JP2003292744A - Polyester elastomer resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an easily producible polyester elastomer composition having excellent mechanical properties such as flexibility, abrasion resistance and tensile strength without using any lubricant and giving stable quality over a relatively wide range of the kneading conditions in production. <P>SOLUTION: This polyester elastomer resin composition is composed of (A) a thermoplastic polyester elastomer and (B) a thermoplastic polyolefin elastomer and the fluidity values of the components (A) and (B) satisfy the formula (1) (MI-A)/(MI-B)/≥10 at a temperature between 180°C and 250°C. In the formula (1), MI-A is the melt flow index of the component A at the processing temperature and MI-B is the melt flow index of the component B at a temperature between 180°C and 250°C (the measuring temperature of MI-A is same as that of MI-B). <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a field which requires flexibility and abrasion resistance, and more particularly to a polyester elastomer composition used for hoses, belts, tubes, grips and the like. . 2. Description of the Related Art Hitherto, the wear resistance of polyester elastomers is inversely proportional to the flexibility, and no material has been found which has both flexibility and abrasion resistance. Therefore, flexibility and abrasion resistance are required. In the field, a material has been used in which a flexible polyester elastomer is blended with a lubricant which bleeds out when used to exhibit abrasion resistance. [0003] However, in the case of the method for imparting abrasion resistance by blending a lubricant, since the lubricant bleeds out during use, problems such as poor appearance, stickiness, hygiene and the like occur. Often do. Therefore, it is strongly desired to provide a polyester elastomer composition having excellent flexibility and abrasion resistance without using the above-mentioned lubricant.
The present inventor has conducted intensive studies to solve the disadvantages of the prior art as described above, and as a result, by blending a thermoplastic polyolefin elastomer having a specific fluidity with a thermoplastic polyester elastomer, sufficient lubrication can be achieved without using any lubricant. Excellent mechanical properties such as flexibility, abrasion resistance and tensile strength
Furthermore, the inventors have found that stable quality can be obtained over a relatively wide range under kneading conditions at the time of production, and that a polyester elastomer composition that is easy to produce can be obtained, and the present invention has been completed. [0004] That is, the present invention provides (A)
Thermoplastic polyester elastomer, (B) made of thermoplastic polyolefin elastomer, 180-250 ° C
The flowability of (A) and (B) at any temperature in equation (1)
A polyester elastomer resin composition characterized by satisfying the following. (MI-A) / (MI-B) ≧ 10 Formula (1) Here, MI-A is the melt flow index at the processing temperature of (A), and MI-B is any of 180 to 250 ° C. of (B). The melt flow index at that temperature (where MI-A and MI-B are the same). Hereinafter, the present invention will be described in detail. The polyester elastomer in the present invention,
It is a copolymer consisting of a high melting point polyester segment having an aromatic ring and a low melting point polymer segment having a molecular weight of 400 to 2,000, and has a melting point of 180 ° C or higher when a high polymer is formed only with the high melting point polyester segment constituent components, It is a polyester elastomer composed of components having a melting point or softening point of 80 ° C. or lower when measured only with the low melting polymer segment components. The polyester elastomer will be described in more detail. The components of the high melting polyester segment having an aromatic ring include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, An aromatic dicarboxylic acid such as 5-naphthalenedicarboxylic acid or 1,4-naphthalenedicarboxylic acid or an ester thereof and one having 1 carbon atom;
~ 25 glycols and their ester-forming derivatives can be used. The glycol having 1 to 25 carbon atoms is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol. , 1,9-nonanediol, neopentyl glycol, dimethylol heptane, dimethylol pentane, tricyclodecane dimethanol, ethylene oxide derivatives of bisphenol X (X is A, S, F) and ester-forming derivatives thereof. Can be Preferably, ethylene glycol, 1,4-butanediol and their ester-forming derivatives are mentioned. In addition,
As the acid component of the high melting point polyester segment constituent component, terephthalic acid is preferably at least 70 mol% of the total acid component. Other acid components include aromatic dicarboxylic acids such as terephthalic acid, diphenyldicarboxylic acid, isophthalic acid and 5-sodium sulfoisophthalic acid. Examples of the alicyclic dicarboxylic acid include cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride.Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, dimer acid, and water. And added dimer acid. These amounts are not more than 30 mol%, preferably not more than 25 mol% of the total acid component. The lower limit of the melting point is not particularly limited, but is generally preferably 150 ° C. or higher, particularly preferably 180 ° C. or higher. In the present invention, examples of the low melting polymer segment having a molecular weight of 400 to 4000 include polyalkylene ether glycols such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol and the like. The mixture may further show a copolymerized polyether glycol obtained by copolymerizing these polyether glycol constitutions. From the viewpoint of increasing the melting point and moldability, poly (tetramethylene oxide) glycol is preferred, and has a molecular weight of 8
00 to 2200 is particularly preferred from the viewpoint of low-temperature properties, and preferably 15 to 75% of the total polyester weight. In particular, the range of 15 to 60% is preferable from the viewpoint of durability and flexibility. In the case of a copolymer, the content of tetramethylene terephthalate or ethylene terephthalate units is preferably 60 mol% or more. Any known method can be applied to the production of the polyester elastomer of the present invention. For example, any of a melt polymerization method, a solution polymerization method, and a solid phase polymerization method may be appropriately used. In the case of melt polymerization, a transesterification method or a direct polymerization method may be used. It is, of course, desirable to carry out solid-phase polymerization after melt polymerization in order to improve the viscosity of the resin, in order to increase the moldability and the durable life of the molded article. As the catalyst used for the reaction of the polyester elastomer, an antimony catalyst, a germanium catalyst and a titanium catalyst are preferred. Particularly preferred are titanium catalysts, more specifically, tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal oxalates such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate. The obtained polyester elastomer may contain a known antioxidant such as a hindered phenol type, a sulfur type or a phosphorus type, a hindered amine type or a triazole type.
Benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, Acid agent, antibacterial agent, fluorescent whitening agent, glass fiber, carbon fiber silica fiber, inorganic fibrous substance such as alumina fiber, carbon black, silica, quartz powder,
Glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron oxide, titanium oxide, zinc oxide, alumina, calcium carbonate, barium carbonate Powder fillers such as metal carbonates and other various metal powders, mica, glass flakes, plate fillers such as various metal powders, flame retardants, flame retardant aids, organic and inorganic pigments, etc. More than one kind can be added. In order to improve the viscosity, after polymerization of the polyester, the chain may be extended with a compound having two or more functional groups capable of reacting at the terminal of the polymer chain. Specific examples include 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, isocyanuric acid triglycidyl ether, Cresol novolak type glycidyl ether, phenol novolak type glycidyl ether, pyromellitic anhydride, phthalic anhydride, polycarbodiimide, bisoxazoline compound and the like can be mentioned. Particularly preferred examples include:
Examples include bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, and isocyanuric acid triglycidyl ether compound. The olefin-based thermoplastic elastomer used for improving the flexibility, friction and wear characteristics is preferably a thermoplastic elastomer having a thermoplastic resin as a continuous phase and an elastomer as a dispersed phase. The dispersed phase is preferably an olefinic elastomer, more preferably an unsaturated elastomeric terpolymer comprising two or more olefinic monomers and one or more diene monomers, wherein the dispersed phase is crosslinked. Is preferred. The thermoplastic resin preferably includes polyethylene, polypropylene, polybutadiene, polystyrene, polyisoprene, and copolymers thereof, and is more preferably a crystalline olefin resin, and particularly preferably polypropylene.
These include, for example, Sarlink manufactured by DSM.
As a method for producing a thermoplastic elastomer comprising a continuous phase and a dispersed phase in which a dispersed phase is cross-linked, for example, a crystalline olefin resin and two or more olefin-based monomers may be used.
Mixing or masticating a mixture of unsaturated elastomeric terpolymers comprising at least one diene monomer in the presence of a crosslinking agent for a time sufficient to melt the crystalline olefin resin and then mixing Alternatively, there is a method in which mastication is dynamically crosslinked at a temperature at which at least partial crosslinking of the elastomer terpolymer occurs. The difference in viscosity (MI-A / MI-B) between (A) the thermoplastic polyester elastomer and (B) the thermoplastic olefin elastomer at the processing temperature is 10 or more, preferably 30 or more, more preferably 50 or more, and most preferably Preferably, 100 or more combinations are desirable. Generally, the processing of the polyester elastomer is performed at 180 to 250 ° C., so that the above relationship needs to be satisfied at any temperature of 180 to 250 ° C. Thus, (MI-A
By setting / MI-B) within the above range, the dispersed particle size of the thermoplastic olefin elastomer can be easily finely dispersed to 5 μm or less. In particular, a twin-screw extruder is used for dispersing the thermoplastic polyester elastomer (A) and the thermoplastic olefin elastomer (B). However, the operating conditions such as the screw configuration of the extruder, the temperature range and the number of rotations are limited. It can be widely used, and the manufacturing advantage is increased. As a result, excellent balance of mechanical properties, especially tensile strength, elongation, tear strength and flexibility, abrasion resistance, scratch resistance, oil resistance, grease resistance, chemical resistance, molded product appearance, non-adhesiveness, etc. Can be produced stably. In general, when kneading and finely dispersing a plurality of types of materials, it is easier to finely disperse as those having a closer viscosity to each other,
In the case of the above elastomer, it is surprising that the higher the viscosity of the thermoplastic elastomer (A) is, the lower the viscosity (the larger the MI) is, the easier it is to finely disperse. The amount of the thermoplastic olefin elastomer can vary depending on the affinity with the polyester type block copolymer used or the required properties of the finally obtained composition. Preferably, 5 parts by weight to 70 parts by weight, more preferably 5 parts by weight to 30 parts by weight, based on 95 to 30 parts by weight of the polyester type block copolymer. Department. If the amount is less than 5 parts by weight, the effect obtained by adding such a thermoplastic olefin elastomer and the effect of improving abrasion resistance are not significantly exhibited. Also 95
If the amount is more than 10 parts by weight, the melt viscosity of the polyester block copolymer will be remarkably reduced, molding will not be possible, physical properties will be impaired, and grease resistance will be deteriorated. The present invention will be described below by way of examples. In these examples, each measurement item followed the following method. 1. Surface hardness: Measured according to a type A durometer hardness measurement method described in JIS K6253. 2. Abrasion resistance: Suzuki-type thrust wear test. Counterpart material SUS
The amount of wear during a test time of 3 minutes was measured under the conditions of 440C, a load of 7 kg / cm ² , and a linear velocity of 7 m / min. 3. Grease resistance: 125 ° C in Toyota Rare Max RB
The volume swelling ratio before and after immersion for 3 days was measured. 3. Volume swelling ratio (%) = (volume after immersion−volume before immersion) / volume before immersion × 100 MI: according to the method described in ASTM D1238
The measurement was performed using a melt indexer T-111 manufactured by Toyo Seiki Seisaku-Sho, Ltd. under the conditions of a temperature of 200 ° C. and a load of 2160 g. Example 1 70 parts by weight of a polyester type block copolymer (Perprene P40H manufactured by Toyobo), olefin elastomer (Sarlink-3150 manufactured by DSM) 30
The weight part was put into a drum tumbler and stirred at room temperature for 10 minutes. The mixture was heated at 200 ° C. with a 40 mmφ co-rotating twin screw extruder.
The mixture was extruded at a rotation speed of 80 rpm, cut into water-cooled chips. The obtained chips were dried at 100 ° C. under reduced pressure to obtain chips of the polyester elastomer composition of the present invention. Example 2 30 parts by weight of a polyester type block copolymer (Perprene P40H manufactured by Toyobo) and 70 olefin elastomers (Sarlink-4155 manufactured by DSM)
The weight part was put into a drum tumbler and stirred at room temperature for 10 minutes. The mixture is mixed with a 40 mmφ co-rotating twin-screw extruder for 200
The mixture was extruded at 100 ° C. and a rotation speed of 100 rpm, cut into water-cooled chips. The obtained chips were dried at 100 ° C. under reduced pressure to obtain chips of the polyester elastomer composition of the present invention. (Embodiment 3) The rotation speed of the twin-screw extruder was set to 200.
A polyester elastomer chip was obtained in the same manner as in Example 1 except that the rpm was changed to rpm. (Embodiment 4) The rotational speed of the twin-screw extruder is 25 r.
A polyester elastomer chip was obtained in the same manner as in Example 1 except that the pm was changed to pm. (Comparative Example 1) 70 parts by weight of a polyester type block copolymer (Toyobo's Perprene P40H) and 30 parts by weight of an olefin elastomer (Oleflex P332G from Nippon Polyolefin Co., Ltd.) were placed in a drum tumbler and stirred at room temperature for 10 minutes. did. The mixture was extruded at 200 ° C. with a 40 mmφ co-rotating twin screw extruder, and after cooling with water, cut into chips. The obtained chips were dried at 100 ° C. under reduced pressure to obtain chips of the polyester elastomer composition of the present invention. (Comparative Example 2) A polyester type block copolymer (Perprene P40H manufactured by Toyobo) alone. (Comparative Example 3) A polyester type block copolymer (Perprene P40B manufactured by Toyobo) alone. Comparative Example 4 A single olefin elastomer (Sarlink-3180 manufactured by DSM) alone. (Comparative Example 5) A single olefin elastomer (Sarlink-3150 manufactured by DSM) alone. Table 1 shows the results of predetermined tests performed on Examples 1 and 2 and Comparative Examples 1 to 5. [Table 1] As described above, a polyester elastomer composition having excellent flexibility, abrasion resistance and grease resistance can be obtained by blending an olefin elastomer having a specific fluidity with a polyester type block copolymer. A polyester elastomer composition which can be provided, has a stable quality over a relatively wide range under kneading conditions during production, and is easy to produce.

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Claims (1)

Claims: 1. A thermoplastic polyester elastomer comprising: (A) a thermoplastic polyester elastomer; and (B) a thermoplastic polyolefin elastomer.
A polyester elastomer resin composition, wherein the fluidity of (B) satisfies the formula (1). (MI-A) / (MI-B) ≧ 10 Formula (1) Here, MI-A is the melt flow index at the processing temperature of (A), and MI-B is any of 180 to 250 ° C. of (B). The melt flow index at that temperature (where MI-A and MI-B are the same).