deeper inner layer is brittle. The part which turned into is not recognized, the relative viscosity fall of internal layer resin is also suppressed to 0.6 or less, and the stability at the time of a fusion | melting is excellent. On the other hand, in the polyether ester block copolymer resin compositions of Comparative Examples 1 to 6, not only the carbonized layer on the surface, but also the inner layer is embrittled, and the portion not embrittled is cut out and sampled. Nevertheless, the relative viscosity was greatly reduced as compared with Examples 1 to 10, and the stability during melting was poor.

[Example 11]
Using the polyether ester block copolymer resin composition of Example 10, slidability evaluation was performed. The results are shown in Table 3.

[Comparative Examples 7 and 8]
Using the polyetherester block copolymer of Comparative Example 1 and the polyetherester block copolymer composition of Comparative Example 4, slidability evaluation was performed. The results are shown in Table 3.

  In Example 11, the sliding start inclination angle in the slidability evaluation is 35 degrees, which is smaller than the sliding start inclination angles of Comparative Examples 7 and 8, and it can be confirmed that the slidability is high.

[Example 12]
After purging 3 kg of the polyetherester block copolymer resin composition of Example 10 dried at 80 ° C. for 3 hours with a hot air dryer at 240 ° C. using an injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. The heater power was turned off and the cylinder was cooled naturally. After standing for 15 hours, it was heated again to 240 ° C., and after 1 hour, 1 kg was purged with the dried polyetherester block copolymer resin composition of Example 10, and then 75 mm long × 125 mm wide × thickness. When a 2 mm square plate was injection-molded, there was no carbide mixed in the molded product.

[Comparative Example 9]
Using the polyether ester block copolymer of Comparative Example 1, a square plate having a length of 75 mm, a width of 125 mm, and a thickness of 2 mm was injection-molded by the same method as in Example 11. 1 to 5 carbides having a diameter of 1 mm or less were contained, and one similar carbide was mixed in the 50th shot molded product.

[Example 13]
The polyether ester block copolymer resin composition of Example 10 dried for 3 hours at 80 ° C. with a hot air dryer was extruded at a temperature of 240 ° C. using a φ30 single screw extruder. Then, the heater was turned off, the inside of the cylinder was naturally cooled, allowed to stand for 15 hours, and then heated up to 240 ° C. again. After 1 hour, 2 kg of the dried polyether ester block copolymer resin composition of Example 10 was flowed, and then an unstretched tube having an outer diameter of φ10 mm and an inner diameter of φ9 mm was formed using water-cooled vacuum sizing, The tube was examined for the presence or absence of carbide, but there was no carbide mixed in the tube.

[Comparative Example 10]
Using the polyether ester block copolymer of Comparative Example 1, an unstretched tube was formed by the same method as in Example 12 and examined for the presence or absence of carbides. Carbide was mixed in the ratio, and even after the tube was extruded 200 m, the carbide was sometimes mixed.

  The polyether ester block copolymer resin composition obtained by the production method of the present invention can give a molded product by various molding methods to injection molding, extrusion molding, blow molding and the like. In addition, the molded article made of the polyether ester block copolymer resin composition of the present invention can be used for various parts for automobiles, electronic / electrical equipment, precision equipment, general consumer goods, etc., tubes, sheets, films Also suitable for fibers.

Claims (6)

Polyether ester block copolymer composed mainly of 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. 0.05 to 5 parts by weight of hindered phenol antioxidant (B), phosphorus antioxidant (C) and / or sulfur antioxidant (D) with respect to 100 parts by weight of combined (A) 0.05 to 5 parts by weight, a polyether ester block copolymer resin composition comprising 0.1 to 3 parts by weight of a glycidyl ether compound (E), wherein the glycidyl ether compound (E) is a molecule Among them, ethylene glycol skeleton, propylene glycol skeleton, neopentyl glycol skeleton, 1,6-hexanediol skeleton, or resorcino Le skeleton, a polyether ester block copolymer resin composition is a diglycidyl ether compound having a hydroquinone skeleton, the relative viscosity of the polyether ester block copolymer resin composition before heat treatment, the polyether ester block A polyether ester block copolymer resin composition that is 0.02 to 0.04 lower than the relative viscosity of the copolymer (A) . Further, a polyether ester block copolymer resin composition comprising 0.01 to 5 parts by weight of a polyolefin-based lubricant (F). After heat treatment in air at a temperature T ° C. satisfying melting point + 15 ≦ T ≦ melting point + 40 for 2 hours, the resin composition has a surface carbonized layer having a thickness of less than 1 mm and an inner layer that is not more brittle than the surface carbonized layer. The relative viscosity ηr (conforming to JIS standard K7367-1, temperature: 25 ° C., solvent: o-chlorophenol) of the resin composition having a depth of 1 to 3 mm from the surface is represented by the following formula (I) The polyether ester block copolymer resin composition according to claim 1, wherein the polyether ester block copolymer resin composition is satisfied.
ηr0−ηr1 ≦ 0.6 (I)
ηr0: relative viscosity of the resin composition before treatment ηr1: relative viscosity of the resin composition at a depth of 1 to 3 mm from the surface after heat treatment The polyether ester block copolymer resin composition according to any one of claims 1 to 3, wherein the high-melting crystalline polymer segment (a) is made of polybutylene terephthalate. The polyether ester block copolymer resin composition according to any one of claims 1 to 4, wherein the low-melting-point polymer segment (b) is made of poly (tetramethylene oxide) glycol. The polyether ester block copolymer resin composition according to any one of claims 2 to 5, wherein the polyolefin-based lubricant (F) is a modified polyethylene wax.