Flame-retardant resin composition using biomass-derived polyester elastomer

Abstract

The present invention provides a resin composition that maintains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy of fossil fuel-derived raw materials, even when the proportion of biomass-derived raw materials in the polyester elastomer is increased. The resin composition contains a polyester elastomer, at least one of whose constituent components is biomass-derived, a flame retardant, and a heat stabilizer, and the content of the flame retardant is 5 parts by mass or more per 100 parts by mass of the polyester elastomer. The resin composition has a biobased content of 8 to 100%, a specific gravity of 1.20 or more, and a tensile elongation at break of 200% or more.

Description

[Technical Field]

[0001] The present invention relates to a biomass resource-derived polyester elastomer resin composition that uses a biomass resource-derived polyester elastomer with a high biobased content, yet retains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy that are characteristic of fossil fuel resource-derived polyester elastomers. [Background technology]

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

[0003] Among these, compositions made by adding flame retardants to polyester elastomers, which have excellent oil and fuel resistance and low-temperature properties, are used as materials for insulated wires and cables used inside and outside of mechanical parts such as railway vehicles, automobiles, and electrical and electronic equipment, as well as transmission equipment.

[0004] Meanwhile, due to concerns about the depletion of fossil fuel resources, the main raw material for polyester elastomers, and the global environmental issues of increased atmospheric carbon dioxide, the shift to biomass polymers is underway. Biomass resources are renewable resources, and their use is expected to become an important design concept in future polymer development from the perspectives of SDGs and carbon neutrality.

[0005] However, because biomass resource-derived raw materials contain impurities that could not be completely removed during the refining process, increasing the proportion of biomass resource-derived raw materials in an attempt to increase the bio-based content of the polyester elastomer increases the amount of impurities, which in turn inhibits the reaction and prevents the reduced viscosity from increasing, making it difficult to maintain the excellent properties of fossil fuel resource-derived polyester elastomers.

[0006] Furthermore, factors such as impurities introduced into biomass-derived raw materials, oligomers, side reaction products, foreign matter, and undesigned polymers generated during polymerization reactions using these materials can make it difficult for polyester elastomers to demonstrate their inherent excellent molding design precision. For example, in extrusion molding, a common molding method for cable and wire coatings, resins tend to deform easily in the high elongation region after exiting the die, and in terms of flow properties, tend to harden due to extensional viscosity and strain rate. Meanwhile, resins that do not exhibit ductile necking in the low elongation region after exiting the die enhance molding stability. Achieving such high molding stability requires high polymer molecular design to control inter-molecular chain entanglement and slippage. However, when using polyester elastomers produced from biomass-derived raw materials, problems such as poor polymer molecular design and the influence of introduced impurities and foreign matter result in low wall thickness precision and increased breakage during production.

[0007] To address this issue, it has been proposed to prevent a decline in the mechanical properties of polyesters made from biomass-derived dicarboxylic acids and / or diols by reducing the sulfur atom content and the amount of acid end groups (see Patent Document 1). While this biomass-derived polyester can prevent a decline in mechanical properties to some extent, it also causes discoloration of the polyester, which can lead to poor appearance of molded articles. Furthermore, it fails to maintain the excellent properties of fossil-fuel-derived polyesters in terms of residence stability, water aging resistance, and heat aging resistance.

[0008] Furthermore, various methods have been proposed for imparting flame retardancy to resins. Generally, methods include adding halogen compounds such as bromine compounds, which have a high flame retardant effect, or antimony oxide as needed, to resins, or using non-halogen flame retardants that do not generate halogen-based gases.

[0009] In recent years, insulated wires and cables used in electronic devices and other devices have required extremely high levels of flame retardancy for safety reasons, making it necessary to incorporate large amounts of flame retardants into polyester elastomer compositions. However, flame retardants generally have low molecular compatibility with polyester elastomers and large differences in specific gravity, resulting in poor dispersibility in polyester elastomer compositions. As a result, polyester elastomer compositions containing large amounts of flame retardants have problems such as reduced mechanical properties such as breaking strength and breaking elongation, poor appearance of molded products due to the formation of flame retardant clumps and flow marks, and accumulation of flame retardants at the extruder die outlet, which can cause die buildup. Furthermore, the use of large amounts of flame retardants can cause screw slippage and uneven feeding during the melt-kneading process, leading to pulsation and reduced extrusion rates. Therefore, obtaining flame-retardant compositions of consistent quality requires highly advanced dispersion technology, which simultaneously restricts the melt-kneading conditions (see Patent Document 2). [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent No. 5303237 [Patent Document 2] Patent No. 5463779 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention was made in view of the current state of the prior art, and an object of the present invention is to provide a biomass resource-derived polyester elastomer resin composition that retains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy of fossil fuel resource-derived polyester elastomers, even when the proportion of biomass resource-derived raw materials used in the polyester elastomer is increased. [Means for solving the problem]

[0012] As a result of extensive research to achieve this object, the present inventors have found that by adjusting the production conditions so that the specific gravity and tensile elongation at break of a biomass resource-derived polyester elastomer resin composition containing a flame retardant fall within predetermined ranges, it is possible to provide a biomass resource-derived polyester elastomer resin composition that retains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy that are characteristic of polyester elastomers derived from fossil fuel resources, and have completed the present invention.

[0013] That is, the present invention comprises the following (1) to (10). (1) A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer, at least one of whose constituent components is derived from a biomass resource, a flame retardant, and a heat stabilizer, wherein the content of the flame retardant is 5 parts by mass or more per 100 parts by mass of the polyester elastomer, wherein the polyester elastomer resin composition has a biobased content of 8 to 100%, a specific gravity of 1.20 or more, and a tensile elongation at break of 200% or more. (2) The polyester elastomer resin composition according to (1), characterized in that the biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components is bonded to a soft segment made of an aliphatic polyether as a constituent component, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from biomass resources. (3) The polyester elastomer resin composition according to (2), wherein the biomass resource-derived aliphatic polyether of the biomass resource-derived polyester elastomer is polytetramethylene ether glycol. (4) The polyester elastomer resin composition according to (1), wherein the biomass resource-derived polyester elastomer has a reduced viscosity of 1.2 dl / g or more. (5) A polyester elastomer resin composition according to any one of (1) to (4), characterized in that the difference in melt flow rate (MFR: g / 10 min) of the polyester elastomer resin composition measured in accordance with the test method (Method A) described in JIS K7210 at 2160 g at 20°C above the melting point of the polyester elastomer, between the MFR value 45 minutes after addition of the polyester elastomer resin composition (MFR45) and the MFR value 5 minutes after addition of the polyester elastomer resin composition (MFR5) (ΔMFR: MFR45 - MFR5) is 25 or less. (6) A polyester elastomer resin composition according to any one of (1) to (4), characterized in that the 3% weight loss temperature when the polyester elastomer resin composition is heated from room temperature to 450°C at a rate of 10°C / min is 300°C or higher. (7) The polyester elastomer resin composition according to any one of (1) to (4), characterized in that the flame retardancy rating measured according to UL94 is V-2, V-1, or V-0. (8) A wire / cable covering material using the polyester elastomer resin composition according to any one of (1) to (4). (9) An electronic device part using the polyester elastomer resin composition according to any one of (1) to (4). (10) A monofilament made from the polyester elastomer resin composition according to any one of (1) to (4). [Effects of the Invention]

[0014] The biomass-derived polyester elastomer resin composition of the present invention can retain the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy of fossil fuel-derived polyester elastomers, even when the proportion of biomass-derived raw materials used is increased. Therefore, the polyester elastomer resin composition of the present invention can be suitably used for hoses, tubes, cables, wire coating materials, etc. DETAILED DESCRIPTION OF THE INVENTION

[0015] The polyester elastomer resin composition of the present invention contains a biomass resource-derived polyester elastomer, at least one of whose constituent components is derived from a biomass resource, a flame retardant, and a heat stabilizer, and is characterized in that the content of the flame retardant is 5 parts by mass or more per 100 parts by mass of the polyester elastomer, the bio-based content of the polyester elastomer resin composition is 8 to 100%, the specific gravity of the polyester elastomer resin composition is 1.20 or more, and the tensile elongation at break is 200% or more.

[0016] The biomass resource-derived polyester elastomer used in the resin composition of the present invention is preferably a polyester elastomer in which a hard segment made of a polyester having, as its constituent components, an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment made of an aliphatic polyether. It is preferable that the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource.

[0017] Typical aromatic dicarboxylic acids are widely used as the aromatic dicarboxylic acid constituting the polyester of the hard segment, 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-sodium sulfoisophthalic 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.

[0018] 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 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.

[0019] 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.

[0020] Alternatively, when an aromatic polyester suitable for forming the hard segment of the polyester elastomer is prepared in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained by a conventional polyester production method. Preferably, the polyester has a number average molecular weight of 10,000 to 40,000.

[0021] The aliphatic polyether constituting the soft segment of the polyester elastomer is preferably a glycol compound because it bonds with the polyester in the hard segment. Specific examples include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, polytetramethylene ether glycol, polytrimethylene ether glycol, poly(hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide adduct of poly(propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol and an ethylene oxide adduct of poly(propylene oxide) glycol are preferred in terms of elastic properties.

[0022] In the present invention, the aliphatic polyether constituting the soft segment is preferably derived from a biomass resource, particularly polytetramethylene ether glycol (PTMG) derived from a biomass resource. Commercially available PTMGs are available, and preferred examples include BioPTMG1000 and BioPTMG2000 manufactured by Mitsubishi Chemical Corporation.

[0023] The polyester elastomer is preferably a copolymer primarily composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol. 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 polytetramethylene ether glycol 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.

[0024] The number-average molecular weight of the polytetramethylene ether glycol is preferably 500 to 4000, more preferably 700 to 3000, and even more preferably 800 to 2500. 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.

[0025] 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 aliphatic dicarboxylic acid and / or an aliphatic polyether. For example, in the case of a polyester elastomer composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol (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 polytetramethylene ether glycol (PTMG).

[0026] 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.

[0027] The polyester elastomer preferably has a melting point of 150 to 230°C. If the melting point is below 150°C, the polyester elastomer may not have the required heat aging resistance and moldability (crystallinity). Conversely, if the melting point is above 230°C, the polyester elastomer may contain a large amount of hard segments, resulting in a correspondingly high glass transition temperature (Tg), and may not have the required impact resilience, flexibility, and low-temperature mechanical properties.

[0028] Examples of methods for producing polyester elastomers include reacting a dicarboxylic acid component with a diol component by a transesterification method, direct esterification method, or the like to form a prepolymer, followed by polycondensation under reduced pressure. In this case, a catalyst for the transesterification reaction or esterification reaction, or a catalyst for the polycondensation reaction can be appropriately used.

[0029] To produce the polyester elastomer of the present invention, it is preferable to extend the polycondensation time compared to conventional methods. For example, in the polycondensation of polyester elastomers using butylene terephthalate units as the hard segment constituent and polytetramethylene ether glycol as the soft segment constituent, the polycondensation time for producing polyester elastomers is typically about 50 to 90 minutes. In the present invention, however, the polycondensation time is preferably 100 to 140 minutes, more preferably 105 to 135 minutes. It is also preferable to control the polycondensation temperature within a narrow range. In the production of polyester elastomers, the polycondensation temperature is typically about 235 to 260°C. In the present invention, however, the polycondensation temperature is preferably 235 to 255°C, more preferably 240 to 250°C. If the polycondensation time is too short or the polycondensation temperature is too low, the polymerization reaction may not proceed smoothly, resulting in a high oligomer content or an increased acid value of the system. Furthermore, the reduced viscosity of the polyester elastomer may not increase, and satisfactory polyester elastomer functionality may not be achieved in terms of elongation at break or tensile strength at break, or the retention stability may deteriorate. Conversely, if the polycondensation time is long or the polycondensation temperature is high, thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and accelerating the formation of oligomers and gelation. The pressure is gradually reduced from the transesterification reaction pressure, with the final pressure preferably being 0.1 to 3 Torr, and more preferably 0.04 to 0.2 kPa. If the pressure exceeds the upper limit, reactivity may decrease, the reaction time may be prolonged, and thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and accelerating the formation of oligomers and gelation. On the other hand, if the pressure is too low, excessive volatilization or distillation of monomers may result in compositional deviations, or excessive reduction in intermolecular collisions may result in delays in the polymerization reaction. The polycondensation conditions described above need to be adjusted appropriately depending on the constituent components.

[0030] The biobased content of the polyester elastomer of the present invention, expressed as the biobased content of the resin composition including components such as flame retardants and thermal stabilizers, is 8 to 100%, preferably 8 to 95%, more preferably 8 to 90%, even more preferably 8 to 70%, and particularly preferably 8 to 50%. The biobased content of the polyester elastomer is preferably 20 to 100%, more preferably 20 to 85%, and even more preferably 20 to 80%. Conventionally, biomass-derived raw materials contain impurities that cannot be completely removed during the purification process. Therefore, increasing the proportion of biomass-derived raw materials in an attempt to increase the biobased content has resulted in problems such as an increase in the amount of impurities, which inhibits the reaction, preventing an increase in reduced viscosity, prolonging the polymerization time, and resulting in discoloration. Therefore, it has been difficult to obtain a biomass-derived polyester elastomer that can maintain excellent flexibility, low-temperature mechanical properties, heat aging resistance, and water resistance while preventing discoloration without reducing production efficiency. In the present invention, as polymerization raw materials for the polyester elastomer, materials derived from fossil fuel resources are used for the hard segments, and an aliphatic polyether is used as a raw material derived from biomass resources only for the soft segments. By adopting an appropriate polycondensation reaction time and temperature, it is possible to obtain a biomass resource-derived polyester elastomer that is free of coloration and that retains the excellent properties of fossil fuel resource-derived polyester elastomers.

[0031] The reduced viscosity (ηsp / c), which is an index of molecular weight, is an important characteristic of the polyester elastomer of the present invention. In the present invention, in order to exhibit the long-term durability (heat aging resistance, water resistance) of a polyester elastomer, the reduced viscosity is preferably 1.2 dL / g or more, more preferably 1.4 dL / g or more, and even more preferably 1.5 dL / g or more. If the reduced viscosity (ηsp / c) is low, the molecular weight will be small, and the long-term durability (heat aging resistance, water resistance) of a polyester elastomer that satisfies these requirements may not be achieved.

[0032] The glass transition temperature (Tg), which is an index of low-temperature mechanical properties, is an important characteristic of the polyester elastomer of the present invention. The glass transition temperature varies depending on the soft segment ratio in the polyester elastomer. In the present invention, the glass transition temperature at which the polyester elastomer exhibits its functions of rebound resilience, flexibility, and low-temperature mechanical properties is preferably -70 to 10°C, more preferably -65 to 10°C. If the glass transition temperature is high, it may not be possible to obtain a polyester elastomer that satisfies the functions of rebound resilience, flexibility, and low-temperature mechanical properties.

[0033] The content of oligomers with a molecular weight of less than 1,000 in the biomass-derived polyester elastomer is an important characteristic of the polyester elastomer of the present invention. The content of oligomers with a molecular weight of less than 1,000 in the biomass-derived polyester elastomer varies depending on the impurities in the biomass-derived raw materials and the polymerization conditions. In the present invention, the oligomer content is 2.5% by mass or less. Preferably, it is 2.4% by mass or less, more preferably 2.3% by mass or less, and even more preferably 2.2% by mass or less. A high oligomer content can result in an insufficient increase in the melt tension of the polyester elastomer composition during compounding during the production of the composition, making it difficult to achieve high-precision moldability. Furthermore, gel formation is more likely when a thickener is added, deteriorating the appearance and properties of molded articles. Furthermore, the thermal stability and water resistance of the molten resin can be impaired, resulting in differences in fluidity between the start and end of molding, impairing stable productivity. Furthermore, molded articles may not have satisfactory rebound resilience, flexibility, or low-temperature mechanical properties.

[0034] The composition and composition ratio of the polyester elastomer 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 in H-NMR.

[0035] The polyester elastomer resin composition of the present invention contains, in addition to the polyester elastomer described above, a flame retardant and a heat stabilizer as essential components. The polyester elastomer resin composition of the present invention may also optionally contain a thickener and / or a hydrolysis inhibitor.

[0036] As the flame retardant, halogen-based flame retardants and non-halogen-based flame retardants can be used, and these may be used alone or in combination. Furthermore, a flame retardant aid can be used in combination, if necessary. Examples of flame retardants include triazine compounds and / or their derivatives, phosphorus-based compounds, silicon-based flame retardants, metal hydroxides, metal borates, and bromine-based compounds. The content of the flame retardant in the polyester elastomer resin composition is 5 parts by mass or more, preferably 10 parts by mass or more, and preferably 100 parts by mass or less, per 100 parts by mass of the biomass resource-derived polyester elastomer. If the content is too low, the flame retardant effect will be insufficient, and if it is too high, physical properties may be reduced.

[0037] Examples of triazine compounds and / or derivatives thereof include melamine, melamine cyanurate, melamine phosphate, and guanidine sulfamate, among which melamine cyanurate is preferred.The content of these compounds is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the polyester elastomer.

[0038] Phosphorus compounds can be broadly classified into organic phosphorus compounds and inorganic phosphorus compounds. Organic phosphorus compounds include phosphates, phosphonates, phosphinates, and phosphites. Specific examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, and bis(1,3-phenylenediphenyl)phosphate. Among these, metal phosphinates are preferred from the standpoint of flame retardancy, with aluminum phosphinates being particularly preferred. Inorganic phosphorus compounds include red phosphorus compounds and inorganic phosphate compounds such as ammonium (poly)phosphate, melamine (poly)phosphate, and piperazine (poly)phosphate. The content ratio of these components is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the polyester elastomer.

[0039] Bromine compounds include hexabromocyclododecane, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, bis(tribromophenoxy)ethane, bis(pentabromophenoxy)ethane, tetrabromobisphenol A epoxy resin, tetrabromobisphenol A carbonate, ethylene (bistetrabromophthal)imide, ethylene bispentabromodiphenyl, tris(tribromophenoxy)triazine, bis(dibromopropyl)tetrabromobisphenol A, bis(dibromopropyl)tetrabromobisphenol A, Examples of suitable brominated polyethers include (dibromo)tetrabromobisphenol S, brominated polyphenylene ether (including poly(di)bromophenylene ether), brominated polystyrene (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene), brominated crosslinked aromatic polymers, brominated epoxy resins, brominated phenoxy resins, brominated styrene-maleic anhydride polymers, tetrabromobisphenol S, tris(tribromoneopentyl)phosphate, polybromotrimethylphenylindane, and tris(dibromopropyl)isocyanurate. Brominated polystyrene is preferred in terms of compatibility with polyester elastomers. The content of these brominated polyethers is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and particularly preferably 15 to 60 parts by mass, per 100 parts by mass of polyester elastomer.

[0040] Examples of flame retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, molybdenum oxide, red phosphorus compounds, ammonium polyphosphate, melamine cyanurate, and tetrafluoroethylene. Among these, antimony trioxide and antimony pentoxide are preferred. The content ratio of these aids is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, per 100 parts by mass of the polyester elastomer.

[0041] Heat stabilizers are used to prevent thermal oxidative decomposition during compounding and molding. Examples of heat stabilizers that can be used include known hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. The amount of heat stabilizer added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.2 to 3.5 parts by mass, per 100 parts by mass of polyester elastomer. If the amount of heat stabilizer is too small, the effect of preventing thermal oxidative decomposition will be insufficient, and if the amount is too large, mechanical properties may be reduced.

[0042] Hindered phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6'-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and calcium (3,5-di-t-butyl-4-hydroxybenzyl-monoethyl-phosphate). , triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3-(3,5-di-t-butylanilino)-1,3,5-triazine, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis[3,3-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid] glycol ester, tripheno 2,2'-Ethylidenebis(4,6-di-t-butylphenol), N,N'-Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-Oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-Tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isopropyl cyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic amide triester with-1,3,5-tris(2-hydroxyethyl)-S-triazine-2,4,6(1H,3H,5H), N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like.

[0043] Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodiuropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, dilaurylthiodipropionate, dioctadecyl sulfide, and pentaerythryl-tetra(β-lauryl-thiopropionate) ester.

[0044] Phosphorus-based antioxidants include tris(mixed, mono- and diolylphenyl)phosphite, tris(2,3-di-t-butylphenyl)phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphanite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene diphosphonite, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite, and the like can be mentioned.

[0045] Examples of the amine antioxidant include amines such as N,N-diphenylethylenediamine, N,N-diphenylacetamidine, N,N-diphenylformamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N,N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane, P,P'-dioctyl-diphenylamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, and 4,4'-bis(4-α,α-dimethyl-benzyl)diphenylamine, and derivatives thereof, reaction products of amines and aldehydes, and reaction products of amines and ketones.

[0046] The thickener is a reactive compound having a functional group capable of reacting with the terminal group of the polyester elastomer and a functional group capable of reacting with the hydroxyl or carboxyl group of the polyester elastomer. The reactive functional group is preferably at least one selected from the group consisting of an epoxy group (glycidyl group), an acid anhydride group, a carbodiimide group, and an isocyanate group, and two or more such functional groups are contained per molecule. The functional group is more preferably an epoxy group (glycidyl group).

[0047] When the thickener is a compound containing epoxy groups, examples of polyfunctional epoxy compounds containing two or more epoxy groups include 1,6-dihydroxynaphthalene diglycidyl ether and 1,3-bis(oxiranylmethoxy)benzene, which contain two epoxy groups; 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and diglycerol triglycidyl ether, which contain three epoxy groups; and 1-chloro-2,3-epoxypropane-formaldehyde-2,7-naphthalenediol polycondensates and pentaerythritol polyglycidyl ether, which contain four epoxy groups. Among these, polyfunctional epoxy compounds with heat resistance in the skeleton are preferred. Difunctional or tetrafunctional epoxy compounds with a naphthalene structure as the skeleton, or trifunctional epoxy compounds with a triazine structure as the skeleton are particularly preferred. Considering the degree of increase in the solution viscosity of the thermoplastic polyester elastomer, the effect of efficiently reducing the acid value of the thermoplastic polyester elastomer, and the degree of gelation due to aggregation and solidification of the epoxy itself, difunctional or trifunctional epoxy compounds are preferred.

[0048] When a thickener is added, the blending amount is preferably 0.1 to 5.0 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.2 to 3.5 parts by mass, per 100 parts by mass of polyester elastomer. If the amount of thickener is too small, the targeted molecular chain extension effect will be insufficient, while if the amount is too large, the thickening effect will be excessive, which will adversely affect moldability and the mechanical properties of the molded product. If the thickener is an epoxy compound, too much may cause unevenness on the surface of the molded product due to the aggregation and hardening of the epoxy compound. If the thickener is a carbodiimide compound, too much may cause hydrolysis of the thermoplastic polyester elastomer due to the basicity of the polycarbodiimide compound, which will tend to affect the mechanical properties.

[0049] Hydrolysis inhibitors are added to improve hydrolysis resistance and flex fatigue resistance through chain extension. Examples of hydrolysis inhibitors that can be used include compounds having functional groups capable of reacting with the terminal functional groups of polyester elastomers. The terminal functional groups of polyester elastomers are carboxyl groups and / or hydroxyl groups. Examples of functional groups capable of reacting with the terminal functional groups of polyester elastomers include carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, carbodiimide groups, and oxazoline groups. Among these, epoxy groups and carbodiimide groups are preferred as the functional groups in terms of changes in melt viscosity during melt retention and reactivity with the terminal functional groups of polyester elastomers. The hydrolysis inhibitor is preferably an epoxy compound and / or a carbodiimide compound.

[0050] The carbodiimide compound is a compound having at least one carbodiimide group represented by (-N=C=N-) in the molecule, and is capable of reacting with the terminal group of the polyester elastomer (A).

[0051] Examples of the carbodiimide compound include diphenylcarbodiimide, dicyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, carbodiimide, di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N,N'-di-o-toluylcarbodiimide, N,N'-diphenyl carbodiimide, N,N'-dioctyldecylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N-toluyl-N'-cyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N' -di-cyclohexylcarbodiimide, N,N'-di-p-toluylcarbodiimide, N,N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-toluylcarbodiimide, N-cyclohexyl-N'-toluylcarbodiimide, N-phenyl-N'-toluylcarbodiimide, N-benzyl-N'-toluylcarbodiimide, N,N'-di-o-ethylphenylcarbodiimide, N,N'-di-p-ethylphenylcarbodiimide, N,Mono- or dicarbodiimide compounds such as N'-di-o-isopropylphenylcarbodiimide, N,N'-di-p-isopropylphenylcarbodiimide, N,N'-di-o-isobutylphenylcarbodiimide, N,N'-di-p-isobutylphenylcarbodiimide, N,N'-di-2,6-diethylphenylcarbodiimide, N,N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N,N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N,N'-di-2,4,6-trimethylphenylcarbodiimide, N,N'-di-2,4,6-triisopropylphenylcarbodiimide, and N,N'-di-2,4,6-triisobutylphenylcarbodiimide; poly(1,6-hexamethylenecarbodiimide); diimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(toluylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), and the like. Among these, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, and polycarbodiimide are preferred, and more preferred are poly(1,6-hexamethylenecarbodiimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), and poly(3,3'-dimethyl-4,Examples of suitable polycarbodiimides include poly(4'-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(toluylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide). Among these, polycarbodiimides are preferred from the viewpoints of improving heat aging resistance and hydrolysis resistance, and reactivity with acid terminals, and particularly preferred are poly(1,4-cyclohexylenecarbodiimide) and poly(triisopropylphenylenecarbodiimide).

[0052] When a hydrolysis inhibitor is added, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.2 to 3.5 parts by mass, per 100 parts by mass of polyester elastomer. If the amount of hydrolysis inhibitor is too small, its effect will be insufficient, while if the amount is too large, there may be a decrease in flame retardancy or a decrease in mechanical properties due to the effect of foreign matter. Note that if a high molecular weight polyester elastomer that does not require chain extension or a polyester elastomer with a sufficiently low terminal acid value is used as the polyester elastomer, the addition of a hydrolysis inhibitor is not necessary.

[0053] In addition to the above components, the polyester elastomer resin composition of the present invention can contain various additives depending on the purpose, including known light stabilizers such as hindered amines, triazoles, benzophenones, benzoates, nickel, and salicylic acids, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, and organic and inorganic pigments.

[0054] The acid value of the polyester elastomer resin composition of the present invention is preferably 0 to 20 eq / ton, more preferably 0 to 15 eq / ton, and even more preferably 0 to 10 eq / ton. When the acid value is within the above range, the melt viscosity during molding is stable, and in the case of extrusion molding of tubular molded products such as cables and hoses, thickness uniformity is improved. In addition, hydrolysis resistance is excellent.

[0055] The method for producing the polyester elastomer resin composition of the present invention is not particularly limited, but it can be produced by melt-kneading each component using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, roll, or the like known to those skilled in the art.

[0056] When using a twin-screw extruder, it is preferable to appropriately select the extruder barrel temperature and screw configuration to control the resin pressure in the extruder plasticization zone. When melt-kneading the above components, it is important to allow the molten components to coexist with the molten polymer phase in the polymer plasticization zone, increase the polymer viscosity as the matrix phase, and use shear stress to uniformly melt the molten components into the polymer phase, while controlling internal heat generation to suppress polymer degradation and side reactions. The resin pressure is preferably about 0.1 to 1 MPa.

[0057] The melting temperature of the resin composition during melt-kneading is preferably 160 to 300° C., and more preferably 180 to 280° C. If the melting temperature is low, melting becomes insufficient and unmelted gels tend to occur frequently, whereas if the resin temperature is high, thermal degradation of the polymer and thermal decomposition of the flame retardant tend to occur.

[0058] In the present invention, it is preferable to reduce the screw rotation speed to suppress polymer degradation and thermal decomposition of the flame retardant, while increasing the discharge rate to speed up the flow of resin through the screw. This prevents the flame retardant from adhering to the screw, barrel, etc., and allows the flame retardant to be dispersed uniformly. In addition, this ensures that the polymer has enough time to react slowly and sufficiently with the thickener, hydrolysis inhibitor, etc., and prevents sudden and / or localized reactions.

[0059] The discharge rate during melt kneading is preferably 20 to 1,000 kg / hr, more preferably 50 to 500 kg / hr, and even more preferably 150 to 400 kg / hr. If the discharge rate is too low, the resin filling rate in the extruder tends to decrease, resulting in uneven kneading. Conversely, if the discharge rate is too high, the resin filling rate in the extruder tends to become too high, resulting in uneven kneading and insufficient time for dispersing the flame retardant and thickening the polymer.

[0060] The screw rotation speed is preferably 50 to 300 rpm, and more preferably 100 to 200 rpm. If the screw rotation speed is low, the dispersion of the flame retardant will be poor and the components will tend to be less uniformly melted and reacted, while if the screw rotation speed is high, shear heat will occur, which may cause polymer degradation or side reactions, or the flame retardant may be thermally decomposed.

[0061] Furthermore, the ratio of screw length L (mm) to screw diameter D (mm), L / D, preferably satisfies the relationship 40≦(L / D)≦100, and even more preferably 45≦(L / D)≦80. If L / D is small, it is difficult to uniformly disperse the flame retardant with small particle size, and when thickening a polymer, it may be difficult to ensure sufficient time for the thickening reaction. On the other hand, if L / D is large, thermal decomposition of the flame retardant and thermal degradation of the polymer tend to occur.

[0062] The polyester elastomer resin composition of the present invention has a tensile elongation at break of 200% or more, preferably 250% or more, and more preferably 300% or more. If the tensile elongation at break is less than the above range, the flexibility required when used as a coating material for cables, electric wires, etc. will be insufficient, resulting in poor overall mechanical properties, and poor water aging resistance and extrusion moldability. Furthermore, there is a tendency for the flame retardancy to vary and for the appearance of molded articles to deteriorate. The main factors that reduce the tensile elongation at break of the polyester elastomer composition are the low degree of polymerization of the biomass resource-derived polyester elastomer, the low reactivity of the thickener, and the poor dispersibility of the flame retardant in the polyester elastomer composition.

[0063] Furthermore, when the hard segment mass% of the polyester elastomer is 50 mass% or more, the tensile break strength is preferably 15 MPa, more preferably 20 MPa or more, and even more preferably 25 MPa or more. When the hard segment mass% is less than 50 mass%, the tensile break strength is preferably 8 MPa, more preferably 9 MPa or more, and even more preferably 10 MPa or more. In applications such as electric wire / cable coating materials, the tensile break strength required varies depending on the application, but it is preferable to obtain characteristics based on the design at the time of polymerization or compounding.

[0064] The tensile elongation at break (%) and tensile strength at break (MPa) of the polyester elastomer resin composition were measured in accordance with JIS K 6251. Test specimens were prepared by injection-molding a resin dried under reduced pressure at 100°C for 5 hours into a 100mm x 100mm x 2mm plate using an injection molding machine at a cylinder temperature (Tm+20°C) and a mold temperature of 30°C, and then punching out a dumbbell-shaped No. 3 test specimen from the plate.

[0065] The polyester elastomer resin composition of the present invention has a specific gravity of 1.20 or more, preferably 1.24 or more, more preferably 1.30 or more, and particularly preferably 1.35 or more. If the specific gravity is below the above range, it is difficult to incorporate a flame retardant in an amount sufficient to ensure flame retardancy. The upper limit of the specific gravity is preferably 2.00 or less. If the specific gravity is too high, the dispersibility of the flame retardant in the composition may decrease, which may result in a decrease in mechanical properties and stable productivity during production.

[0066] The polyester elastomer resin composition of the present invention preferably has a melt flow rate (MFR) of 1 to 20 g / 10 min, more preferably 2 to 15 g / 10 min, measured at a melting point of 20°C and a load of 2.16 kg according to the flow test method for thermoplastics specified in JIS K7210. If the MFR value falls outside this range, extrusion molding may become impossible. Furthermore, the difference between the MFR value 45 minutes after addition (MFR45) and the MFR value 5 minutes after addition (MFR5) (ΔMFR:MFR45-MFR5), which is an index of retention stability, is preferably 0 to 25 g / 10 min, more preferably 0 to 20 g / 10 min, even more preferably 0 to 15 g / 10 min, and particularly preferably 0 to 10 g / 10 min. If the ΔMFR is greater than this range, retention stability may be poor, and the decrease in melt viscosity during molding may not be suppressed, preventing stable extrusion molding. This may result in uneven thickness when molding cables or hoses. On the other hand, if the content is less than the above range, the melt viscosity increases significantly during molding, and there is a risk that stable moldability cannot be obtained.

[0067] While there are no particular limitations on the method for adjusting the MFR and ΔMFR within the above ranges, it is preferable to incorporate a specific amount of thickener using a specific method. This allows the acid value of the polyester elastomer resin composition to be controlled within a specific range, thereby adjusting the MFR and ΔMFR within the above ranges. The acid value can be adjusted appropriately depending on the thickening characteristics (e.g., acid value of the polyester elastomer, number of reactive groups of the thickener and hydrolysis inhibitor, molecular weight), the increase in acid value due to decomposition of the polyester elastomer through hydrolysis, and reactivity with other additives. When an epoxy compound and a polycarbodiimide are used in combination as a thickener and / or hydrolysis inhibitor, unreacted reactive compounds tend to remain in the resin composition. These unreacted reactive compounds react with the polyester elastomer during retention during molding, increasing its molecular weight and contributing to a decrease in MFR and ΔMFR. However, this can also lead to a decrease in long-term extrusion moldability, such as a larger difference between the initial and final thicknesses.

[0068] The polyester elastomer resin composition of the present invention preferably has a 3% weight loss temperature of 300°C or higher when heated from room temperature to 450°C at a rate of 10°C / min. If the 3% weight loss temperature is lower than 300°C, the residence stability and moist heat resistance of the polyester elastomer resin composition may be impaired. The biomass resource-derived components used in the polyester elastomer of the present invention tend to thermally decompose faster than fossil fuel resource-derived components, accelerating the weight loss of the polyester elastomer composition. In particular, the higher the molecular weight of the aliphatic polyol and the higher its proportion in the polyester elastomer, the more rapid the weight loss. Furthermore, radicals generated by the thermal decomposition of the flame retardant may accelerate the polymer decomposition reaction, lowering the weight loss temperature.

[0069] The 3% weight loss temperature can be measured using a differential thermal and thermogravimetric simultaneous analyzer (Shimadzu Corporation, DTG-60). 50 mg of the polyester elastomer resin composition was placed in a platinum cell and heated to 450°C at a heating rate of 5°C / min in a nitrogen atmosphere with a flow rate of 20 ml / min. Decomposition proceeds at high temperatures, and the temperature at which the weight is 97% of the initial weight is defined as the 3% weight loss temperature.

[0070] Because the polyester elastomer resin composition of the present invention is configured as described above, it retains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy of fossil fuel-derived polyester elastomers, despite using a polyester elastomer derived from a biomass resource with a high biomass content. Therefore, it can be used in a wide range of applications, including electronic device components, hoses, tubing, wire and cable coating materials, and monofilaments. In particular, the polyester elastomer resin composition of the present invention has excellent extrusion moldability, making it suitable for applications such as films and sheets. Furthermore, the polyester elastomer resin composition of the present invention can be molded into various shapes by methods other than extrusion molding, such as injection molding, transfer molding, and blow molding, and therefore can be used in a wide range of applications as a flame-retardant polyester elastomer. [Example]

[0071] 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. The raw materials used in the examples, and those not otherwise specified, are derived from fossil fuel resources.

[0072] (1) Bio-based content The bio-based content of a polyester elastomer is the ratio of the biomass-derived monomer components to the total mass of the monomer components that make up the polyester elastomer, calculated from the mass of the biomass-derived monomer components. The bio-based content is the ratio of the carbon content of the polyester elastomer that is only contained in the biomass-derived raw materials. 14 C carbon ( 12 The biobased content (%) of the polyester elastomer was measured using an accelerator mass spectrometer (AMS) in accordance with ASTM D6866. On the other hand, the bio-based content of a polyester elastomer resin composition is the ratio of carbon elements in the biomass resource-derived monomer components calculated from the mass of the biomass resource-derived monomer components relative to the mass of all the monomer components constituting the polyester elastomer resin composition. The bio-based content is the ratio of carbon elements contained only in the biomass resource-derived raw materials to the total carbon contained in the polyester elastomer resin composition. 14 C carbon ( 12 The biobased content (%) of the polyester elastomer resin composition was measured using an accelerator mass spectrometer (AMS) in accordance with ASTM D6866.

[0073] (2) Reduced viscosity (ηsp / c) 0.05 g of the polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane=60 / 40), and the reduced viscosity (dl / g) was measured at 30° C. using an Ubbelohde viscometer.

[0074] (3) Melting point (Tm) Using a differential scanning calorimeter "DSC220" manufactured by Seiko Electronics Co., Ltd., 5 mg of the measurement sample was placed in an aluminum pan, the lid was pressed down to seal it, and the sample was melted in nitrogen at 250°C for 2 minutes. The temperature was then lowered to 50°C at a rate of 20°C / min, and the temperature was then raised from 50°C to 250°C at a rate of 20°C / min. The endothermic peak due to melting was determined from the obtained thermogram curve, and this was taken as the melting point (°C).

[0075] (4) Glass transition temperature (Tg) A measurement sample was prepared by pressing a 0.4 mm thick sheet with a hot plate heated to 200-250°C using an NF-type single-action compression molding machine (manufactured by Shinto Metal Industries Co., Ltd.). Measurements were performed using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) at a measurement frequency of 11 Hz and a heating rate of 2°C / min, and the peak position of tan δ from -150°C to 150°C was taken as Tg (°C).

[0076] (5) Acid value (AV) 0.2 g of sample was accurately weighed, and benzyl alcohol was added and heated to dissolve. It was then dissolved in 20 ml of chloroform and titrated with 0.08 N potassium hydroxide (ethanol solution). The acid value (eq / ton) was calculated from the amount of potassium hydroxide required for neutralization. Phenol red ethanol solution was used as an indicator.

[0077] (6) Oligomer content The oligomer content in polyester elastomer (A) was measured as follows: 8 mg of the resin component was weighed and dissolved in 4 ml of HFIP / 10 mM sodium trifluoroacetate. The solution was filtered through a 0.2 μm membrane filter, and the resulting sample solution was subjected to GPC analysis under the following conditions. The molecular weight was calculated in terms of polymethyl methacrylate (PMMA), and the ratio (percentage) of the peak area showing a molecular weight of 1000 or less to the total peak area of ​​the polymer in the GPC analysis chart was calculated, and this area ratio was taken as the oligomer amount (wt%). Equipment: TOSOH HLC-8320GPC Column: TOSOH TSKgel SuperHM-H x 2 +TSKgel SuperH2000 Solvent: HFIP / sodium trifluoroacetate 10mM Flow rate: 0.2ml / min Injection volume: 10μl Temperature: 40℃ Detector: RI Concentration: 0.05%

[0078] (7) Specific gravity Measurement was performed using an automatic gravity meter D-H100 manufactured by Toyo Seiki Co., Ltd. The flat plate formed in (8) was cut into a size of 10 mm x 10 mm to obtain a sample for specific gravity measurement. Using the prepared sample for specific gravity measurement, specific gravity measurement was performed by the underwater displacement method.

[0079] (8) Tensile elongation and tensile strength The tensile elongation at break (%) and tensile strength at break (MPa) of the polyester elastomer resin composition were measured in accordance with JIS K 6251. The test specimens used for the measurements were prepared by injection-molding the resin composition, which had been dried under reduced pressure at 100°C for 5 hours, into a 100 mm x 100 mm x 2 mm flat plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) at a cylinder temperature (Tm+20°C) and a mold temperature of 30°C, and then punching out a dumbbell-shaped No. 3 test specimen from the flat plate.

[0080] (9)UL-94 flame retardant Using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV), test specimens with a thickness of 1 / 16 inch conforming to the UL-94 standard (a standard established by Underwriters Laboratories Inc., USA) were injection molded at a cylinder temperature of (Tm+20°C). The test specimens obtained by the above method were evaluated in accordance with the UL-94 flammability test method. The burning time was shown as the total burning time of five samples after two exposures to flame.

[0081] (10) Flame retardancy variation The flame retardancy of the test pieces was evaluated 5 minutes, 35 minutes, 65 minutes, 90 minutes, and 125 minutes after the start of injection molding as described in (9), and the flame retardancy variation was evaluated according to the following criteria. 〇: The flame retardancy of all five test pieces is the same ×: The flame retardancy of one or more of the five test pieces is different.

[0082] (11)ΔMFR The melt flow rate (MFR: g / 10 min) of the polyester elastomer resin composition was measured at 2160 g at 20°C above the melting point of the polyester elastomer (A) according to the test method (Method A) described in JIS K7210. A composition with a moisture content of 0.1% by mass or less was used for the measurement. The difference (ΔMFR: MFR45 - MFR5) between the MFR value 45 minutes after addition of the composition (MFR45) and the MFR value 5 minutes after addition of the composition was measured.

[0083] (12)3% weight loss temperature Measurements were performed using a differential thermal and thermogravimetric simultaneous analyzer (Shimadzu Corporation, DTG-60). 50 mg of the polyester elastomer resin composition was placed in a platinum cell and heated to 450°C at a heating rate of 5°C / min in a nitrogen atmosphere with a flow rate of 20 ml / min. Decomposition progressed at high temperatures, and the temperature at which the weight was 97% of the initial weight was defined as the 3% weight loss temperature.

[0084] (13) Evaluation of gelled products Approximately 50 g of polyester elastomer resin composition was weighed into a 250 ml glass bottle (approximately 4 cm diameter x 20 cm high), immersed in a 250°C silicone oil bath, and heated for 4 hours while stirring and blowing nitrogen into it from above (approximately 30 ml / min). After treatment, the contents were dissolved in 500 ml of a mixed solvent of tetrachloroethane and phenol (1 / 1 by weight) (the glass bottle was also rinsed with some of the mixed solvent). The insoluble matter was then separated using a 100-mesh stainless steel wire mesh (weight V') of known weight, visually inspected, and evaluated according to the following criteria. ○: No gel was observed. ×: Gelled matter was observed.

[0085] (14) Extrusion moldability (pulsation) The pellets melt-kneaded in the twin-screw extruder were extruded again from a round die in a single-screw extruder to extrude strands with a diameter of 3 mm. From this state, the extrusion moldability (fluctuation in the extrusion rate) was evaluated according to the following criteria. ◯: No fluctuation in discharge amount occurs and extrusion is stable. △: The discharge amount fluctuated and the extrusion properties were unstable. ×: The discharge rate fluctuates greatly, and strand breakage occurs frequently.

[0086] (15) Extrusion moldability (smoothness) The pellets melt-kneaded in the twin-screw extruder were extruded again through a T-die in a single-screw extruder to produce a 0.2 mm thick sheet. The smoothness of the extrusion molded product was evaluated based on the appearance of the sheet according to the following criteria. ◯: No roughness or bubbles were observed, and the sheet appearance and surface smoothness were good. △: Sheet irregularities (melt fracture) and foaming do not occur, but there is uniform roughness like embossing. ×: Sheet irregularities (melt fracture) and foaming occurred, and the sheet appearance was poor.

[0087] [Polyester elastomer (A)] Polymerization Example 1 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2750 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1380 parts by mass, biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 710 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 150 minutes to carry out an ester exchange reaction. The pressure inside the autoclave 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 then carried out for 135 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (A1).

[0088] Polymerization Example 2 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1550 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1170 parts by mass, biomass-derived polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 2140 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 200 ° C over 180 minutes to carry out a transesterification reaction. The pressure inside the autoclave 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 90 minutes. The polymerization reaction was then carried out for 115 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 28 / 72 (mass%) was obtained in pellet form. The resulting polymer was designated as polyester elastomer (A2).

[0089] Polymerization Example 3 2750 parts by weight of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1380 parts by weight of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 710 parts by weight of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by weight of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by weight of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245°C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated polyester elastomer (A3).

[0090] Polymerization Example 4 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2750 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1380 parts by mass, biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 710 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, and AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 150 minutes to carry out an ester exchange reaction. The pressure inside the autoclave 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 then carried out for 90 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (A4).

[0091] Polymerization Example 5 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2750 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1380 parts by mass, biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 710 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, and AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 150 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 230 ° C over 65 minutes, at 0.7 Torr or less, to carry out an initial condensation reaction. The polymerization reaction was then carried out for 130 minutes at 255 ° C and 0.7 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was obtained in pellet form. The resulting polymer was designated as polyester elastomer (A5).

[0092] Polymerization Example 6 2,6-dimethyl naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical), 2200 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1250 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 90 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 ° C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. The polymerization reaction was then carried out for 110 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 56 / 44 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (A6).

[0093] Polymerization Example 7 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1450 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1720 parts by mass, biomass-derived dimer acid (C36DiCOOH, manufactured by Croda Propol 1009) 1670 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, and AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 120 minutes to carry out transesterification and esterification reactions. The pressure inside the autoclave 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 then carried out for 60 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 66 / 34 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (A7).

[0094] Table 1 shows the compositions and evaluation results of the polyester elastomers (A1) to (A7).

[0095] [Table 1]

[0096] [Flame retardant (B)] (B1) Brominated polystyrene: PDBS-80, manufactured by LANXESS (B2) Aluminum diethylphosphinate: EXOLIT OP1230, manufactured by Clariant K.K.

[0097] [Flame retardant synergist (C)] (C1) Antimony trioxide: Twinkling Star, manufactured by Chugoku Kogyo Co., Ltd.

[0098] [Heat stabilizer (D)] Hindered phenol antioxidant: Irganox 1010 (manufactured by BASF)

[0099] [Hydrolysis inhibitor (E)] Alicyclic polycarbodiimide: Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Inc.

[0100] [Thickener (F)] Triglycidyl isocyanurate compound: "TEPIC-S", manufactured by Nissan Chemical Co., Ltd., epoxy valence (average number of epoxy groups per molecule): 3

[0101] [Comparative Examples 1 to 3, Reference Example 1, Examples 2 and 3] The above components were weighed in the proportions shown in Table 2, premixed in a mixer for 90 seconds, and then fed into the first main feed port from the upstream end of a 51 mm screw diameter, 48 L / D (14 barrel) co-rotating twin-screw extruder (STS-50, manufactured by Coperion). The extruder barrel temperature was set to 180°C to 240°C, the screw rotation speed was 180 rpm, and the output rate was 50 kg / h. Finally, the mixture was taken up in the form of a strand from the die, passed through a water bath to cool and solidify, and then cut into pellets using a pelletizer to obtain polyester elastomer resin composition pellets. The resulting polyester elastomer resin composition pellets were vacuum dried overnight at 80°C and then subjected to various tests.

[0102] [Comparative Examples 4 and 5] The above components were weighed out in the blending ratios shown in Table 2 and fed into the main feed port of a co-rotating twin-screw extruder (TEM58BS, manufactured by Toshiba Machine Co., Ltd.) with a screw diameter of 58 mm and an L / D ratio of 37 (9 barrels). The extruder barrel temperature was set to 180°C to 240°C, the screw rotation speed was 360 rpm, and the extrusion rate was 100 kg / h, and melt-kneading was performed. Finally, the mixture was taken up in the form of a strand from the die, passed through a water bath to cool and solidify, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried at 80°C overnight and then subjected to various tests.

[0103] [Examples 1, 4 to 8, Comparative Examples 6 to 8] The above components were weighed out in the proportions shown in Table 2. The components other than the hydrolysis inhibitor were premixed in a mixer for 90 seconds, and then fed into the first main feed port from the upstream end of a 58 mm screw diameter, L / D = 53 (15 barrels) co-rotating twin-screw extruder (TEX54αII, manufactured by The Japan Steel Works, Ltd.). The extruder barrel temperature was set to 180°C to 240°C, the screw rotation speed was 160 rpm, and the output rate was 200 kg / h. When a hydrolysis inhibitor was included, it was added to the 10th barrel from the upstream end of the extruder and melt-kneaded. Finally, the mixture was drawn out in strand form from the die, passed through a water bath, cooled, and solidified. It was then cut into pellets using a pelletizer to obtain polyester elastomer resin composition pellets. The resulting polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to various tests.

[0104] [Table 2]

[0105] As is clear from Table 2, Examples 1 to 8, in which the specific gravity and tensile elongation at break of the polyester elastomer resin compositions were within the ranges specified in the claims, were excellent not only in mechanical properties (tensile elongation at break and tensile strength), but also in retention stability (ΔMFR), flame retardancy (UL-94: V-2 or higher, variability), gelled product evaluation, and extrusion moldability (pulsation, smoothness). Furthermore, as can be seen from a comparison between Comparative Example 1 and Reference Example 1, even when prepared under the same polymerization conditions, composition formulation, and melt-kneading conditions, the biomass-derived polyester elastomer resin composition (Comparative Example 1) was inferior in mechanical properties, retention stability, and extrusion moldability (smoothness) to the fossil-fuel-derived polyester elastomer resin composition (Reference Example 1). Furthermore, Comparative Example 2, which used a polyester elastomer (A4) with a low reduced viscosity, was significantly inferior in mechanical properties, retention stability, and extrusion moldability to Comparative Example 1 and Reference Example 1. Furthermore, in Comparative Example 5, in which the screw rotation speed was increased to intensify kneading compared to Comparative Example 1, mechanical properties and retention stability were further improved, but the flame retardant thermally decomposed due to shear heat generated during kneading, deteriorating extrusion moldability. In addition, the flame retardant was less absorbed into the resin, resulting in variations in the flame retardant content and poor dispersion. On the other hand, in Example 1, in which the screw rotation speed was reduced compared to Comparative Example 1 and the L / D ratio was increased to set melt-kneading conditions over a longer period of time, both the thickening of the polymer and the dispersibility of the flame retardant were significantly improved, resulting in mechanical properties and extrusion moldability equivalent to those of Reference Example 1, which used a polyester elastomer derived from fossil fuel resources. Furthermore, even when the melt-kneading conditions were set similar to those of Example 1, Comparative Example 6, which used a polyester elastomer (A4) with a low reduced viscosity and a high oligomer content, and Comparative Example 7, which used a polyester elastomer (A5) with a similar reduced viscosity but a high oligomer content, were significantly inferior in mechanical properties and extrusion moldability to Reference Example 1. In Comparative Example 8, in which the content of the flame retardant was reduced to a level where the specific gravity was less than 1.20 compared to Example 4, V-2 was not achieved.

[0106] In Example 2, which used polyester elastomer (A2) with a high soft segment ratio and a high reduced viscosity, the tensile elongation at break and extrusion moldability were excellent, even though no thickener was contained. Furthermore, in Comparative Example 1 and Examples 3 and 4, in which the polyester elastomer (A1) in Example 1 was changed to polyester elastomer (A2), the tensile elongation at break was further improved.

[0107] In Example 5, in which a hydrolysis inhibitor was added to the composition of Example 1, the retention stability was improved. In Example 6, in which the flame retardant (B1) in the composition of Example 1 was replaced with a non-halogen flame retardant (B2), the mechanical properties and extrusion moldability were excellent, but the flame retardancy remained at V-2. [Industrial Applicability]

[0108] Despite using a polyester elastomer derived from a biomass resource with a high bio-based content, the polyester elastomer resin composition of the present invention retains the excellent mechanical properties, retention stability, extrusion moldability, and flame retardancy of polyester elastomers derived from fossil fuel resources, and is suitable for applications requiring flame retardancy and high-precision moldability, such as hoses, tubes, cables, and electric wire coating materials. Therefore, the polyester elastomer resin composition of the present invention will make a significant contribution to solving environmental problems such as the depletion of fossil fuel resources, and is extremely useful in this industry.

Claims

1. A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer, the soft segment of which is derived from a biomass resource, a flame retardant, and a heat stabilizer, wherein the content of the flame retardant is 5 to 100 parts by mass per 100 parts by mass of the polyester elastomer, wherein the biomass resource-derived polyester elastomer has a melting point of 150 to 230°C, a glass transition temperature of -70 to 10°C, a content of oligomers with a molecular weight of less than 1000 of 2.5% or less by mass, and a reduced viscosity of 1.2 dl / g or more, the content of the heat stabilizer is 0.1 to 5 parts by mass per 100 parts by mass of the polyester elastomer, the biobased content of the polyester elastomer resin composition is 8 to 100%, the specific gravity of the polyester elastomer resin composition is 1.20 or more, the tensile elongation at break of the polyester elastomer resin composition is 200% or more, and the melt flow rate (MFR) value of the polyester elastomer resin composition satisfies JIS A polyester elastomer resin composition characterized in that, when measured in accordance with the flow test method for thermoplastics specified in JIS K7210 at a melting point +20°C and a load of 2.16 kg, the polyester elastomer resin composition has a melt flow rate of 1 to 20 g / 10 min, and, with respect to the melt flow rate (MFR: g / 10 min) of the polyester elastomer resin composition measured in accordance with the test method (Method A) described in JIS K7210 at a melting point +20°C of the polyester elastomer and a load of 2,160 g, the difference (ΔMFR: MFR45 - MFR5) between the MFR value 45 minutes after addition of the polyester elastomer resin composition (MFR45) and the MFR value 5 minutes after addition (MFR5) is 25 or less.

2. 2. The polyester elastomer resin composition according to claim 1, wherein the biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of a polyester having as its constituent components an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment made of an aliphatic polyether, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource.

3. 3. The polyester elastomer resin composition according to claim 2, wherein the biomass resource-derived aliphatic polyether of the biomass resource-derived polyester elastomer is polytetramethylene ether glycol.

4. 4. The polyester elastomer resin composition according to claim 1, wherein the polyester elastomer resin composition has a 3% weight loss temperature of 300°C or higher when heated from room temperature to 450°C at a rate of 10°C / min.

5. 4. The polyester elastomer resin composition according to claim 1, wherein the flame retardancy rating measured according to UL94 is V-2, V-1, or V-0.

6. A wire / cable covering material using the polyester elastomer resin composition according to any one of claims 1 to 3.

7. An electronic device part using the polyester elastomer resin composition according to any one of claims 1 to 3.

8. A monofilament made from the polyester elastomer resin composition according to any one of claims 1 to 3.

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