Polyester elastomer composition

Abstract

The present invention provides a polyester elastomer which is derived and polymerized from a PTMG made from a biomass resource and including fluorine atoms, and from which it is possible to mass-produce a molded product having excellent heat resistance without undergoing foaming in mid-course of casting the polyester elastomer after polymerization and having a superior color tone and a superior reduced viscosity. This polyester elastomer composition contains a polyester elastomer in which a hard segment formed of a polyester including, as constituent components, an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bound to a soft segment including an aliphatic polyether as a constituent component. The aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are made from a fossil fuel resource, and the aliphatic polyether is a polytetramethylene ether glycol made from a biomass resource and including fluorine atoms. A peroxide degradation agent is included at a proportion of 0.01-1 part by mass with respect to 100 parts by mass of the polyester elastomer.

Description

Polyester elastomer composition

[0001] The present invention relates to a polyester elastomer composition containing a polyester elastomer derived from biomass resource-derived polytetramethylene ether glycol (PTMG) and polymerized therefrom, and in particular to a polyester elastomer composition containing a biomass resource-derived polyester elastomer that has excellent heat resistance, allows for mass production of pellets without foaming during casting after polymerization of the polyester elastomer, and is excellent in reduced viscosity and color.

[0002] Polyester elastomers are excellent in injection and extrusion moldability, and have high mechanical strength, rubber-like properties such as elastic recovery, impact resistance, and flexibility, as well as excellent heat and cold resistance. As such, they are used in a wide range of applications, including automotive parts, electrical and electronic parts, fibers, films, and sports parts.

[0003] In recent years, concerns about the depletion of fossil fuel resources and the increase in atmospheric carbon dioxide have become global environmental issues, leading to the promotion of the use of biomass in various polymers. For example, PTMG derived from biomass resources is used as the soft segment of polyester elastomers. Because biomass resources are renewable, they are expected to become an important design concept in future polymer development from the perspectives of SDGs and carbon neutrality.

[0004] Commercially available biomass-derived PTMG is produced using a batch process with a fluorine-based catalyst, resulting in the inclusion of fluorine atoms instead of terminal hydroxyl groups. When polyester elastomers are derived from PTMG containing such fluorine atoms, the resulting polymers have poor heat resistance.

[0005] In order to address the problem of deterioration in heat resistance due to fluorine atoms, Patent Document 1 proposes using PTMG with a fluorine content of 100 ppm or less. To produce PTMG with such a low fluorine content, the document also proposes a method of using a strong acid catalyst other than a fluorine-based catalyst, or, when a fluorine-based catalyst is used, removing fluorine-based impurities by washing with an alkaline aqueous solvent after polymerization. However, the former method cannot be used for PTMG derived from biomass resources, and the latter method also places a heavy load on industrial wastewater, and therefore has not been adopted in the production process of PTMG derived from biomass resources.

[0006] Furthermore, Patent Document 2 proposes adding a larger amount of oleum than is required for dehydration in order to obtain PTMG with a low fluorine content. However, this method also has a very large load on the industrial wastewater side and low productivity, and therefore has not been adopted in the production process of PTMG derived from biomass resources.

[0007] Furthermore, Patent Document 3 proposes the use of a non-fluorine-based strong acid catalyst or washing with an alkaline aqueous solvent to remove fluorine-based impurities to obtain PTMG with a fluorine content of 100 ppm or less (preferably 20 ppm or less). In addition, Patent Document 3 also proposes the inclusion of 5 to 20 ppm of phosphoric acid in PTMG to reduce the tetrahydrofuran content in polyester elastomers derived and polymerized from PTMG, thereby improving heat resistance. However, this phosphoric acid inclusion method merely reduces the amount of tetrahydrofuran produced by deactivating the polymerization catalyst, thereby delaying the time until foaming occurs during casting. However, because phosphoric acid does not act on peroxides generated by the presence of fluorine atoms, foaming itself cannot be suppressed. Furthermore, in the examples of Patent Document 3, improvement in heat resistance is only observed when PTMG with a fluorine content of less than 20 ppm is used.

[0008] Currently, PTMG derived from fossil fuel resources can be successfully mass-produced using a continuous process without using a fluorine-based catalyst, thereby solving the above-mentioned problems caused by the inclusion of fluorine atoms. However, when commercially available PTMG derived from biomass resources is used as described above, the PTMG contains approximately 20 to 200 ppm of fluorine atoms, which still causes the above-mentioned problems. Therefore, when a polyester elastomer is polymerized by directly deriving PTMG derived from biomass resources, the resulting polyester elastomer has low heat resistance, and foaming occurs during casting to produce pellets due to heat retention in the reactor after polymerization, making it very difficult to obtain a large amount of sample at one time.

[0009] JP-A No. 57-117527 JP-A No. 6-206998 JP-A No. 8-302000

[0010] The present invention has been made in view of the current state of the prior art, and an object of the present invention is to provide a polyester elastomer composition containing a biomass resource-derived polyester elastomer, which has excellent heat resistance despite using a polyester elastomer derived and polymerized from fluorine atom-containing biomass resource-derived PTMG, which allows mass production of pellet products without foaming during casting after polymerization of the polyester elastomer, and which also has excellent reduced viscosity and color, and a method for producing the same.

[0011] In order to achieve the above-mentioned object, the present inventors have conducted extensive research into the causes of decreased heat resistance of polyester elastomers derived from fluorine-containing biomass-derived PTMG and polymerized therefrom, particularly foaming during casting in the production of molded articles, and have found that fluorine atoms in PTMG promote the production of peroxides during casting, and that these peroxides cause a decrease in heat resistance and foaming during casting. Based on this finding, the present inventors have discovered that by adding a specific amount of a peroxide decomposer after polymerization to suppress the production of peroxides, foaming that occurs during casting can be suppressed and the deterioration of heat resistance can be prevented.

[0012] The present invention was completed based on these findings and comprises the following (1) to (6): (1) a polyester elastomer composition comprising a polyester elastomer having a hard segment composed of a polyester containing an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components, and a soft segment composed of an aliphatic polyether as constituent component, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, the aliphatic polyether is polytetramethylene ether glycol derived from biomass resources, and the polyester elastomer composition contains fluorine atoms, and the peroxide decomposer is contained in an amount of 0.01 to 1 part by mass per 100 parts by mass of the polyester elastomer; (2) the polyester elastomer composition according to (1), wherein the aliphatic polyether contains fluorine atoms in an amount of 20 to 200 ppm; (3) the polyester elastomer composition according to (1), wherein the peroxide decomposer is at least one selected from the group consisting of phosphonites, phosphites, and hindered amine stabilizers. (4) The polyester elastomer composition according to (1), characterized in that the polyester elastomer composition has a reduced viscosity of 1.2 dl / g or more. (5) The polyester elastomer composition according to (1), characterized in that the polyester elastomer composition has a Co-b value of 7 or less. (6) The method for producing the polyester elastomer composition according to any one of (1) to (5), characterized in that the peroxide decomposer is added after the completion of polymerization of the polyester elastomer and before casting.

[0013] Although the polyester elastomer composition of the present invention uses a polyester elastomer derived and polymerized from fluorine-containing biomass-derived PTMG, the incorporation of a peroxide decomposer suppresses the generation of peroxides due to fluorine atoms during casting, resulting in high heat resistance, no foaming during casting after polymerization of the polyester elastomer, and mass production of pelletized products is possible. Furthermore, despite the use of biomass-derived PTMG as the raw material for the polyester elastomer, the polyester elastomer composition of the present invention has excellent reduced viscosity and color. Therefore, because the polyester elastomer composition of the present invention can effectively use biomass-derived PTMG as a raw material, it will make a significant contribution to solving global environmental problems such as the depletion of fossil fuel resources.

[0014] The polyester elastomer composition of the present invention comprises a polyester elastomer in which a hard segment composed of a polyester having, as its constituent components, an aromatic dicarboxylic acid derived from a fossil fuel resource and an aliphatic and / or alicyclic diol derived from a fossil fuel resource, and a soft segment composed of a fluorine-containing biomass resource-derived PTMG are bonded, and is characterized in that a peroxide decomposer is contained in an amount of 0.01 to 1 part by mass relative to 100 parts by mass of the polyester elastomer.

[0015] As the aromatic dicarboxylic acid constituting the polyester of the hard segment of the polyester elastomer, ordinary aromatic dicarboxylic acids are widely used, and the main aromatic dicarboxylic acid is preferably terephthalic acid or naphthalenedicarboxylic acid (among its isomers, 2,6-naphthalenedicarboxylic acid is preferred). The content of these aromatic dicarboxylic acids is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, and may even be 100 mol% of the total dicarboxylic acids constituting the polyester of the hard segment. Examples of dicarboxylic acid components other than terephthalic acid and naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid, and 5-sodiumsulfoisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride; and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These dicarboxylic acids can be used in a range that does not significantly lower the melting point of the resin, and the amount is preferably 30 mol % or less of the total acid components, more preferably 20 mol % or less, and even more preferably 10 mol % or less, and may be 0 mol %. When these dicarboxylic acids are used as raw materials for polyester elastomers, they may be in the form of esters of the dicarboxylic acids. For example, terephthalic acid and dimethyl terephthalate can also be used as raw materials.

[0016] Furthermore, as the aliphatic or alicyclic diol constituting the polyester of the hard segment, general aliphatic or alicyclic diols are widely used and are not particularly limited, but alkylene glycols mainly having 2 to 8 carbon atoms are preferred. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. Of these, either ethylene glycol or 1,4-butanediol is preferred.

[0017] As the component constituting the polyester of the hard segment, those comprising butylene terephthalate units (units consisting of terephthalic acid and 1,4-butanediol) or butylene naphthalate units (units consisting of 2,6-naphthalenedicarboxylic acid and 1,4-butanediol) are preferred in terms of physical properties, moldability, and cost performance.

[0018] Furthermore, when an aromatic polyester suitable as the polyester constituting the hard segment of the polyester elastomer is produced in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained according to a conventional polyester production method. Furthermore, such a polyester preferably has a number-average molecular weight of 10,000 to 40,000. In the present invention, the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol constituting the hard segment are derived from fossil fuel resources.

[0019] PTMG is used as the aliphatic polyether constituting the soft segment of the polyester elastomer. The PTMG used in the present invention is derived from biomass resources. Commercially available PTMG can be used; for example, BioPTMG1000 and BioPTMG2000 manufactured by Mitsubishi Chemical Corporation are preferably used. Because biomass-derived PTMG is produced batchwise using a fluorine-based catalyst, fluorine atoms are incorporated in place of terminal hydroxyl groups. Therefore, the PTMG used in the present invention also contains fluorine atoms. The fluorine atom content is generally 20 to 200 ppm, preferably 40 to 180 ppm, and particularly 50 to 160 ppm.

[0020] The number-average molecular weight of PTMG is preferably 500 to 4,000, more preferably 700 to 3,000, and even more preferably 800 to 2,500. If the number-average molecular weight is below the above range, it may be difficult to exhibit elastomeric properties. On the other hand, if the number-average molecular weight exceeds the above range, compatibility with the hard segment component may decrease, making it difficult to copolymerize in a block form.

[0021] The polyester elastomer is preferably a copolymer primarily composed of terephthalic acid, 1,4-butanediol, and PTMG. In this case, of the dicarboxylic acid components constituting the polyester elastomer, terephthalic acid preferably accounts for 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Of the glycol components constituting the polyester elastomer, the total of 1,4-butanediol and PTMG is preferably 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0022] In the present invention, the mass of the hard segment refers to the mass of the component composed of an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol, and the mass of the soft segment refers to the mass of the component composed of an aromatic dicarboxylic acid and an aliphatic polyether. For example, in the case of a polyester elastomer composed of terephthalic acid, 1,4-butanediol, and PTMG, the mass of the hard segment is the mass of butylene terephthalate units (condensation units of terephthalic acid and 1,4-butanediol), and the mass of the soft segment is the mass of the condensation units of terephthalic acid and PTMG.

[0023] The mass ratio of hard segments to soft segments in the polyester elastomer is preferably 5 / 95 to 90 / 10, more preferably 10 / 90 to 85 / 15, and even more preferably 15 / 85 to 80 / 20. If the amount of hard segments is low (the amount of PTMG is high), the polyester elastomer may not have satisfactory heat aging resistance and moldability (crystallinity). Conversely, if the amount of hard segments is high (the amount of PTMG is low), the compatibility between the hard segment components and the soft segment components may decrease, making it difficult to copolymerize them into blocks.

[0024] The melting point of the polyester elastomer is preferably 150 to 230° C. If the melting point is less than 150° C., it may be impossible to obtain a polyester elastomer that satisfies the heat aging resistance and moldability (crystallinity) required for the polyester elastomer. Conversely, if the melting point is more than 230° C., the polyester elastomer will contain a large amount of hard segments, which will increase the glass transition temperature (Tg) accordingly, and it may be impossible to obtain a polyester elastomer that satisfies the impact resilience, flexibility, and low-temperature mechanical properties required for the polyester elastomer.

[0025] The polyester elastomer composition of the present invention contains 0.01 to 1 part by mass, preferably 0.02 to 0.8 parts by mass, and more preferably 0.03 to 0.7 parts by mass of a peroxide decomposer per 100 parts by mass of polyester elastomer. The peroxide decomposer is a compound capable of decomposing peroxides into alcohols and is different from a simple stabilizer. In the present invention, even if peroxides that cause foaming are generated during casting to produce pellets due to fluorine atoms contained in PTMG derived from biomass resources, which is the raw material for the polyester elastomer, the peroxide decomposer decomposes the generated peroxides. Therefore, foaming during casting is suppressed, and the heat resistance of the polyester elastomer is not reduced. If the content of the peroxide decomposer is less than the above range, the effect is not fully exerted. On the other hand, if the content of the peroxide decomposer is greater than the above range, the effect is not further improved and, conversely, the color may be impaired. Examples of peroxide decomposers include phosphonites (compounds having one carbon-phosphorus bond and two phosphorus-oxygen bonds, R-P-(O-R) ２ ), phosphites (compounds with three phosphorus-oxygen bonds, P—(O—R) ３), or hindered amine stabilizers (HALS). The peroxide decomposer is preferably at least one of a phosphonite and a phosphite, because of its greater foaming suppression effect during casting. In the chemical formulas of the phosphonite and the phosphite, R represents a hydrocarbon group, which may be the same or different and may be linked to each other. The hydrocarbon group may have a structure in which a substituent such as a hydroxyl group or a halogen group is bonded to a hydrocarbon. Generally, the peroxide decomposer exhibits better peroxide decomposition effect as the steric hindrance around the phosphorus atom decreases. However, this tends to impair the heat resistance of the peroxide decomposer itself. Therefore, it is preferable that R has at least one aromatic structure, alicyclic structure, or linked ring structure. Phosphonites in which R has an aromatic structure or phosphites in which R has an alkyl cyclic structure are more preferred. This allows for the desired effect to be obtained with a lower addition amount, making it possible to achieve both a foaming suppression effect during casting and pellet quality, such as color, at a higher level.

[0026] In order to achieve long-term durability (heat aging resistance, water resistance, etc.), the polyester elastomer composition preferably has a reduced viscosity of 1.2 dL / g or more, more preferably 1.3 dL / g or more, and even more preferably 1.4 dL / g or more. If the reduced viscosity is below the lower limit, the molecular weight will be small, and the polyester elastomer composition may not exhibit satisfactory long-term durability.

[0027] From the viewpoint of the appearance of molded articles, the polyester elastomer composition preferably has a Co-b value of not more than 7, more preferably not more than 6, and even more preferably not more than 5.5. If the Co-b value exceeds the upper limit, the prepared pellets will turn yellow, which may significantly impair the appearance of the molded article, making it impossible to obtain a satisfactory product.

[0028] The composition and composition ratio of the polyester elastomer composition of the present invention can be determined by dissolving a sample in a solvent such as deuterated chloroform and measuring the composition. １ It can also be calculated from the proton integral ratio of H-NMR.

[0029] Next, a method for producing the polyester elastomer composition of the present invention will be described. The polyester elastomer composition of the present invention is produced by polymerizing a polyester elastomer using a catalyst such as tetrabutyl titanate according to a conventional method, followed by adding a peroxide decomposer. The peroxide decomposer must be added after the polymerization of the polyester elastomer is complete and before casting to produce a molded product. If added before the completion of polymerization, the above-mentioned effects of the peroxide decomposer cannot be fully exerted. Furthermore, since peroxides, which cause foaming, are generated during casting to produce a molded product, the peroxide decomposer must be added before casting.

[0030] The following examples are provided to demonstrate the effects of the present invention, but the present invention is not limited to these examples. The property values ​​were evaluated by the following methods.

[0031] (1) Fluorine Content The fluorine content in PTMG was measured by combustion ion chromatography using an automatic sample combustion device (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

[0032] (2) Heat Resistance Heat resistance was evaluated based on whether sampling was possible during casting to produce pellets from the polyester elastomer composition. If the strands foamed during casting, making sampling impossible due to foam inclusions, the heat resistance was evaluated as poor. Conversely, if there was no foaming or only a small amount of foaming and sampling was consistently possible, the heat resistance was evaluated as excellent. Specifically, if there was no foaming in the strands and sampling was possible, the rating was "excellent." If there was some foam in the strands but sampling was possible, the rating was "fair." If there was severe foaming in the strands and sampling was impossible, the rating was "poor."

[0033] (3) Reduced Viscosity (ηsp / c) 0.05 g of a polyester elastomer composition was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane=60 / 40), and the reduced viscosity was measured at 30° C. using an Ubbelohde viscometer.

[0034] (4) Color Difference The Co-b value of the polyester elastomer composition was measured using an automatic color difference meter (manufactured by Toyorika Kogyo Co., Ltd.) The larger the Co-b value, the greater the yellowness.

[0035] Example 1: 56 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 36 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), and 8 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, manufactured by Mitsubishi Chemical, molecular weight 1000 g / mol) were each charged into a reactor. Furthermore, a solution of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) as a catalyst diluted to a 1% by mass concentration with 1-butanol was charged into the reactor at a ratio of 0.08 parts by mass per 100 parts by mass of the polymer to be purified. The temperature was raised from room temperature to 220°C over 150 minutes, and a transesterification reaction was carried out. The pressure inside the reactor was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245°C and 1 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C and at a pressure of 1 Torr or less for 135 minutes. After completion of the polymerization reaction, peroxide decomposer A (phosphorus-based antioxidant (phosphite), Adekastab PEP-36, manufactured by ADEKA) was added to the reactor in a ratio of 0.05 part by mass per 100 parts by mass of the purified polymer, and the mixture was stirred. After stirring, the polymer was taken out in the form of pellets, and the final polyester elastomer composition of Example 1 was obtained.

[0036] Examples 2 and 3 The final polyester elastomer compositions of Examples 2 and 3 were obtained in the same manner as in Example 1, except that the addition ratio of peroxide decomposer A was changed to 0.5 parts by mass and 0.15 parts by mass, respectively, per 100 parts by mass of the purified polymer.

[0037] Example 4 The final polyester elastomer composition of Example 4 was obtained in the same manner as in Example 1, except that the blending ratios of dimethyl terephthalate and 1,4-butanediol in Example 1 were changed as shown in Table 1, and BioPTMG2000 (manufactured by Mitsubishi Chemical Corporation, molecular weight 2000 g / mol) was used as the biomass resource-derived polytetramethylene ether glycol in the blending ratio shown in Table 1.

[0038] Example 5 The final polyester elastomer composition of Example 5 was obtained in the same manner as in Example 2, except that the blending ratios of dimethyl terephthalate and 1,4-butanediol in Example 2 were changed as shown in Table 1, and BioPTMG2000 (manufactured by Mitsubishi Chemical Corporation, molecular weight 2000 g / mol) was used as the biomass resource-derived polytetramethylene ether glycol in the blending ratio shown in Table 1.

[0039] Example 6 The final polyester elastomer composition of Example 6 was obtained in the same manner as in Example 1, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0040] Example 7 The final polyester elastomer composition of Example 7 was obtained in the same manner as in Example 2, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0041] Example 8 A final polyester elastomer composition of Example 8 was obtained in the same manner as in Example 6, except that the blending ratios of dimethyl 2,6-naphthalenedicarboxylate, 1,4-butanediol, and biomass resource-derived polytetramethylene ether glycol in Example 6 were changed as shown in Table 1.

[0042] Example 9 A final polyester elastomer composition of Example 9 was obtained in the same manner as in Example 7, except that the blending ratios of dimethyl 2,6-naphthalenedicarboxylate, 1,4-butanediol, and biomass resource-derived polytetramethylene ether glycol in Example 7 were changed as shown in Table 1.

[0043] Example 10 The final polyester elastomer composition of Example 10 was obtained in the same manner as in Example 3, except that peroxide decomposer B (phosphorus-based antioxidant (phosphonite), HOSTANOX P-EPQ, manufactured by Clariant Japan) was used instead of peroxide decomposer A.

[0044] Example 11 A final polyester elastomer composition of Example 11 was obtained in the same manner as in Example 10, except that the blending ratios of dimethyl terephthalate and 1,4-butanediol in Example 10 were changed as shown in Table 1, and BioPTMG2000 (manufactured by Mitsubishi Chemical Corporation, molecular weight 2000 g / mol) was used as the biomass resource-derived polytetramethylene ether glycol in the blending ratio shown in Table 1.

[0045] Example 12 A final polyester elastomer composition of Example 12 was obtained in the same manner as in Example 10, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0046] Example 13 A final polyester elastomer composition of Example 13 was obtained in the same manner as in Example 10, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0047] Example 14 The final polyester elastomer composition of Example 14 was obtained in the same manner as in Example 3, except that peroxide decomposer C (hindered amine-based HALS, Chimassorb 944 FDL, manufactured by BASF Japan) was used instead of peroxide decomposer A.

[0048] Example 15 A final polyester elastomer composition of Example 15 was obtained in the same manner as in Example 14, except that the blending ratios of dimethyl terephthalate and 1,4-butanediol in Example 14 were changed as shown in Table 1, and BioPTMG2000 (manufactured by Mitsubishi Chemical Corporation, molecular weight 2000 g / mol) was used as the biomass resource-derived polytetramethylene ether glycol in the blending ratio shown in Table 1.

[0049] Example 16 A final polyester elastomer composition of Example 16 was obtained in the same manner as in Example 14, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0050] Example 17 A final polyester elastomer composition of Example 17 was obtained in the same manner as in Example 14, except that dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical) was used in place of dimethyl terephthalate in the blending ratio shown in Table 1, and the blending ratios of 1,4-butanediol and biomass resource-derived polytetramethylene ether glycol were changed as shown in Table 1.

[0051] Comparative Example 1 The final polyester elastomer composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that the peroxide decomposer A was not added after the completion of the polymerization reaction.

[0052] Comparative Example 2 The final polyester elastomer composition of Comparative Example 2 was obtained in the same manner as in Example 1, except that the blending ratio of peroxide decomposer A in Example 1 was changed as shown in Table 1.

[0053] Comparative Example 3 The final polyester elastomer composition of Comparative Example 3 was obtained in the same manner as in Example 1, except that the blending ratio of peroxide decomposer A in Example 1 was changed as shown in Table 1.

[0054] Comparative Example 4 The final polyester elastomer composition of Comparative Example 4 was obtained in the same manner as in Example 1, except that a stabilizer A (hindered phenol-based antioxidant, Irganox 1098, manufactured by BASF Japan) not having peroxide decomposing ability was used in place of the peroxide decomposer A in the blending ratio shown in Table 1.

[0055] Comparative Example 5 A final polyester elastomer composition of Comparative Example 5 was obtained in the same manner as in Example 1, except that in place of the peroxide decomposing agent A in Example 1, a stabilizer B (semi-hindered phenol-based antioxidant, Adeka STAB AO-80, manufactured by ADEKA Corporation) not having peroxide decomposing ability was used in the blending ratio shown in Table 1.

[0056] Comparative Example 6 The final polyester elastomer composition of Comparative Example 6 was obtained in the same manner as in Example 1, except that in Example 1, a stabilizer C (sulfur-based antioxidant, Lasmit LG, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) not having peroxide decomposing ability was used in place of the peroxide decomposing agent A in the blending ratio shown in Table 1.

[0057] Comparative Example 7 The final polyester elastomer composition of Comparative Example 7 was obtained in the same manner as in Example 1, except that in Example 1, stabilizer D (amine-based antioxidant, Nonflex DCD, manufactured by Seiko Chemical Industry Co., Ltd.), which does not have peroxide decomposing ability, was used in place of peroxide decomposer A, in the blending ratio shown in Table 1.

[0058] The compositions and evaluation results of the polyester elastomer compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 7 are shown in Table 1.

[0059]

[0060] As is clear from Table 1, all of Examples 1 to 17, which satisfy the requirements of the present invention, used polyester elastomers derived from fluorine-containing biomass-derived PTMG and polymerized therefrom, but the incorporation of a peroxide decomposer suppressed the generation of peroxides due to fluorine atoms during casting, resulting in high heat resistance, little or no foaming during casting after polymerization of the polyester elastomer, and enabling sampling. Furthermore, despite the use of biomass-derived PTMG as the raw material for the polyester elastomer, the reduced viscosity and color were excellent.

[0061] In contrast, Comparative Example 1, which did not contain any peroxide decomposer, and Comparative Example 2, which contained too little peroxide decomposer, both exhibited poor heat resistance and foamed during casting, making sampling impossible. Comparative Example 3, which contained too much oxide decomposer, had sufficient heat resistance, but had a high Co-b value and poor color. Comparative Examples 4 to 7, which used a stabilizer without peroxide decomposition ability instead of a peroxide decomposer, all exhibited poor heat resistance and foamed during casting, making sampling impossible. In addition, Comparative Examples 4 and 5 exhibited high Co-b values ​​and poor color.

[0062] Although the polyester elastomer composition of the present invention uses a polyester elastomer derived from and polymerized with fluorine-containing biomass-derived PTMG, the incorporation of a peroxide decomposer suppresses the generation of peroxides due to fluorine atoms during casting, resulting in high heat resistance, no foaming during casting after polymerization of the polyester elastomer, and mass production of pelletized products is possible. Furthermore, despite the use of biomass-derived PTMG as the raw material for the polyester elastomer, the polyester elastomer composition of the present invention exhibits excellent reduced viscosity and color. Therefore, because the polyester elastomer composition of the present invention can effectively use biomass-derived PTMG as a raw material, it significantly contributes to solving global environmental problems such as the depletion of fossil fuel resources and is extremely useful in the industry.

Claims

1. A polyester elastomer composition comprising a polyester elastomer having a hard segment composed of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as its constituent components, and a soft segment composed of an aliphatic polyether as its constituent component, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, the aliphatic polyether is polytetramethylene ether glycol derived from biomass resources, and contains fluorine atoms, and a peroxide decomposer is contained in an amount of 0.01 to 1 part by mass per 100 parts by mass of the polyester elastomer.

2. The polyester elastomer composition according to claim 1, wherein the aliphatic polyether contains 20 to 200 ppm of fluorine atoms.

3. The polyester elastomer composition according to claim 1, wherein the peroxide decomposer is at least one member selected from the group consisting of phosphonites, phosphites, and hindered amine stabilizers.

4. The polyester elastomer composition according to claim 1, characterized in that the reduced viscosity of the polyester elastomer composition is 1.2 dl / g or more.

5. The polyester elastomer composition according to claim 1, characterized in that the Co-b value of the polyester elastomer composition is 7 or less.

6. A method for producing a polyester elastomer composition according to any one of claims 1 to 5, characterized in that the peroxide decomposer is added after the polymerization of the polyester elastomer is completed and before casting.

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