Resin composition using biomass resource-derived polyester elastomer

Abstract

The present invention provides a biomass resource-derived polyester elastomer resin composition that can maintain the properties of a fossil fuel resource-derived polyester elastomer even when the proportion of biomass resource-derived raw materials used in the polyester elastomer is increased. The present invention provides a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the chemiluminescence emission amount of the polyester elastomer resin composition is set to a specific range, and the oligomer content of the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000, the 3% weight loss temperature, the difference between the melting point and the Vicat softening point of the polyester elastomer resin composition, or the MFR value of the polyester elastomer resin composition is set to a specific range.

Description

[Technical Field]

[0001] The present invention relates to a biomass resource-derived polyester elastomer resin composition that, despite using a biomass resource-derived polyester elastomer with a high bio-based content, can retain the excellent mechanical properties, storage stability, elongation retention rate after humid heat treatment, extrusion moldability, water aging resistance, flame retardancy, strength, elastic properties, elongation recovery properties, filament processability, and high-precision moldability of a fossil fuel resource-derived polyester elastomer. [Background technology]

[0002] Polyester elastomers are materials with excellent injection and extrusion moldability, 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 components, textiles, films, and sports parts.

[0003] Another reason why polyester elastomers are used in a wide range of applications is their extremely high molding design accuracy in various molding methods, including not only general injection molding, but also extrusion molding into thin film shapes, tube and hose shapes, and blow molding into duct shapes.

[0004] In recent years, concerns about the depletion of fossil fuel resources and the global environmental problem of increasing carbon dioxide in the atmosphere have led to the advancement of biomass-based polymers. Since biomass resources are renewable, they are expected to become an important design concept in future polymer development from the perspective of SDGs and carbon neutrality.

[0005] However, since biomass-derived raw materials contain impurities that could not be completely removed during the refining process, increasing the proportion of biomass-derived raw materials in an attempt to increase the bio-based degree of the polyester elastomer increases the amount of impurities. As a result, the reaction is inhibited, the reduced viscosity does not increase, and it becomes difficult to maintain the excellent properties of fossil fuel-derived polyester elastomers.

[0006] Furthermore, factors such as impurities introduced into biomass-derived raw materials, oligomers generated by polymerization reactions using these materials, by-reactants, foreign substances, and polymers different from the design make it difficult for polyester elastomers to exhibit their inherently excellent molding design precision.

[0007] In film molding, high molding stability is achieved when the resin is easily deformable in the high-elongation region as it exits the die, has high extensional viscosity and hardens easily at a strain rate in terms of flow properties, and does not exhibit ductile necking in the low-elongation region after exiting the die. To obtain such high molding stability, high polymer molecular design capability is required to control entanglement and slippage between molecular chains. However, when using polyester elastomers manufactured from biomass resource raw materials, problems arise such as low polymer molecular design capability, poor wall thickness accuracy due to the influence of introduced impurities and foreign substances, and a tendency for breakage during production.

[0008] To address the problems in film molding, it has been proposed to reduce the sulfur atom content and acid-end group content in polyesters made from biomass-derived dicarboxylic acids and / or diols to prevent a decline in the mechanical properties of the polyester (see Patent Document 1). While this biomass-derived polyester can prevent a decline in mechanical properties to some extent, it has the problem of causing discoloration of the polyester and degrading the appearance of the molded product. Furthermore, it could not maintain the excellent properties of fossil fuel-derived polyester in terms of storage stability, water aging resistance, and heat aging resistance.

[0009] In recent years, insulated wires and cables used in electronic equipment and other devices require extremely high levels of flame retardancy for safety reasons, necessitating the inclusion of large amounts of flame retardants in polyester elastomer compositions. Commonly used flame retardants include halogen compounds such as bromine compounds, which have high flame-retardant effects, as well as, if necessary, antimony oxide and non-halogen flame retardants that do not pose a risk of generating halogen gases.

[0010] However, flame retardants generally have low molecular-level compatibility with polyester elastomers, and the difference in specific gravity is also significant, resulting in poor dispersibility within polyester elastomer compositions. Therefore, polyester elastomer compositions containing large amounts of flame retardants may suffer from reduced mechanical properties such as tensile strength and elongation at break, the formation of flame retardant clumps and flow marks which degrade the appearance of molded products, and the accumulation of flame retardants at the die outlet of the extruder, causing eye deposits. Furthermore, the use of large amounts of flame retardants can cause slippage and uneven feeding within the screw during the melt-mixing process, leading to pulsation and a decrease in extrusion volume. Therefore, obtaining a flame-retardant composition of stable quality requires extremely advanced dispersion technology, which simultaneously limits the setting of melt-mixing conditions (see Patent Document 2).

[0011] Furthermore, for monofilament applications, in order to design monofilaments that possess sufficient mechanical properties as fabric constituent materials to support static loads, and that exhibit little deterioration in mechanical properties even when deformed by repeated external forces, fossil fuel-derived polyester elastomers have been proposed in which the properties of the soft segment constituent components in the polyester elastomer and the soft segment content are specified (see Patent Document 3). However, with biomass resource-derived raw material polyester elastomers, there are problems such as low polymer molecular designability, as well as the influence of introduced impurities and foreign substances, which prevent the acquisition of the desired properties.

[0012] To address the problems in monofilament applications, it has been proposed to reduce the sulfur atom content and acid-end group content in polyesters made from biomass-derived dicarboxylic acids and / or diols to prevent a decline in the mechanical properties of the polyester (see Patent Document 1). While this biomass-derived polyester can prevent a decline in mechanical properties to some extent, it has the problem of causing discoloration of the polyester and degrading the appearance of molded products. Furthermore, it could not maintain the excellent properties of fossil fuel-derived polyesters in terms of elasticity, elongation recovery, and filament processability.

[0013] Furthermore, in foam molding resin compositions based on fossil fuel-derived polyester elastomers, by blending a thickener with the polyester elastomer and adjusting it to a specific acid value and MFR, good foam moldability is achieved, enabling weight reduction through high-magnification foaming, thereby obtaining a resin foam with extremely high rebound modulus and repeated compressive stress (see Patent Document 4).

[0014] However, when using polyester elastomers derived from biomass resources, impurities and foreign substances introduced by the biomass-derived raw materials had an impact. Factors such as oligomers, by-reactants, and polymers different from the design, generated by the polymerization reaction using these materials, prevented the polyester elastomer from exhibiting its inherently excellent molding design precision. In particular, compared to polyester elastomers derived from fossil fuel resources, it was difficult to control the melt flowability, and when foamed molded products were formed, coarse bubbles and open bubbles were easily created. As a result, the rebound modulus and 50% constant displacement cyclic compression set of the foamed molded products were poor.

[0015] To address the problems associated with such resin compositions for foam molding, a method has been proposed that prevents deterioration of the mechanical properties of polyester by reducing the content of sulfur atoms and the amount of acid terminal groups in polyester produced using dicarboxylic acid and / or diol derived from biomass resources as raw materials (see Patent Document 1). Although this biomass resource-derived polyester prevents deterioration of mechanical properties to a certain extent, it employs the same compounding conditions as those for fossil fuel resource-derived polyesters. As a result, the thickening reaction does not proceed sufficiently, the melt viscosity does not increase, which leads to thermal degradation of the biomass resource-derived polyester and causes variations in resin properties. [Prior Art Documents] [Patent Documents]

[0016] [Patent Document 1] Japanese Patent No. 5303237 [Patent Document 2] Japanese Patent No. 5463779 [Patent Document 3] Japanese Patent No. 4018251 [Patent Document 4] Japanese Patent No. 7103003 [Summary of the Invention] [Problem to be Solved by the Invention]

[0017] The present invention was devised in view of the current state of such prior art. An object of the present invention is to provide a polyester elastomer resin composition derived from biomass resources that can retain the properties of polyester elastomers derived from fossil fuel resources even when the proportion of raw materials derived from biomass resources in the polyester elastomer is increased. Specifically, a first object is to provide a polyester elastomer resin composition derived from biomass resources that can retain the excellent mechanical properties, storage stability, elongation after moist heat treatment, and flame retardancy possessed by polyester elastomers derived from fossil fuel resources. A second object is to provide a polyester elastomer resin composition derived from biomass resources that combines the excellent strength, elastic properties, elongation recovery properties, and filament processability possessed by polyester elastomers derived from fossil fuel resources, as well as a monofilament, a composite monofilament, and a highly elastic fabric containing the same. A third object is to provide a resin composition that can retain the excellent mechanical properties, storage stability, and high-precision moldability possessed by polyester elastomers derived from fossil fuel resources, and is excellent in foam moldability, as well as a foamed molded article obtained from the resin composition, which is lightweight, excellent in compression recovery, and has a high impact resilience. [Means for Solving the Problem]

[0018] As a result of diligent research to achieve the above objective, the inventors have discovered that conventional biomass resource-derived polyesters are more susceptible to oxidative degradation than those derived from fossil fuel resources, and that this is a factor preventing them from maintaining the excellent properties of fossil fuel resource-derived polyesters in terms of storage stability, water aging resistance, and heat aging resistance. Furthermore, the inventors have discovered that this oxidative degradation is likely to occur during the melt-kneading process when preparing biomass resource-derived polyester elastomer resin compositions. Furthermore, we have found that in a polyester elastomer resin composition containing a highly bio-based biomass resource-derived polyester elastomer and a heat stabilizer, by reducing the content of oligomers with a number average molecular weight of less than 1000 in the biomass resource-derived polyester elastomer to a specific amount or less, or by controlling the 3% weight loss temperature when the polyester elastomer resin composition is heated from room temperature to 450°C at 10°C / min to a specific range, and then controlling the chemiluminescence emission amount of the polyester elastomer resin composition to a specific amount or less, we can provide a biomass resource-derived polyester elastomer resin composition that retains the excellent mechanical properties, storage stability, and elongation after humid heat treatment that are present in fossil fuel resource-derived polyester elastomers. We have also found that such a polyester elastomer resin composition does not suffer from problems such as a decrease in mechanical properties, and retains the excellent flame retardancy that is present in fossil fuel resource-derived polyester elastomers, even when it contains a flame retardant.

[0019] Furthermore, the inventors have discovered that in a polyester elastomer resin composition containing a highly bio-based polyester elastomer derived from biomass resources and a heat stabilizer, by controlling the melting point and Vicat softening point of the polyester elastomer resin composition to satisfy a specific relationship, and further controlling the chemiluminescence emission amount of the polyester elastomer resin composition to be below a specific value, it is possible to provide a biomass resource-derived polyester elastomer resin composition that combines the excellent strength, elastic properties, stretch recovery properties, and filament processability of a fossil fuel resource-derived polyester elastomer.

[0020] Furthermore, the inventors have found that by adjusting the manufacturing conditions so that the MFR and chemiluminescence emission amount of the biomass resource-derived polyester elastomer resin composition are within a predetermined range, the biomass resource-derived polyester elastomer resin composition can maintain excellent mechanical properties, storage stability, and high-precision moldability. They have also found that the foamed molded articles obtained from this resin composition have a high rebound modulus, a low 50% fixed position cyclic compression residual strain, and a uniform cell diameter.

[0021] In other words, the present invention was completed based on the above findings and consists of the following (1) to (36). (1) A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the oligomer content of the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000 is 2.5% by weight or less, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 A polyester elastomer resin composition characterized by having a count of less than or equal to a certain value. (2) A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the 3% weight loss temperature when the polyester elastomer resin composition is heated from room temperature to 450°C at 10°C / min is 300°C or higher, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 A polyester elastomer resin composition characterized by having a count of less than or equal to a certain value. (3) The polyester elastomer resin composition according to (1) or (2), characterized in that the polyester elastomer resin composition further contains a thickening agent. (4) The polyester elastomer resin composition according to (1) or (2), characterized in that the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN. (5) The polyester elastomer resin composition according to (1) or (2), characterized in that the polyester elastomer resin composition further contains a hydrolysis inhibitor. (6) A hose obtained by extruding the polyester elastomer resin composition described in (1) or (2). (7) A film obtained by extruding the polyester elastomer resin composition described in (1) or (2). (8) A wire and cable covering material obtained by extruding the polyester elastomer resin composition described in (1) or (2). (9) The polyester elastomer resin composition according to (1) or (2), characterized in that the polyester elastomer resin composition further contains a flame retardant. (10) The polyester elastomer resin composition according to (9), characterized in that the flame retardant content is 5 parts by mass or more per 100 parts by mass of polyester elastomer. (11) The polyester elastomer resin composition according to (10), characterized in that the specific gravity of the polyester elastomer resin composition is 1.20 or more, and the tensile elongation at break of the polyester elastomer resin composition is 200% or more. (12) The polyester elastomer resin composition according to (11), characterized in that the difference (ΔMFR: MFR45-MFR5) between the MFR value after 45 minutes of adding the polyester elastomer resin composition (MFR45) and the MFR value after 5 minutes of adding the polyester elastomer resin composition (MFR5), measured in accordance with the test method (Method A) described in JIS K7210 at the melting point of the polyester elastomer + 20°C and 2160g, is 25 or less. (13) The polyester elastomer resin composition according to (11), 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. (14) The polyester elastomer resin composition according to (11), characterized in that the flame retardancy rating measured by UL94 is V-2, V-1, or V-0. A wire and cable covering material using the polyester elastomer resin composition described in (15)(11). Electronic component using the polyester elastomer resin composition described in (16)(11). (17) A monofilament using the polyester elastomer resin composition described in (11). (18) A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy 10°C ≤ Tm - VST ≤ 43°C, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 A polyester elastomer resin composition characterized by having a count of less than or equal to a certain value. (19) The polyester elastomer resin composition according to (18), characterized in that the number average molecular weight (Mn) of the polyester elastomer resin composition is 9,000 or more. (20) The polyester elastomer resin composition according to (18), characterized in that when the weight-average molecular weight (Mw) of the polyester elastomer resin composition is defined as Mw / Mn ≤ 5.0. (21) The polyester elastomer resin composition according to (18), characterized by containing a polyester elastomer having a hard segment / soft segment mass ratio of 40 / 60 to 80 / 20. A monofilament using the polyester elastomer resin composition described in any of (22), (18), to (21). (23) The monofilament according to (22), characterized in that the elongation at break is 80% or more, the tensile strength is 1.2 cN / dtex or more, the elongation recovery rate after 30% elongation at 23°C is 90% or more, and the elongation recovery rate after 20% elongation at 80°C is 80% or more. A woven fabric, knitted fabric, or nonwoven fabric characterized by containing the monofilament described in (24)(22) as a constituent material. (25) A composite monofilament having a core-sheath structure using a polyester elastomer resin composition according to any one of (18) to (21) of two components with different melting points, characterized in that the core is formed from a high-melting-point component and the sheath from a low-melting-point component. A highly elastic fabric made of a woven, knitted, or nonwoven fabric containing the composite monofilament described in (26)(25) as a constituent material, characterized in that the low melting point component of the composite filament is fused at the monofilament intersection. (27) A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the MFR value of the polyester elastomer resin composition at a load of 2.16 kg measured in accordance with the flow test method for thermoplastics specified in JIS K7210 is 0.5-20 g / 10 min (measurement temperature: melting point + 20°C), and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 A polyester elastomer resin composition for foam molding, characterized by having a count of less than or equal to a certain value. (28) The polyester elastomer resin composition for foam molding according to (27), characterized in that the acid value of the polyester elastomer resin composition is 50 eq / ton or less. A polyester elastomer foam molded article obtained from the polyester elastomer resin composition described in (29), (27), or (28), characterized in that the rebound modulus of the polyester elastomer foam molded article is 60% or more. A polyester elastomer foam molded article obtained from the polyester elastomer resin composition described in (30), (27), or (28), characterized in that the 50% constant displacement cyclic compression residual strain of the polyester elastomer foam molded article is 10% or less. A polyester elastomer foam molded article obtained from the polyester elastomer resin composition described in (31), (27), or (28), characterized in that the volume average cell diameter Dv and the number average cell diameter Dn of the polyester elastomer foam molded article satisfy Dv / Dn ≤ 4. A footwear component characterized by comprising the polyester elastomer foam molded body described in (32)(29). (33) A polyester elastomer resin composition according to any one of (1), (2), (18), or (27), wherein the biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of a polyester comprising 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 biomass resources. (34) The polyester elastomer resin composition according to (33), characterized in that the aliphatic polyether derived from biomass resources in the biomass resource-derived polyester elastomer is polytetramethylene ether glycol. (35) The polyester elastomer resin composition according to (33), characterized in that the reduced viscosity of the biomass resource-derived polyester elastomer is 1.2 dl / g or more. A method for producing a polyester elastomer resin composition according to any one of (36)(1), (2), (18), or (27), wherein the method comprises melt-kneading a biomass resource-derived polyester elastomer and a heat stabilizer using an extruder, and the conditions for melt-kneading satisfy at least one of the following (i) to (v): (i) The melting temperature of the resin composition during melt mixing is 100 to 300°C; (ii) The screw rotation speed of the extruder during melt mixing is 60 to 300 rpm; (iii) Vacuum degassing is performed in the molten kneading section after plasticization is complete; (iv) The ratio of the screw length L (mm) to the diameter D (mm) of the extruder is 20 ≤ (L / D) ≤ 70; (v) The discharge rate Q of the extruder is 30 to 500 kg / hr. [Effects of the Invention]

[0022] The biomass resource-derived polyester elastomer resin composition of the present invention can maintain the excellent mechanical properties, storage stability, elongation retention rate after moisture heat treatment, extrusion moldability, water aging resistance, strength, elastic properties, elongation recovery properties, filament processability, high-precision moldability, and flame retardancy of fossil fuel resource-derived polyester elastomers, even when the proportion of biomass resource-derived raw materials is increased. Therefore, the polyester elastomer resin composition of the present invention can be suitably used for extruded hoses, films, wire coatings, tubes, cables, etc. Furthermore, the polyester elastomer resin composition of the present invention can be used as a substitute for fossil fuel-derived polyester elastomers, for example, as a reinforcing material for various membrane materials, nets and meshes, seat materials for chairs used for office and vehicle use, high-elasticity composite monofilaments, and high-elasticity fabrics using the same. In addition, the polyester elastomer resin composition of the present invention can be suitably used, for example, as a cushioning functional member for sporting goods, such as shoe soles, preferably insoles or midsoles, golf balls, mattresses, chairs, beds, etc. Therefore, the present invention can make a significant contribution to solving global environmental problems such as the depletion of fossil fuel resources. [Modes for carrying out the invention]

[0023] The polyester elastomer resin composition of the present invention can be broadly described in the following three forms.

[0024] A first aspect of the present invention is a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 100%, the oligomer content in the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000 is 2.5% by weight or less, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It is characterized by being less than or equal to the count.

[0025] This first embodiment can also be expressed as follows: The first embodiment is a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the 3% weight loss temperature when the polyester elastomer resin composition is heated from room temperature to 450°C at 10°C / min is 300°C or higher, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It can be characterized as being less than or equal to the count.

[0026] Furthermore, in the first embodiment of the present invention, it is also conceivable that the polyester elastomer resin composition of the present invention further contains a flame retardant.

[0027] A second aspect of the present invention is a polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 100%, the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy 10°C ≤ Tm - VST ≤ 43°C, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It is characterized by being less than or equal to the count.

[0028] A third aspect of the present invention is a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 100%, the MFR value of the polyester elastomer resin composition at a load of 2.16 kg measured in accordance with the flow test method for thermoplastics specified in JIS K7210 is 0.5 to 20 g / 10 min (measurement temperature: melting point + 20°C), and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It is characterized by being less than or equal to the count.

[0029] As described above, the first, second, and third embodiments of the present invention share common features in the composition of the polyester elastomer resin composition, the bio-basedness of the polyester elastomer resin composition, and the chemiluminescence emission amount of the polyester elastomer resin composition. Therefore, these common features will be explained, followed by a description of the unique features of each embodiment.

[0030] (Composition of polyester elastomer resin composition) The polyester elastomer resin composition of the present invention contains a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer.

[0031] In the present invention, it is preferable that the biomass resource-derived polyester elastomer used in its raw materials contains an aliphatic polyether such as polytetramethylene ether glycol, a dimer acid, and / or an aliphatic or alicyclic diol such as 1,4-butanediol, all of which are derived from biomass resources. Specifically, it is preferable that the biomass resource-derived polyester elastomer used in the resin composition of the present invention satisfies any one of the following requirements (i), (ii), or (iii). (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising 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 is derived from fossil fuel resources, and the aliphatic and / or alicyclic diol and the aliphatic polyether are derived from biomass resources. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment comprising a dimer acid, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the dimer acid is derived from biomass resources. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and 1,4-butanediol is bonded to a soft segment made of an aliphatic polyether, wherein the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and the aliphatic polyether are derived from biomass resources.

[0032] As aromatic dicarboxylic acids constituting the hard segment polyester, ordinary aromatic dicarboxylic acids are widely used, and the main aromatic dicarboxylic acid is preferably terephthalic acid or naphthalenedicarboxylic acid (among the 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, even more preferably 90 mol% or more, and may be 100 mol% of the total dicarboxylic acids constituting the hard segment polyester. Examples of dicarboxylic acid components other than terephthalic acid and naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as diphenyl dicarboxylic acid, isophthalic acid, and 5-sodium sulfisoisophthalic acid, alicyclic dicarboxylic acids such as cyclohexane dicarboxylic 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 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 component, more preferably 20 mol% or less, even more preferably 10 mol% or less, and may even be 0 mol%. When these dicarboxylic acids are used as raw materials for polyester elastomers, esters of the dicarboxylic acids may also be used. For example, terephthalic acid and dimethyl terephthalate can be used as raw materials.

[0033] Furthermore, while there are no particular limitations, the aliphatic or alicyclic diols that constitute the polyester of the hard segment are generally used and are not limited to any particular aliphatic or alicyclic diols, but are preferably alkylene glycols having 2 to 8 carbon atoms. Specifically, examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. Among these, ethylene glycol and 1,4-butanediol are preferred.

[0034] As for the components constituting the polyester of the hard segment described above, those consisting of 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.

[0035] Furthermore, when an aromatic polyester suitable for constituting the hard segment of a polyester elastomer is manufactured in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained according to the usual polyester manufacturing method. Preferably, such a polyester has a number average molecular weight of 10,000 to 40,000.

[0036] The aliphatic polyether constituting the soft segment of the polyester elastomer is preferably a glycol compound because it bonds with the polyester of the hard segment. Specifically, examples include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, polytetramethylene ether glycol, polytrimethylene ether glycol, poly(hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide adducts of poly(propylene oxide) glycol, and copolymers of ethylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol and ethylene oxide adducts of poly(propylene oxide) glycol are preferred from the viewpoint of elastic properties.

[0037] In the present invention, it is preferable to use aliphatic polyether derived from biomass resources, particularly polytetramethylene ether glycol (PTMG) derived from biomass resources, as the aliphatic polyether that constitutes the soft segment. Such PTMG can be obtained commercially and used, and for example, BioPTMG1000 and BioPTMG2000 manufactured by Mitsubishi Chemical are preferably used.

[0038] The polyester elastomer is preferably a copolymer mainly composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol. In the dicarboxylic acid component constituting the polyester elastomer, terephthalic acid 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. In the glycol component 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.

[0039] 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 elastomer properties. On the other hand, if the number-average molecular weight exceeds the above range, the compatibility with hard segment components decreases, and copolymerization into block-like structures may become difficult.

[0040] In this 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 the butylene terephthalate unit (the condensation unit of terephthalic acid and 1,4-butanediol), and the mass of the soft segment is the mass of the polytetramethylene ether glycol (PTMG).

[0041] 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 too low (the amount of PTMG is too high), it may not be possible to obtain a polyester elastomer that satisfies the functions of heat aging resistance and moldability (crystallinity). Conversely, if the amount of hard segments is too high (the amount of PTMG is too low), the compatibility between the hard segment components and the soft segment components decreases, making it difficult to copolymerize them into blocks.

[0042] Furthermore, the melting point of the polyester elastomer is preferably between 150 and 230°C. If the melting point is below 150°C, it may not be possible to obtain a polyester elastomer that satisfies the functions of heat aging resistance and moldability (crystallinity). Conversely, if the melting point is above 230°C, it contains a large amount of hard segments, which increases the glass transition temperature (Tg), and may not satisfy the functions of rebound elasticity, flexibility, and low-temperature mechanical properties of the polyester elastomer.

[0043] In the present invention, in order to exhibit long-term durability (heat aging resistance, water resistance) as a polyester elastomer, the reduced viscosity is preferably 1.2 dl / g or higher, more preferably 1.4 dl / g or higher, and even more preferably 1.8 dl / g or higher. If the reduced viscosity (ηsp / c) is low, the molecular weight is small, and it may not be possible to obtain a polyester elastomer that satisfies the function of long-term durability (heat aging resistance, water resistance).

[0044] In the present invention, the glass transition temperature at which the polyester elastomer exhibits its functions of rebound elasticity, flexibility, and low-temperature mechanical properties is preferably -70 to 20°C, more preferably -65 to 20°C. If the glass transition temperature is too high, it may not be possible to obtain a polyester elastomer that satisfies the functions of rebound elasticity, flexibility, and low-temperature mechanical properties.

[0045] In the polyester elastomer of the present invention, in order to obtain a good appearance, Co-b is preferably 10 or less, more preferably 7 or less, and still more preferably 4 or less. The value of Co-b varies depending on impurities in raw materials derived from biomass resources and polymerization conditions. When Co-b is large, the prepared pellets turn yellow and greatly impair the appearance of molded articles, so there is a possibility that a satisfactory product cannot be obtained.

[0046] As a method for determining the composition and composition ratio of the polyester elastomer of the present invention, measurement is performed by dissolving a sample in a solvent such as deuterated chloroform 1 Calculation can also be performed from the proton integral ratio of H-NMR.

[0047] As a method for producing the polyester elastomer, any known method can be employed. For example, any of melt polymerization, solution polymerization, solid phase polymerization and the like can be appropriately used. In the case of the melt polymerization method, either a transesterification method or a direct polymerization method may be used. Examples thereof include a method in which a dicarboxylic acid component and a diol component are reacted by a transesterification method, a direct esterification method or the like to obtain a prepolymer, followed by a polycondensation reaction under reduced pressure. In this case, a catalyst for transesterification reaction or esterification reaction, and a polycondensation reaction catalyst can be appropriately used. Further, chain extension may be performed with an isocyanate compound, an epoxy compound or the like after polymerization. Furthermore, when solid phase polymerization is used, melt tension can be improved in the polymerization step.

[0048] To produce the polyester elastomer of the present invention, it is preferable to lengthen the polycondensation time compared to conventional methods. For example, in the polycondensation of a polyester elastomer using butylene terephthalate units as the hard segment component and polytetramethylene ether glycol as the soft segment component, the polycondensation time in the production of polyester elastomers is usually about 50 to 90 minutes, but in the present invention, 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. The polycondensation temperature in the production of polyester elastomers is usually about 235 to 260°C, but in the present invention, the polycondensation temperature is preferably 235 to 255°C, more preferably 240 to 250°C. If the polycondensation time is shorter than the above lower limit, or if the polycondensation temperature is lower than the above lower limit, the polymerization reaction may not proceed smoothly, which may result in a higher oligomer content or an increase in the acid value of the system. Furthermore, if the reduced viscosity of the polyester elastomer does not increase, the elongation at break and tensile strength at break may not satisfy the function of a polyester elastomer, and oxidative degradation may progress easily, worsening the retention stability. Conversely, if the polycondensation time is longer than the above upper limit, or if the polycondensation temperature is higher than the above upper limit, thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and promoting the formation of oligomers and gelation. In addition, oxidative degradation will progress more easily. The pressure is gradually reduced from the pressure of the transesterification reaction, but it is preferable that the final pressure be 0.1 to 3 Torr, and more preferably 0.04 to 0.2 kPa. If this pressure exceeds the above upper limit, the reactivity will decrease, the reaction time will be longer, and thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and promoting the formation of oligomers and gelation. In addition, oxidative degradation will progress more easily. On the other hand, if the pressure is too low, there is a risk of compositional shifts due to excessive volatilization and distillation of monomers, or delays in the polymerization reaction due to a decrease in intermolecular collisions. Note that the above polycondensation conditions need to be adjusted as appropriate depending on the constituent components.

[0049] The polyester elastomer resin composition of the present invention contains a heat stabilizer as an essential component in addition to the polyester elastomer described above.

[0050] 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 antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. The amount of heat stabilizer 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. Too little heat stabilizer may result in insufficient prevention of thermal oxidative decomposition, while too much may lead to a decrease in mechanical properties.

[0051] Examples of hindered phenol 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)butyrate] glycol ester, tripheno 1,2'-ethylidenebis(4,6-di-t-butylphenol), N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxamidebis[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)iso Examples include cyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic ahydrotriester with-1,3,5-tris(2-hydroxyethyl)-S-triazine-2,4,6(1H,3H,5H), N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnaamide), and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0052] Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodiuropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, dilaurylthiodipropionate, dioctadecyl sulfide, and pentaerythryl-tetra(β-lauryl-thiopropionate) ester.

[0053] Phosphorus-based antioxidants include tris(mixed, mono, and dinolylphenyl) 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, and tetrakis(2,4-di Examples include -t-butylphenyl)-4,4'-biphenylene phosphanite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylenediphosphonite, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, trioctyl phosphite, toridedecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, and toridedecyltrithiophosphite.

[0054] Examples of amine-based antioxidants include amines and their derivatives such as N,N-diphenylethylenediamine, N,N-diphenylacetamidine, N,N-diphenylfluamidine, 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-dimethylpentyl)-p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, and 4,4'-bis(4-α,α-dimethylbenzyl)diphenylamine, as well as reaction products of amines and aldehydes, and reaction products of amines and ketones.

[0055] (Chemiluminescence emission level) The chemiluminescence emission amount of the polyester elastomer resin composition of the present invention is 4.0 × 10⁻⁶ 5 It is less than or equal to the count. Preferably 3.5 × 10 5 Count less than or equal to, more preferably 3.0 × 10 5 count or less, more preferably 2.5 × 10 5 The value is below count. If it is within the above range, it is less susceptible to oxidative degradation, and a significant decrease in initial or over time mechanical properties and retention stability can be suppressed. By measuring the amount of chemiluminescence emission, it is possible to measure the weak emission that occurs when peroxides or peroxide radicals are generated in the resin composition, allowing for highly sensitive detection of oxidation reactions in the resin composition at an early stage, and enabling the degree of oxidative degradation to be understood even before any change occurs in the mechanical properties of the resin composition.

[0056] The chemiluminescence emission amount of the polyester elastomer resin composition of the present invention is the value obtained by holding a test piece of the resin composition in an oxygen atmosphere with a flow rate of 100 ml / min at 160°C and measuring the cumulative chemiluminescence emission amount every second from the start of measurement to 300 seconds.

[0057] The measurement temperature for chemiluminescence emission is preferably below the melting point of the polyester elastomer resin composition being measured. In this invention, 160°C is used to satisfy this condition. If the measurement temperature is above the melting point of the material being measured, the polyester elastomer resin composition may melt during measurement, making measurement difficult.

[0058] The shape of the test specimen of the resin composition is not particularly limited, but it is preferable that the surface area and thickness are the same. In this invention, the test specimen was measured in a shape of 10 mm × 10 mm × 2 mm.

[0059] In order to reduce the amount of chemiluminescence emission as in the present invention, it is preferable to employ a method to suppress oxidative degradation of the resin composition in addition to controlling the time and temperature of polycondensation as described above. For example, when melting and kneading each component of the resin composition, it is advisable to avoid kneading conditions of high temperature, long duration, and high shear, and to avoid the presence of oxygen to make it difficult for oxidation reactions to proceed. In particular, optimizing the melting and kneading conditions of each component of the resin composition is important.

[0060] Resin compositions made from biomass-derived polyester elastomers tend to exhibit higher chemiluminescence emission compared to those made from fossil fuel-derived polyester elastomers. This is thought to be because biomass-derived polyester elastomers are more prone to molecular chain cleavage at the polymer stage and contain higher levels of peroxides. Therefore, even if biomass-derived polyester elastomers have the same reducing viscosity as those derived from fossil fuels at the polymer stage, oxidative degradation progresses more rapidly during the process of melt-kneading the polymer with additives to form a resin composition, leading to a decrease in molecular weight and a decline in mechanical properties and melt tension.

[0061] Similarly, even if a biomass-derived polyester elastomer has the same mechanical properties and melt tension as one derived from fossil fuels at the resin composition stage, the biomass-derived polyester elastomer resin composition tends to emit more chemiluminescence than one derived from fossil fuels. This is also thought to be because the molecular chains of the biomass-derived polyester elastomer resin composition are more easily cleaved at the polymer stage, or because it contains a larger amount of peroxides. Therefore, even if a biomass-derived polyester elastomer resin composition has the same initial melt tension and mechanical properties as one derived from fossil fuels, oxidative degradation tends to decrease more over time, and the rate of decrease tends to be larger.

[0062] The amount of chemiluminescence emitted by the polyester elastomer resin composition of the present invention can be efficiently suppressed by appropriately combining the melt kneading conditions shown below in the manufacturing method.

[0063] The method for producing the polyester elastomer resin composition of the present invention is not particularly limited and can be produced by melt-kneading each component using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, roll, etc., as known to those skilled in the art. However, when using a single-screw or twin-screw extruder, it is preferable to control the resin pressure in the extruder's plasticizing section by appropriately selecting the extruder barrel temperature and screw configuration. When melt-kneading each of the above components, it is important to allow the molten components to coexist with the molten polymer phase in the polymer plasticizing region, and to increase the polymer viscosity as the matrix phase so that the molten components are uniformly melted into the polymer phase by shear stress, while controlling internal heat generation to suppress polymer degradation and side reactions, thereby suppressing the amount of chemiluminescence emission. If it is desired to suppress thermal history, it is preferable to select a single-screw extruder. The resin pressure is preferably around 0.1 to 1 MPa.

[0064] When using a twin-screw extruder, the screws of the twin-screw extruder are used in appropriate combinations of full-flight screws, reverse full-flight screws, orthogonal kneading discs, progressive kneading discs, and reverse kneading discs. In the present invention, in order to prevent excessive shearing and localized heat generation and suppress the amount of chemiluminescence emission, it is preferable to incorporate a progressive kneading disc in the screw configuration of the plasticizing region and to minimize the number of kneading discs. Furthermore, by incorporating a deep flight screw, the resin is spread thinly and the surface area is increased, thereby improving the kneading efficiency. When designing the screws, care must be taken to prevent localized heating and stagnation.

[0065] Furthermore, the melting temperature of the resin composition during melt mixing is preferably 100 to 300°C, and more preferably 100 to 280°C. If the melting temperature is too low, melting will be insufficient, and a large amount of unmelted gel is likely to occur. Conversely, if the resin temperature is too high, the resin composition is more susceptible to thermal and oxidative degradation, resulting in a higher amount of chemiluminescence emission. Generally, the resin temperature increases as it approaches the die outlet of the extruder, but from the viewpoint of suppressing thermal and oxidative degradation, it is preferable that the resin temperature at the die outlet be 50°C or less above the melting point.

[0066] While there are no particular limitations on the method for controlling the resin temperature as described above, it is effective to set the barrel temperature lower from the kneading and conveying zone after mixing and plasticization in the extruder to the die outlet.

[0067] During melt mixing, it is preferable to perform vacuum degassing in the melt mixing section after plasticization is complete, in order to remove substances that cause an increase in chemiluminescence emission, such as moisture and volatile impurities introduced into the raw materials. In particular, it is preferable to provide two or more degassing ports to remove (i) moisture and low-boiling point components, and (ii) decomposition gases and high-boiling point components.

[0068] Furthermore, it is preferable that the ratio L / D, which is the ratio of the screw length L (mm) to the screw diameter D (mm), satisfies the relationship 20 ≤ (L / D) ≤ 70. If there are no other operational problems, a smaller L / D is preferable from the viewpoint of speeding up the resin transport and preventing the resin from being subjected to thermal history. However, if the above upper limit is exceeded, the amount of chemiluminescence emission tends to increase due to thermal degradation of the polymer or, if a flame retardant is contained, its thermal decomposition, which is undesirable.

[0069] The screw rotation speed during melt mixing is preferably 60 to 300 rpm, and more preferably 100 to 200 rpm. If the screw rotation speed is too low, the components tend not to melt and react uniformly, and the residence time of the resin may be extended, potentially leading to thermal degradation. Conversely, if the rotation speed is too high, shear heating may accelerate molecular severance and oxidative degradation.

[0070] Furthermore, the discharge rate Q is preferably 30 to 500 kg / hr, and more preferably 60 to 300 kg / hr. If the discharge rate is too low, the resin filling rate in the extruder decreases, and the mixing tends to become uneven. Conversely, if the discharge rate is too high, the resin filling rate in the extruder becomes too high, and the mixing tends to become uneven. In particular, it is preferable to keep the resin filling rate in the degassing zone low in order to remove substances that cause an increase in chemiluminescence emission, such as moisture and volatile impurities.

[0071] Furthermore, in the manufacturing process of the polyester elastomer resin composition of the present invention, moisture, contained oligomers and impurities, particularly sulfur compounds, may act as nuclei for reactions that generate peroxide radicals. Therefore, it is preferable to reduce these beforehand by vacuum drying or the like.

[0072] (Bio-basedness of polyester elastomer resin composition) The biobase of the polyester elastomer of the present invention, expressed as the biobase of the resin composition including components such as heat stabilizers, is 20-100%, preferably 20-99.9%, more preferably 20-99%, even more preferably 20-85%, and particularly preferably 20-80%. Conventionally, because biomass resource-derived raw materials contain impurities that could not be completely removed in the purification process, increasing the proportion of biomass raw materials to increase the biobase leads to an increase in the amount of impurities, which inhibits the reaction, prevents the reduction viscosity from increasing, lengthens the polymerization time, and causes discoloration. Therefore, it has been difficult to obtain a biomass resource-derived polyester elastomer that can prevent discoloration without reducing production efficiency, while maintaining excellent flexibility and low-temperature mechanical properties. In this invention, even when raw materials derived from biomass resources are used as polymerization raw materials for polyester elastomers, by employing appropriate reaction time and temperature for polycondensation, it is possible to obtain a biomass resource-derived polyester elastomer that exhibits slow oxidative degradation and retains the excellent properties of fossil fuel resource-derived polyester elastomers.

[0073] Next, the features of the first, second, and third embodiments of the polyester elastomer resin composition of the present invention will be described, respectively.

[0074] (First aspect) A first aspect of the polyester elastomer resin composition of the present invention is a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, characterized in that the bio-basedness of the polyester elastomer resin composition is 20 to 100%, the oligomer content of the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000 is 2.5% by weight or less, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁵ counts or less.

[0075] In the first embodiment of the polyester elastomer resin composition of the present invention, a unique feature is that the oligomer content of the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000 is 2.5% by weight or less. The oligomer content of the biomass resource-derived polyester elastomer with a molecular weight of less than 1000 varies depending on impurities in the biomass resource-derived raw material and polymerization conditions. In the present invention, the oligomer content is 2.5% by weight or less. Preferably it is 2.4% by weight or less, more preferably 2.3% by weight or less, and even more preferably 2.2% by weight or less. If the oligomer content is high, the melt tension of the polyester elastomer composition will not rise sufficiently in the compound during the manufacture of the composition, and high-precision moldability cannot be obtained. In addition, when a thickener is added, gel is more likely to occur, deteriorating the appearance and properties of the molded product. Furthermore, the thermal stability and water resistance of the molten resin deteriorate, and the fluidity differs between the start and end of molding, impairing stable productivity. Moreover, even in the molded product, it may not be possible to obtain one that satisfies the functions of rebound elasticity, flexibility, and low-temperature mechanical properties.

[0076] Furthermore, a first embodiment of the polyester elastomer resin composition of the present invention may be characterized in that, instead of having a feature relating to the oligomer content of fewer than 1000 number average molecular weight in the biomass resource-derived polyester elastomer, 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.

[0077] If the 3% weight loss temperature is below 300°C, the retention stability and 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 decompose faster than fossil fuel-derived components, and tend to accelerate the weight loss of the polyester elastomer composition. In particular, the larger the molecular weight of the aliphatic polyol and the higher its proportion in the polyester elastomer, the faster the weight loss tends to be.

[0078] Here, the 3% weight loss temperature was measured using a differential thermal and thermogravimetric simultaneous measurement device (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 under a nitrogen atmosphere with a flow rate of 20 ml / min. The temperature at which decomposition at high temperatures progresses and the weight becomes 97% of the initial weight is defined as the 3% weight loss temperature.

[0079] The polyester elastomer resin composition of the present invention may optionally further contain a thickener and / or a hydrolysis inhibitor.

[0080] The thickener is a reactive compound having a functional group that can react with the terminal groups of the polyester elastomer, and a functional group that can react with the hydroxyl groups or carboxyl groups of the polyester elastomer. Preferably, the reactive functional group is at least one selected from epoxy groups (glycidyl groups), acid anhydride groups, carbodiimide groups, and isocyanate groups, and the molecule contains two or more of these functional groups. The epoxy group (glycidyl group) is more preferred.

[0081] When the thickener is a compound having epoxy groups, specific examples of polyfunctional epoxy compounds having two or more epoxy groups include 1,6-dihydroxynaphthalenediglycidyl ether and 1,3-bis(oxyranylmethoxy)benzene, which have 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 have three epoxy groups; and 1-chloro-2,3-epoxypropane-formaldehyde-2,7-naphthalenediol polycondensate and pentaerythritol polyglycidyl ether, which have four epoxy groups. Among these, polyfunctional epoxy compounds with heat resistance in their skeleton are preferred. Particularly preferred are bifunctional or tetrafunctional epoxy compounds with a naphthalene structure as the skeleton, or trifunctional epoxy compounds with a triazine structure as the skeleton. 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, bifunctional or trifunctional epoxy compounds are preferred.

[0082] When a thickening agent is added, the 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 thickening agent is too little, the target molecular chain extension effect will be insufficient, and if it is too much, the thickening effect will be excessive, which tends to adversely affect moldability and the mechanical properties of the molded article. If the thickening agent is an epoxy compound, if it is too much, the cohesive hardening of the epoxy compound may cause unevenness on the surface of the molded article. If the thickening agent is a carbodiimide compound, if it is too much, the basicity of the polycarbodiimide compound may cause hydrolysis of the thermoplastic polyester elastomer, which tends to affect the mechanical properties.

[0083] Hydrolysis inhibitors are added to improve hydrolysis resistance and enhance bending fatigue resistance through chain extension. For example, compounds having functional groups that can react with the terminal functional groups of the polyester elastomer can be used as hydrolysis inhibitors. The terminal functional groups of the polyester elastomer are carboxyl groups and / or hydroxyl groups. Examples of functional groups that can react with the terminal functional groups of the polyester elastomer include carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, carbodiimide groups, and oxazoline groups. Of these, epoxy groups or carbodiimide groups are preferred due to their reactivity with the melt viscosity change during melt retention and their interaction with the terminal functional groups of the polyester elastomer. The hydrolysis inhibitor is preferably an epoxy compound and / or a carbodiimide compound.

[0084] Carbodiimide compounds are compounds that have at least one (-N=C=N-) carbodiimide group in their molecule and can react with the terminal groups of polyester elastomer (A).

[0085] Examples of carbodiimide compounds 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, and di-3,4-dichlorophenylcarbodiimide. Lubodiimide, 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 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 dicarbodimide 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, N,N'-di-2,4,6-triisobutylphenylcarbodiimide, poly(1,6-hexamethylenecarb) Examples of polycarbodiimides include 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), and poly(triisopropylphenylenecarbodiimide). Among these, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, and polycarbodiimide are preferred, and more preferably 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 polycarbodiimides include 4'-diphenylmethanecarbodiimide, poly(naphthylenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(toluylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide). Of these, polycarbodiimides are preferred from the viewpoint of improving heat aging resistance and hydrolysis resistance, and reactivity with acid ends, with poly(1,4-cyclohexylenecarbodiimide) and poly(triisopropylphenylenecarbodiimide) being particularly preferred.

[0086] When a hydrolysis inhibitor is included, 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 it is too large, a decrease in flame retardancy or a decrease in mechanical properties due to foreign matter effects may occur. However, if a high molecular weight polyester elastomer that does not require chain extension is used, or if a polyester elastomer with a sufficiently low terminal acid value is used, the addition of a hydrolysis inhibitor is not necessary.

[0087] The polyester elastomer resin composition of the present invention may further contain a flame retardant. When a flame retardant is included, halogen-based flame retardants and non-halogen-based flame retardants can be used, and these may be used alone or in combination. In addition, a flame retardant aid may be used as needed. Examples of flame retardants include triazine compounds / or derivatives thereof, phosphorus compounds, silicon-based flame retardants, metal hydroxides, metal borates, and bromine compounds. The content ratio 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 biomass resource-derived polyester elastomer. If the content ratio is too low, the flame retardant effect will be insufficient, and if it is too high, a decrease in physical properties may occur.

[0088] 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 ratio 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, per 100 parts by mass of polyester elastomer.

[0089] Phosphorus compounds are broadly classified into organophosphorus compounds and inorganic phosphorus compounds. Organophosphorus compounds include phosphates, phosphonates, phosphinates, and phosphites, specifically trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyldiphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, and bis(1,3-phenylenediphenyl) phosphate. Among these, metal phosphinate salts are preferred from the viewpoint of flame retardancy, and aluminum phosphinate salts are particularly preferred. Inorganic phosphorus compounds include red phosphorus compounds and inorganic phosphate compounds such as (poly)ammonium phosphate, (poly)melamine phosphate, and (poly)piperazine phosphate. The content ratio of these 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, per 100 parts by mass of polyester elastomer.

[0090] Brominated 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, ethylenebispentabromodiphenyl, tris(tribromophenoxy)triazine, bis(dibromopropyl)tetrabromobisphenol A, bis(dibromopropyl Examples include tetrabromobisphenol S, brominated polyphenylene ethers (including poly(di)bromophenylene ethers, etc.), brominated polystyrene (including polydibromostyrene, polytribromostyrene, cross-linked brominated polystyrene, etc.), brominated cross-linked aromatic polymers, brominated epoxy resins, brominated phenoxy resins, brominated styrene-maleic anhydride polymers, tetrabromobisphenol S, tris(tribromoneopentyl)phosphate, polybromotrimethylphenylindan, tris(dibromopropyl)-isocyanurate, etc. Among these, brominated polystyrene is preferred in terms of compatibility with polyester elastomers. The content ratio of these 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.

[0091] Examples of flame retardant additives 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 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 polyester elastomer.

[0092] In addition to the components mentioned above, the polyester elastomer resin composition of the present invention may contain various additives depending on the purpose. Examples of additives include known light stabilizers such as hindered amines, triazoles, benzophenones, benzoates, nickels, and salicyls; antistatic agents; lubricants; molecular modifiers such as peroxides; metal deactivators; organic and inorganic nucleating agents; neutralizing agents; antacids; antibacterial agents; fluorescent whitening agents; fillers; and organic and inorganic pigments.

[0093] The melt tension of the polyester elastomer resin composition of the present invention is preferably 1.0 to 50 cN. More preferably, this melt tension is 1.2 to 48 cN, even more preferably 1.4 to 47 cN, and particularly preferably 1.5 to 45 cN. Within this range, the extrusion moldability of tubular molded bodies, thin film moldability, thin film moldability such as films, and wire / cable coating moldability are excellent. For example, in extrusion molding of hoses, uniform tubular molded bodies without thickness variations can be obtained, and mechanical properties such as bending resistance after molding are also excellent. Also, for example, in film extrusion molding, even with a thin film thickness of 20 μm or less, a uniform thin film with high toughness and a smooth surface can be obtained. Below the above range, it is difficult to extrude a uniform film thickness in the width direction when extruding from the die, and there is a risk that a uniform thin film cannot be obtained due to pulsation, etc. Also, there is a risk that the appearance will be poor, such as when flow marks occur. On the other hand, if it is greater than the above range, it is difficult to increase the film formation speed, and there is a risk that wrinkles will occur or surface roughness will occur. The melt tension can be controlled by conventionally known methods, for example, by increasing the reducing viscosity of the polyester elastomer, using a thickening agent, or adjusting the melt kneading conditions during the production of the polyester elastomer resin composition, thereby controlling it within the aforementioned range.

[0094] Here, the melt tension was measured using a Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd., with a capillary diameter of 2.0 mm, a length of 20 mm, a cylinder diameter of 9.55 mm, a temperature of melting point + 10°C, and a cylinder extrusion speed of 20 mm / min, until the take-up speed reached 10 m / min, with a take-up acceleration of 40 m / min. 2 This is the melt tension measured at [location / device].

[0095] 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 uniform thickness is improved in the case of extrusion molding of tubular molded products such as cables and hoses. Furthermore, it exhibits excellent hydrolysis resistance.

[0096] The polyester elastomer resin composition of the present invention, when further containing a flame retardant, preferably has a tensile elongation of 200% or more, more preferably 250% or more, and even more preferably 300% or more. If the tensile elongation is below the above range, the overall mechanical properties will be reduced, such as insufficient flexibility required when used as a covering material for cables and electric wires, and water aging resistance and extrusion moldability may also be poor. Furthermore, variations in flame retardancy may occur, and the appearance of molded products tends to deteriorate. The main factors that reduce the tensile elongation of polyester elastomer compositions are the low degree of polymerization of biomass resource-derived polyester elastomers, the low reactivity due to thickeners, and the poor dispersibility of flame retardants in the polyester elastomer composition.

[0097] Furthermore, the tensile breaking strength is preferably 15 MPa, more preferably 20 MPa or higher, and even more preferably 25 MPa or higher when the mass% of the hard segments of the polyester elastomer is 50% or more by mass. When the mass% of the hard segments is less than 50%, the tensile breaking strength is preferably 8 MPa, more preferably 9 MPa or higher, and even more preferably 10 MPa or higher. For applications such as wire and cable coatings, the required tensile breaking strength varies depending on the application, but it is preferable to obtain characteristics based on the design during polymerization or compounding.

[0098] The tensile elongation at break (%) and tensile strength at break (MPa) of the polyester elastomer resin composition were measured in accordance with JIS K6251. The test specimens were prepared by injection molding a 100mm × 100mm × 2mm flat plate using an injection molding machine, after the resin, which had been dried under reduced pressure at 100°C for 5 hours, was injected at a cylinder temperature (Tm + 20°C) and a mold temperature of 30°C. A dumbbell-shaped No. 3 test specimen was then punched out from the flat plate.

[0099] Furthermore, the polyester elastomer resin composition of the present invention preferably has a tensile elongation retention rate of 60% or more after heat treatment of the above-mentioned dumbbell-shaped test piece at 140°C for 1000 hours. More preferably 70% or more, particularly preferably 75% or more, even more preferably 80% or more, and even more preferably 85% or more. This tensile elongation retention rate can be achieved in particular by setting the chemiluminescence emission amount of the polyester elastomer resin composition within the range defined in the present invention.

[0100] Furthermore, when the polyester elastomer resin composition of the present invention further contains a flame retardant, its specific gravity is 1.20 or higher, preferably 1.24 or higher, more preferably 1.30 or higher, and particularly preferably 1.35 or higher. If the specific gravity is below the above range, it is difficult to include an amount of flame retardant sufficient to ensure flame retardancy. The upper limit of the specific gravity is preferably 2.00 or lower. If the specific gravity is too high, the dispersibility of the flame retardant in the composition decreases, which may reduce mechanical properties and stable productivity during manufacturing.

[0101] 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, when measured in accordance with the thermoplastic flow test method specified in JIS K7210 at a melting point of +20°C and a load of 2.16 kg. If the MFR value deviates from the above range, extrusion molding may become impossible. Furthermore, the difference between the MFR value 45 minutes after adding the resin composition (MFR45) and the MFR value 5 minutes after adding it (MFR5) (ΔMFR: MFR45-MFR5), which is an indicator 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 ΔMFR is greater than the above range, retention stability is poor, the decrease in melt viscosity during molding is not suppressed, stable extrusion molding cannot be performed, and there is a risk of uneven thickness when molding cables or hoses. On the other hand, if the value is below the aforementioned range, the melt viscosity may increase significantly during molding, and it may become impossible to obtain stable moldability.

[0102] The method for adjusting the MFR value and ΔMFR to the above range is not particularly limited, but it is preferable to blend a predetermined amount of thickener in a specific manner. This makes it possible to control the acid value of the polyester elastomer resin composition to a predetermined range and adjust the MFR value and ΔMFR to the above range. The acid value of the polyester elastomer, the number of reactive groups of the thickener and hydrolysis inhibitor, the molecular weight and other thickening characteristics, the increase in acid value due to the decomposition reaction of the polyester elastomer by hydrolysis, and the reactivity with other additives can be appropriately adjusted. When epoxy compounds and polycarbodiimides are used in combination as thickeners and / or hydrolysis inhibitors, unreacted reactive compounds tend to remain in the resin composition. These unreacted reactive compounds react with the polyester elastomer during molding, increasing the molecular weight and contributing to a decrease in MFR and ΔMFR. On the other hand, this can reduce long-term extrusion moldability, such as by increasing the difference between the initial thickness and the final thickness.

[0103] The polyester elastomer resin composition of the present invention preferably has an elongation retention rate at break of 50% or more after moist heat treatment at 85°C, 95% RH, for 750 hours, more preferably 60% or more, and particularly preferably 70% or more. This elongation retention rate at break can be achieved in particular by setting the chemiluminescence emission amount of the polyester elastomer resin composition within the range defined in the present invention.

[0104] As described above, the polyester elastomer resin composition according to the first aspect of the present invention is configured to retain the excellent mechanical properties, storage stability, elongation retention rate after humid heat treatment, extrusion moldability, water aging resistance, and flame retardancy of polyester elastomers derived from fossil fuel resources, even though it uses polyester elastomers derived from biomass resources with a high biomass content. Therefore, it can be used in a wide range of applications, such as electronic equipment components, hoses, tubes, wire coatings, and cable coatings. In particular, the polyester elastomer resin composition of the present invention is suitable for applications such as films and sheets because of its excellent extrusion moldability. 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, blow molding, and melt spinning, and can be widely used in applications as a flame-retardant polyester elastomer.

[0105] The various molded products manufactured by the above processing method can be suitably used for a wide range of components, including automotive parts, electrical and electronic components, building materials, various containers, daily necessities, household goods, cosmetic components, sanitary products, and medical (medical and therapeutic) components.

[0106] More specifically, examples of automotive parts include interior parts such as R&P boots, suspension boots, constant velocity joint boots, dust covers, floats, gears, joint bushings, tire bumper parts, seat belt parts, emblems, slide plates, various switches, various sealing materials, knobs, levers, clips, etc.; electrical system parts including meters, connectors, automotive cable covers, wire insulation materials, corrugated tubes, and various other cable and hose parts; in-vehicle electrical and electronic components such as audio equipment and car navigation equipment; parts that come into contact with metal, such as the carrier plate of a window regulator; air conditioning parts such as A / C hoses and A / C seals; door lock actuator parts such as door latch strikers; mirror parts; wiper motor system parts; fuel system mechanical parts such as air ducts, fuel hoses, emission control hoses, inlet filler hoses, and diaphragms; vibration damping parts such as engine mounts and in-tank pump mounts; and various tire components such as tire treads, carcasses, sidewalls, inner liners, undertreads, and belt sections.

[0107] Examples of electrical and electronic components (mechanical components) include rubber parts for audio equipment, video equipment, projectors or copiers, fax machines, office automation (OA) equipment such as personal computers, toys, and telephones, as well as optical and magnetic media components.

[0108] Furthermore, it is suitably used in a wide range of lifestyle-related, cosmetic, and medical-related parts, including building materials and plumbing parts such as lighting fixtures, fittings, pipes, and toilet peripheral equipment parts; apparel-related materials such as fasteners (slide fasteners, snap fasteners, hook-and-loop fasteners, rail fasteners, etc.), breathable waterproof films; footwear such as sports shoes, leisure shoes, fashion sandals, leather shoes, and ski boots; balls such as golf balls and tennis balls; various brushes such as hairbrushes; combs; hot curlers; watch bands and other daily necessities; stationery; cosmetic containers including lip balm and lipstick; washing machines, water purifiers, spray nozzles, spray containers, aerosol containers, general containers; food packaging; daily necessities packaging; films such as elastic tapes used in disposable diapers; syringe covers and sealing; office furniture such as office chairs; and cushioning materials for furniture such as cushions and beds.

[0109] It can be used in applications in the textile and nonwoven fabric fields, such as fibers including continuous spinning, staple fibers, and monofilaments; sanitary materials such as disposable diapers; medical applications such as surgical gowns and gloves; carpets, their linings, and ropes. Furthermore, it can be used in canvas, tent materials, and synthetic leather materials by laminating these nonwoven fabrics, monofilaments, and knitted fabrics with films or sheets.

[0110] Furthermore, it can be suitably used in various applications such as hot-melt adhesives and other adhesives, various resin modifiers, road paving materials, waterproof sheets, asphalt blend materials for pipe coatings, industrial material packaging, lamination of various rubber products, resin products, fabrics, and leather products, retainers, conveyor belts and other components for industrial machinery, and 3D printer filaments.

[0111] (Second aspect) In a second aspect of the polyester elastomer resin composition of the present invention, the polyester elastomer resin composition contains a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from a biomass resource, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 100%, the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy 10°C ≤ Tm - VST ≤ 43°C, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It is characterized by being less than or equal to the count.

[0112] A second aspect of the polyester elastomer resin composition of the present invention is unique in that the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy 10°C ≤ Tm-VST ≤ 43°C. Here, the melting point (Tm) of the polyester elastomer resin composition is a value measured in accordance with ASTM D-3418. The Vicat softening point (VST) of the polyester elastomer resin composition is a value measured in accordance with ISO 306 (2013) A50 method. Specifically, it is the temperature when a needle with a flat tip penetrates 1 mm into a test specimen while the test specimen is heated in an oil bath at a heating rate of 50°C / hr with a test load of 10 N perpendicularly applied to the test specimen. Tm-VST is preferably 11 to 42°C, more preferably 12 to 41°C, and particularly preferably 13 to 40°C. By satisfying the above range for Tm-VST, a polyester elastomer resin composition with a balanced mechanical strength and elongation recovery rate can be obtained. If Tm-VST is smaller than the above range, the elongation recovery rate tends to decrease, and if it is larger than the above range, the mechanical strength, such as tensile breaking strength, tends to decrease. The melting point (Tm) tends to be determined by the ratio of hard segment components to soft segment components during polymerization, assuming the same constituent components of the polyester elastomer. On the other hand, the Vicat softening point also depends on the block state and tends to fluctuate depending on the polymerization conditions.

[0113] In order for the Tm-VST of the polyester elastomer resin composition of the present invention to satisfy the above range, it is preferable to set the mass ratio of the hard segment / soft segment of the polyester elastomer used to preferably 35 / 65~90 / 10, more preferably 38 / 62~85 / 15, even more preferably 40 / 60~80 / 20, and particularly preferably 42 / 58~75 / 25, and to take measures such as taking a long polymerization time. By setting the above mass ratio within the above range, it becomes easier to satisfy the Tm-VST conditions when adjusting the polymerization conditions, and it becomes easier to obtain a polyester elastomer resin composition with a good balance between mechanical strength and elongation recovery rate.

[0114] The polyester elastomer resin composition of the present invention preferably has a number average molecular weight (Mn) of 9,000 or more. More preferably, Mn is 10,000 or more, even more preferably 11,000 or more, and particularly preferably 12,000 or more. By setting the number average molecular weight to the above value or higher, excellent mechanical strength, mechanical elongation, elongation recovery rate, and filament processability are obtained.

[0115] Furthermore, the polyester elastomer resin composition of the present invention preferably satisfies Mw / Mn ≤ 5.0. This tends to yield a polyester elastomer with a good balance between mechanical strength and elongation recovery rate. The method for satisfying Mw / Mn ≤ 5.0 is not particularly limited, but since a faster polymerization rate tends to result in a larger Mw / Mn ratio, it is preferable to adjust it, for example, by extending the polycondensation time to 100 minutes or more. Here, Mn and Mw are the number-average molecular weight and weight-average molecular weight, respectively, of the polyester elastomer resin composition obtained by gel permeation chromatography (GPC).

[0116] In addition to the components described above, the polyester elastomer resin composition of the present invention may contain various additives depending on the purpose, and the polyester elastomer resin composition according to the second aspect of the present invention may further contain rigid polyester. By adding rigid polyester, the strength and processability of the resulting polyester elastomer resin composition can be adjusted.

[0117] Rigid polyesters are obtained by polycondensation of at least one acid component selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, etc., and at least one diol component selected from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, or polyalkylene glycols such as polyethylene glycol and polytetramethylene glycol. Specifically, examples include polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene terephthalate (PET), polyhexylene terephthalate (PHT), polyethylene naphthalate, polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polycyclohexane-1,4-dimethylol terephthalate, and copolymerized polyesters such as polyethylene isophthalate / terephthalate (PET / I) and polybutylene isophthalate / isophthalate (PET / I). Among these rigid polyesters, PBT is most preferred from the viewpoint of compatibility with polyester elastomers.

[0118] The amount of rigid polyester blended is preferably a maximum of 150 parts by mass per 100 parts by mass of polyester elastomer, and more preferably a maximum of 100 parts by mass. If too much rigid polyester is blended, the elastic properties may decrease and the elongation recovery rate may decrease.

[0119] The acid value of the polyester elastomer resin composition of the present invention is preferably 0 to 8 eq / ton, more preferably 0 to 6 eq / ton, and even more preferably 0 to 4 eq / ton. When the acid value is within the above range, the melt viscosity during molding is stable, and in the case of monofilament extrusion molding, the fiber diameter is stable and thread breakage tends to decrease. Furthermore, it exhibits excellent hydrolysis resistance.

[0120] The method for producing the polyester elastomer resin composition of the present invention is not particularly limited, but it can be produced in the same manner as the polyester elastomer resin composition according to the first aspect of the present invention.

[0121] As described above, the polyester elastomer resin composition of the present invention, despite using a polyester elastomer derived from biomass resources with a high biomass content, possesses the excellent strength, elastic properties, stretch recovery properties, and filament processability of polyester elastomers derived from fossil fuel resources, and is resistant to oxidative degradation. Therefore, it can be used in applications in the fields of fibers and nonwoven fabrics, such as fibers like continuous spinning, staple fibers, and monofilaments; sanitary materials such as disposable diapers; medical applications such as surgical gowns and gloves; carpets, their linings, and ropes. Furthermore, it can be used in canvas, tent materials, synthetic leather materials, etc., by laminating these nonwoven fabrics, monofilaments, and knitted fabrics with films or sheets.

[0122] Specifically, monofilaments can be manufactured using the polyester elastomer resin composition of the present invention. The manufacturing process can be carried out using a conventional melt spinning apparatus. The polyester elastomer resin composition is supplied to a known melt spinning machine, melt-kneaded, and then extruded through the spinneret hole.

[0123] Furthermore, from the viewpoint of spinnability, the number average molecular weight (Mn) of the polyester elastomer resin composition is preferably 9,000 or higher. If Mn is low, the strength is insufficient, making it difficult to withstand high-speed spinning and prone to yarn breakage. Also, from the same viewpoint, Mw / Mn is preferably 5 or less. If Mw / Mn is high, the polyester elastomer resin composition is prone to thermal degradation and breakage, and may contain more gel-like substances that contribute to breakage. In addition, variations in the properties of the resin composition are more likely to occur, which can also be a cause of yarn breakage.

[0124] The monofilament made from the polyester elastomer resin composition of the present invention preferably has a diameter of 0.10 mm or more. If a monofilament with a diameter of less than 0.10 mm is used, there is a concern that the strength of the impact-absorbing structure made from the monofilament will be inferior. On the other hand, the diameter of the monofilament is preferably 1.5 mm or less. If a monofilament with a diameter greater than 1.5 mm is used, the process passability during processing tends to be poor.

[0125] The monofilament made from the polyester elastomer resin composition of the present invention can be used to create a composite filament using a polyester elastomer resin composition of two components with different melting points. In this case, it is preferable that the area ratio occupied by the low-melting-point component in any cross-section is 50% or less. Furthermore, in this composite filament using polyester elastomers of two components with different melting points, it is preferable that the melting point of the high-melting-point component constituting the monofilament is 150°C or higher and less than 200°C, and that the melting point of the low-melting-point component is 20°C or higher and less than 50°C lower than the melting point of the high-melting-point component.

[0126] The composite monofilament of the present invention is composed of two polymer components, a high-melting-point component and a low-melting-point component, compounded anisotropically with respect to the cross-sectional direction of the filament. The two components can take the form of a core-sheath type, a side-by-side type, a radial type, or a so-called sea-island type in which the other component is dispersed as several small island-like structures within one component, or even a form in which the two components are joined at a part of the outer circumference. The shape and form are not particularly limited, but it is preferable to have a core-sheath structure composite monofilament in which the core is formed from the high-melting-point component and the sheath is formed from the low-melting-point component.

[0127] Knitted fabrics, woven fabrics, or nonwoven fabrics can be obtained by using monofilaments made from the polyester elastomer resin composition of the present invention as a constituent material. In order to obtain a highly elastic fabric such as a knitted fabric, woven fabric, or nonwoven fabric that has sufficient mechanical strength to support a load, as well as cushioning and its repeated durability, the elongation at break of the monofilament is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more. If the elongation at break is below the above range, the resulting fabric will not be given sufficient elastomeric properties.

[0128] Furthermore, the tensile strength of the monofilament is preferably 1.2 cN / dtex or higher, more preferably 1.3 cN / dtex or higher, and even more preferably 1.4 cN / dtex or higher. If the tensile strength is below the above range, the strength of the resulting fabric will be insufficient and will likely be weak against static loads. However, if the fiber strength exceeds 4.0 cN / dtex, the initial load gradient of the fabric will rise sharply, which is undesirable from a fabric design perspective.

[0129] Furthermore, the monofilament preferably has an elongation recovery rate of 80% or more after 30% elongation at 23°C, more preferably 85% or more, even more preferably 90% or more, and particularly preferably 95% or more. Also, the monofilament preferably has an elongation recovery rate of 70% or more after 20% elongation at 80°C, more preferably 75% or more, even more preferably 80% or more, and particularly preferably 85% or more. If these elongation recovery rates are lower than the above ranges, the elastic properties will deteriorate with repeated use and the fabric will be prone to sagging. This elongation recovery rate can be achieved by setting the chemiluminescence emission amount of the polyester elastomer resin composition to the range specified in the present invention. In particular, the presence of peroxides generates peroxide radicals at high temperatures, which promotes oxidative degradation, so the above elongation recovery rate can be achieved by reducing the chemiluminescence emission amount of the polyester elastomer resin composition to below a specific value.

[0130] The composite monofilament of the present invention, in order to improve the binding force of the fabric, can be used in one or both of the warp and weft to form a woven, knitted, or nonwoven fabric. After that, the low-melting-point component of the two components can be partially melted or fused at the filament intersections without substantially affecting the high-melting-point component, thereby forming joints. This prevents deformation of the knitted or woven structure during repeated deformation of the fabric, providing long-term durability, and as a result, it is possible to provide a highly elastic fabric that maintains a high level of stretch recovery over the long term.

[0131] The polyester elastomer resin composition of the present invention can be molded into various shapes not only through monofilament processing, but also through extrusion molding, injection molding, transfer molding, blow molding, and the like.

[0132] The various molded products manufactured by the above processing method can be suitably used for a wide range of components, including automotive parts, electrical and electronic components, building materials, various containers, daily necessities, household goods, cosmetic components, sanitary products, and medical (medical and therapeutic) components.

[0133] (Third aspect) In a third aspect of the polyester elastomer resin composition of the present invention, the polyester elastomer resin composition contains a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-100%, the MFR value of the polyester elastomer resin composition at a load of 2.16 kg measured in accordance with the flow test method for thermoplastics specified in JIS K7210 is 0.5-20 g / 10 min (measurement temperature: melting point + 20°C), and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ 5 It is characterized by being less than or equal to the count.

[0134] A third aspect of the polyester elastomer resin composition of the present invention is unique in that its melt flow rate (MFR) value, when measured in accordance with the thermoplastic flow test method specified in JIS K7210 at a melting point of +20°C, a load of 2.16 kg, and a residence time of 5 minutes, is 0.5 to 20 g / 10 min. Preferably, it is 0.5 to 18 g / 10 min, and more preferably 1 to 16 g / 10 min. If the MFR is lower than the above range, the number of bubbles in the foamed molded article decreases, the bubble diameter does not increase, and high-magnification foaming becomes difficult. Also, gel-like material is more likely to be generated. If it is higher than the above range, the percentage of closed cells in the foamed molded article decreases, the bubble diameter becomes non-uniform, and mechanical properties such as rebound elasticity and compression recovery force decrease. Also, the properties tend to fluctuate during continuous molding.

[0135] Methods for adjusting the MFR value to the above range are not particularly limited, but include controlling the molecular weight during polyester elastomer polymerization and extending the chain during compounding. In the present invention, it is preferable to incorporate a predetermined amount of thickener in a specific way during compounding, as this allows for control of the MFR value in conjunction with the acid value.

[0136] The acid value of the polyester elastomer resin composition of the present invention is 50 eq / ton or less. Preferably, it is 45 eq / ton or less, more preferably 40 eq / ton or less, and even more preferably 35 eq / ton or less. When the acid value is within the above range, the melt viscosity during foam molding is stable, and even during long-term continuous foam molding, there is little change in the state of the bubbles, and the properties of the foamed molded article are stable. Furthermore, it exhibits excellent hydrolysis resistance. On the other hand, if the acid value of the polyester elastomer resin composition exceeds the above range, when a thickener is included, localized reactions with the thickener tend to proceed easily, raising concerns about the generation of gelled products. Furthermore, hydrolysis is more likely to occur, so when the residence time is long at high temperatures, such as during compounding or molding, the melt viscosity of the resin composition decreases, the properties during molding tend to change easily, and even after becoming a foamed molded article, the heat and humidity resistance is poor.

[0137] When using a thickening agent in the polyester elastomer resin composition of the present invention, in order to keep the acid value of the resin composition within the above range, it is preferable not only to keep the acid value of the polyester elastomer within the same range, but also to control the reaction between the thickening agent and the carboxyl group ends of the polyester elastomer.

[0138] In the present invention, the oligomer content of the biomass resource-derived polyester elastomer with a molecular weight of less than 1000 is preferably 2.5% by weight or less, more preferably 2.4% by weight or less, and even more preferably 2.3% by weight or less. If the oligomer content is high, the MFR of the polyester elastomer resin composition may not decrease sufficiently in the compound during the production of the composition, and high-precision moldability may not be obtained. In addition, when a thickener is added, gel formation may occur easily, which may worsen the appearance and properties of the molded product. Furthermore, the thermal stability and water resistance of the molten resin may deteriorate, causing differences in fluidity between the start and end of molding, which may impair stable productivity. Moreover, even in the molded product, it may not be possible to obtain one that satisfies the functions of rebound elasticity, flexibility, and low-temperature mechanical properties.

[0139] The method for producing the polyester elastomer resin composition of the present invention is not particularly limited, but it can be produced in the same manner as the polyester elastomer resin composition according to the first aspect of the present invention.

[0140] The foaming method for the polyester elastomer resin composition of the present invention is not particularly limited, but a foaming method in which the resin composition is impregnated with high-pressure gas and then the pressure is reduced (pressure is released) is preferred. As a method that is excellent in terms of molding cycleability and cost and obtains a homogeneous foam, a method in which a foaming agent and the polyester elastomer resin composition of the present invention are melt-mixed and the cavity volume is expanded during injection molding to obtain a foamed molded article is preferred. The foamed molded article of the present invention usually has a sandwich structure in which non-foamed skin layers are provided on both sides of the foamed layer (in other words, a structure in which the foamed layer is sandwiched between non-foamed skin layers on both sides). The size of the foamed molded article is not particularly limited, but the thickness in the sandwich structure direction is expected to be about 1 to 30 mm.

[0141] The foamed layer of the foamed molded article of the present invention is composed of a continuous resin phase and independent foamed cells. Here, the continuous resin phase refers to the portion without voids formed by the cured polyester elastomer resin composition. The diameter of the foamed cells (cell diameter) is preferably uniform and without variation. The average cell diameter is preferably 10 to 400 μm, more preferably 50 to 400 μm, even more preferably 100 to 400 μm, and particularly preferably 150 to 300 μm. If the average cell diameter is small, the internal pressure of the molded article is low, resulting in insufficient pressure during the formation of the non-foamed skin layer, which tends to lead to poor appearance such as sink marks. On the other hand, if the average cell diameter is large, the load-bearing capacity tends to be low.

[0142] The non-foamed skin layer is laminated on the foamed layer and preferably has a thickness of 100 to 800 μm. If the thickness of the non-foamed skin layer is too small, a good appearance tends not to be obtained, while if the thickness is too large, the specific gravity of the foamed layer becomes too low, and the foamed molded article as a whole tends not to be obtained in a uniform cellular state. The thickness of the non-foamed skin layer is more preferably 200 to 600 μm, and even more preferably 300 to 400 μm.

[0143] The foamed molded article obtained from the polyester elastomer resin composition of the present invention can achieve a volume-average cell diameter of Dv and a number-average cell diameter of Dn, where Dv is ≤ 4, preferably Dv / Dn ≤ 3.7, and more preferably Dv / Dn ≤ 3. When Dv / Dn is within the above range, closed-cell bodies are easily obtained. In addition, the number of coarse bubbles with a diameter exceeding 800 μm is small, resulting in less impact on the overall physical properties of the phase, and excellent rebound elasticity and compressive recovery. If Dv / Dn is larger than the above range, the number of coarse bubbles exceeding 800 μm increases, and extra-large bubbles of several thousand μm also appear, increasing the number of open-cell bodies and affecting the overall physical properties of the foamed phase. As a result, rebound elasticity and compressive recovery decrease.

[0144] As a method for controlling the Dv / Dn of a foamed molded article obtained from the polyester elastomer resin composition of the present invention, a general method for controlling the bubble diameter in each foaming molding method can be employed, but it is preferable to appropriately control the melt flowability of the resin composition during foaming. If the melt flowability is too low, the resin cannot keep up with the force of bubble enlargement, resulting in large variations in bubble diameter and making it easier for large bubbles to form. On the other hand, if the melt flowability is too high, it is undesirable because it hinders the generation and growth of bubbles. MFR can be used as an indicator of melt flowability when controlling Dv / Dn.

[0145] When a foamed molded article obtained from the polyester elastomer resin composition of the present invention is subjected to continuous molding, if the Dv / Dn of the foamed molded article obtained after 5 shots from the start of foam molding is (Dv / Dn)5 and the Dv / Dn of the foamed molded article obtained after 40 shots from the start of foam molding is (Dv / Dn)40, then Δ(Dv / Dn) = (Dv / Dn)40 - (Dv / Dn)5, then Δ(Dv / Dn)≦1 can be achieved. More preferably, Δ(Dv / Dn)≦0.8, even more preferably Δ(Dv / Dn)≦0.5, and particularly preferably Δ(Dv / Dn)≦0.4. When Δ(Dv / Dn) is within the above range, there is little change in physical properties even during continuous molding, and a foamed molded article of stable quality can be obtained.

[0146] Furthermore, the rate of change of Dv / Dn, obtained by dividing Δ(Dv / Dn) by Dv / Dn, is preferably 25% or less. More preferably 20% or less, and even more preferably 15% or less. This rate of change of Dv / Dn can be achieved by reducing the chemiluminescence emission amount and acid value to the range defined in this invention.

[0147] In this invention, Dn and Dv are calculated as follows. First, the diameter of each bubble is determined as follows. The photograph of the foamed cross-section of the sample taken with an electron microscope is image-processed, and the equivalent circular diameter of at least 100 adjacent bubbles (if the bubbles are observed to be elliptical, the average of the major and minor axes is used as the equivalent circular diameter) is taken as the bubble diameter and measured with calipers, and this is taken as the diameter of each bubble. The average value of these 100 values ​​is calculated and this is done at three arbitrary locations, and the average of the three average values ​​obtained at the three locations is taken as the average bubble diameter di. Then, Dn and Dv are calculated using the following formulas. Dn = Σdi / n Dv = Σ(Vi·di) / Σ(Vi) (Here, n is the total number of bubbles measured, and Vi is the volume of each bubble calculated by di, assuming each bubble is a perfect sphere.)

[0148] The chemical blowing agent used to obtain the foamed molded article of the present invention is a gas component that acts as a foaming nucleus or is added to the resin molten in the resin molten zone of the molding machine as a source of foaming. Specifically, the chemical blowing agent can be an inorganic compound such as ammonium carbonate and sodium bicarbonate, or an organic compound such as azo compounds, sulfohydrazide compounds, nitroso compounds, or azide compounds. Examples of the above azo compounds include diazocarbonamide (ADCA), 2,2-azoisobutyronitrile, azohexahydrobenzonitrile, and diazoaminobenzene, with ADCA being preferred. Examples of the sulfohydrazide compounds include benzenesulfohydrazide, benzene 1,3-disulfohydrazide, diphenylsulfon-3,3-disulfonhydrazide, and diphenyloxide-4,4-disulfonhydrazide. Examples of the nitroso compounds include N,N-dinitrosopentaethylenetetramine (DNPT). Examples of the azide compounds include terephthalazide and p-ter-butylbenzazide.

[0149] The density (apparent density) of the foamed molded article obtained from the polyester elastomer resin composition of the present invention is preferably 0.01 to 0.30 g / cm³. The density of general polyester elastomers is around 1.0 to 1.4 g / cm³, so within the above range, the weight reduction is sufficient. More preferably, it is 0.1 to 0.25 g / cm³, and even more preferably 0.1 to 0.20 g / cm³. If the density is below the above range, sufficient strength cannot be obtained and the mechanical properties tend to be inferior, and if it exceeds the above range, sufficient flexibility cannot be obtained, and the weight reduction is not sufficient.

[0150] The foamed molded article of the present invention has a uniform and fine cell structure when the above-mentioned Dv / Dn is within a predetermined range, and as a result, it can achieve a high rebound modulus of 60% or more.

[0151] The rebound modulus is a value measured according to the method described in JIS K 6400. Specifically, a steel ball is dropped onto a test piece from a specified height using a manual measuring test machine, and the maximum height at which it bounces is read. The rebound modulus can be calculated by taking three measurements within one minute and finding the median value.

[0152] The foamed molded article of the present invention has a uniform and fine cell structure when Dv / Dn is within a predetermined range, and as a result, it is possible to achieve a 50% constant displacement cyclic compressive residual strain of 10% or less. More preferably it is 8% or less, and even more preferably 6% or less. If the 50% constant displacement cyclic compressive residual strain exceeds the above range, the thickness will decrease with long-term use, making it undesirable as a cushioning material. There is no particular lower limit for the 50% constant displacement cyclic compressive residual strain, but in the foamed molded article obtained in the present invention, it is 1% or more.

[0153] The 50% constant displacement cyclic compressive residual strain is determined as follows: The sample is cut to a size of 50 mm x 50 mm, and the height of the four corners is measured with a caliper. The average value is taken as the initial thickness (a). The sample with the measured thickness is compressed and recovered repeatedly at a cycle of 1 Hz using a pressure plate of φ200 mm in a 20°C ± 2°C environment until it reaches 50% of the initial thickness. After 80,000 cycles, the sample is left to stand for one day, and the height of the four corners of the post-test sample is measured with a caliper. The average value is taken as the post-test thickness (b). The 50% constant displacement cyclic compressive residual strain is calculated using the formula {(a)-(b)} / (a)×100.

[0154] As the polyester elastomer resin composition of the present invention is configured as described above, it can maintain the excellent mechanical properties, storage stability, and high-precision moldability of polyester elastomers derived from fossil fuel resources, even though it uses a polyester elastomer derived from biomass resources with a high biomass content, and it also has excellent foam moldability. Furthermore, the foamed molded articles obtained from the resin composition of the present invention are lightweight, have excellent compression recovery, and have a high rebound modulus, making them suitable for use in various parts such as automobile parts, electrical and electronic components, building materials, various containers, daily necessities, household goods, cosmetic parts, sanitary products, and medical (medical and therapeutic) parts.

[0155] More specifically, the foamed molded articles obtained from the resin composition of the present invention can be used for footwear components such as midsoles, insoles, and outsoles that constitute the soles of shoes; core materials for sports equipment such as rackets and bats, and for balls such as golf balls; protective gear for sports equipment such as pads and protectors; medical, nursing, welfare, and healthcare products such as pads and protectors; tire core materials for bicycles and wheelchairs; interior materials, seat core materials, shock-absorbing materials, and vibration-absorbing materials for transportation equipment such as automobiles, railway vehicles, and airplanes; shock-absorbing materials such as fenders and floats; toys, beds, mattresses, cushions, and the like. [Examples]

[0156] Examples are given below to demonstrate the effects of the present invention, but the present invention is not limited in any way by these examples. The characteristic values ​​in each embodiment were evaluated by the following method. In addition, the raw materials of the polyester elastomer used in the examples are derived from fossil fuel resources unless otherwise specified.

[0157] (1) Bio-basedness The bio-basedness of polyester elastomers is calculated from the mass of monomer components derived from biomass resources relative to the total mass of monomer components constituting the polyester elastomer. The bio-basedness is determined by the proportion of carbon contained in the polyester elastomer that is found only in raw materials derived from biomass resources. 14 C carbon ( 12 The measured proportion of carbon isotopes is consistent with the values ​​obtained. The biobase (%) of the polyester elastomer was measured by accelerator mass spectrometer (AMS) according to ASTM D6866. On the other hand, the bio-basedness of a polyester elastomer resin composition is the ratio of monomer components derived from biomass resources to the total mass of monomer components constituting the polyester elastomer resin composition. The bio-basedness is calculated based on the proportion of carbon contained in the polyester elastomer resin composition that is found only in raw materials derived from biomass resources. 14 C carbon ( 12 The measured proportion of carbon isotopes is consistent with the values ​​obtained. The biobase (%) of the polyester elastomer resin composition was measured by accelerator mass spectrometer (AMS) according to ASTM D6866.

[0158] (2) Reduced viscosity (ηsp / c) 0.05 g of 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 viscous tube.

[0159] (3) Melting point (Tm) Using a differential scanning calorimetry analyzer "DSC220" manufactured by Seiko Electronics Industries, Ltd., 5 mg of the sample was placed in an aluminum pan, sealed by pressing down on the lid, melted in nitrogen at 250°C for 2 minutes, then cooled to 50°C at a rate of 20°C / min, and further heated from 50°C to 250°C at a rate of 20°C / min. The endothermic peak due to melting was determined from the resulting thermogram curve and defined as the melting point (°C).

[0160] (4) Glass transition temperature (Tg) For the measurement samples, 0.4 mm thick sheets were prepared by pressing them with a hot plate heated to 200-250°C using an NF-type single-acting compression molding machine (manufactured by Shinto Metal Industries Co., Ltd.). Measurements were performed using a dynamic viscoelasticity analyzer Rheogel-E4000 (manufactured by UBM Co., Ltd.) under conditions of a measurement frequency of 11 Hz and a heating rate of 2°C / min. The peak position of the tanδ from -150°C to 150°C was defined as Tg(°C).

[0161] (5) Acid value (AV) 0.2 g of the sample was accurately weighed, and dissolved in benzyl alcohol by heating. 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 determined from the amount of potassium hydroxide titrated for neutralization. Phenol red ethanol solution was used as an indicator.

[0162] (6) Oligomer content The oligomer content in the polyester elastomer was measured as follows: 8 mg of the resin component was weighed and dissolved in 4 ml of 10 mM HFIP / 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. Molecular weight was calculated in terms of polymethyl methacrylate (PMMA), and in the GPC analysis chart, the percentage of the peak area showing a molecular weight of 1000 or less relative to the total peak area of ​​the polymer was calculated, and this area ratio was defined as the oligomer content (wt%). Equipment: TOSOH HLC-8320GPC Column: TOSOH TSKgel SuperHM-H x 2 +TSKgel SuperH2000 Solvent: HFIP / Sodium trifluoroacetate 10 mM Flow rate: 0.2ml / min Injection volume: 10μl Temperature: 40℃ Detector: RI Concentration: 0.2%

[0163] (7) Chemiluminescent emission Measurements were taken using an extremely weak emission detection spectrometer (CLA-FS5, manufactured by Tohoku Electronics Industry Co., Ltd.) in accordance with JIS K7351. Test specimens formed from polyester elastomer compositions were placed in a sample chamber (heated sample chamber "GLS-ST5", manufactured by Tohoku Electronics Industry Co., Ltd.) and held at 160°C for 300 seconds under an oxygen atmosphere with a flow rate of 100 ml / min. The cumulative chemiluminescence emission of the test specimen was measured every second from the start of measurement to 300 seconds. The 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 flat plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) with a cylinder temperature of Tm + 20°C and a mold temperature of 30°C. The resulting pieces were then cut into 10mm x 10mm x 2mm sections.

[0164] (8) Melt tension The melt tension of the polyester elastomer resin composition was measured using a Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd., with the following conditions: capillary: diameter 2.0 mm, length 20 mm, cylinder diameter: 9.55 mm, temperature: melting point + 10°C, cylinder extrusion speed: 20 mm / min, and take-up acceleration 40 m / min until the take-up speed reached 10 m / min. 2 It was measured using [this method].

[0165] (9)3% weight loss temperature The measurements were performed using a differential thermal and thermogravimetric simultaneous measurement device (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 under a nitrogen atmosphere with a flow rate of 20 ml / min. The temperature at which decomposition at high temperatures progressed and the weight became 97% of the initial weight was defined as the 3% weight loss temperature.

[0166] (10) Evaluation of gels Approximately 50 g of polyester elastomer resin composition was accurately weighed into a glass bottle of approximately 250 ml (approximately 4 cm in diameter x 20 cm in height). This was immersed in a silicone oil bath at 250°C, and the mixture was heated for 4 hours while being stirred and nitrogen was blown in from above (approximately 30 ml / min). After treatment, the contents were dissolved in a mixed solvent of tetrachloroethane and phenol (1 / 1 by weight ratio) (500 ml) (the glass bottle was also rinsed with a portion of the above mixed solvent). Subsequently, insoluble matter was separated using a 100-mesh stainless steel mesh of known weight (weight V'), observed visually, and evaluated according to the following criteria. ○: No gel material was observed at all. △: A slight amount of gel is observed. ×: Significant gelation is observed.

[0167] (11) MFR, ΔMFR In accordance with the test method (Method A) described in JIS K7210, the melt flow rate (MFR: g / 10min) of the polyester elastomer resin composition was measured 5 minutes after immersion at a melting point of polyester elastomer +20°C and 2160g. Compositions with a moisture content of 0.1% by mass or less were used for the measurement. The MFR value after 45 minutes (MFR45) was also measured, and the difference (ΔMFR: MFR35-MFR5) between the MFR value after 5 minutes (MFR5) and the MFR value after 5 minutes (MFR5) was defined as ΔMFR.

[0168] (12) Tensile elongation and tensile strength at break The tensile elongation (%) and tensile strength (MPa) at break of the polyester elastomer resin composition were measured in accordance with JIS K6251. Test specimens were prepared by injection molding a 100mm × 100mm × 2mm flat plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) with a cylinder temperature (Tm + 20°C) and a mold temperature of 30°C, after which dumbbell-shaped test specimens (type 3) were punched out from the flat plate.

[0169] (13) Tensile elongation retention rate at break The test specimens were left in an 85°C × 95%RH environment for 750 hours, then removed, and the tensile elongation at break was measured using the method described above in (11). The tensile elongation at break was also measured for the test specimens that had not undergone moist heat treatment, and this was taken as the initial tensile elongation at break. The retention rate of the tensile elongation at break after moist heat treatment (tensile elongation retention rate at break) was calculated as follows. Tensile elongation retention rate at cutting (%) = (Tensile elongation at cutting after moist heat treatment / Initial tensile elongation at cutting) × 100

[0170] (14) Extrusion moldability (pulsation) The pellets, which had been melt-kneaded in a twin-screw extruder, were then extruded again from a circular die using a single-screw extruder to produce strands with a diameter of 3 mm. From this state, the extrusion moldability (variation in extrusion volume) was evaluated according to the following criteria. ○: No fluctuations in discharge volume, and extrusion properties are stable. ×: Discharge volume fluctuates, making collection impossible.

[0171] (15) Extrusion moldability (smoothness) Pellets, melt-kneaded in a twin-screw extruder, were then extruded again from a T-die using a single-screw extruder to produce 0.2 mm thick sheet molded products. The smoothness of the extruded products was evaluated from the appearance of the sheets according to the following criteria. ○: No roughness or foaming occurs, and the sheet appearance and surface smoothness are excellent. △: No sheet irregularities (melt fracture) or foaming occur, but there is a uniform roughness similar to a textured finish. ×: Sheet irregularities (melt fracture) and foaming occur, resulting in an unsatisfactory appearance.

[0172] (16) Water aging resistance A resin hose with an outer diameter of 17.5 mm was manufactured using the obtained polyester elastomer composition (A) as the resin for the inner tube, polyester yarn (1500d, 1 mm thick) as the reinforcing material, and a polyether-type urethane elastomer with a surface hardness of 98A for the outer tube. This hose was cut to a length of 200 mm, immersed in boiling water at 100°C for 20 days, then removed and subjected to a bending test at a diameter of 80 mm. The presence or absence of cracks or fractures was observed and evaluated according to the following criteria. ○: No cracks or fractures are observed. △: No cracks or fractures are present, but the surface is rough and clear embrittlement is observed. ×: Cracks or fractures are observed.

[0173] (17) Vicat softening point (VST) In accordance with ISO 306 (2013) A50 method, the Vicat softening point (VST) was defined as the temperature at which a flat-tipped needle penetrated 1 mm into the test specimen when it was subjected to a test load of 10 N while being heated in an oil bath at a heating rate of 50 °C / hr. The test specimens were prepared according to the following procedure. (Method for preparing test specimens) The test specimens were prepared by injection molding a polyester elastomer resin composition, dried under reduced pressure at 100°C for 5 hours, into a 100mm x 100mm x 2mm flat plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) at a cylinder temperature of Tm + 20°C and a mold temperature of 30°C. Dumbbell-shaped test specimens (type 3) were then punched out from the flat plate.

[0174] (18) Tm-VST (3) and (17) were used to determine the difference between the Tm value and the VST value.

[0175] (19) Mn, Mw / Mn 8 mg of polyester elastomer resin composition was weighed and dissolved in 4 ml of 10 mM HFIP / 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 number-average molecular weight (Mn) and weight-average molecular weight (Mw) were calculated in terms of polymethyl methacrylate (PMMA), and Mw / Mn was calculated from these values. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated excluding molecules with a molecular weight of less than 1000. The molecular weight distribution (Mw / Mn) was also calculated in the same manner as above, using the weight-average molecular weight and number-average molecular weight excluding molecules with a molecular weight of less than 1000, by dividing the weight-average molecular weight by the number-average molecular weight. Equipment: TOSOH HLC-8320GPC Column: TOSOH TSKgel SuperHM-H x 2 +TSKgel SuperH2000 Solvent: HFIP / Sodium trifluoroacetate 10 mM Flow rate: 0.2ml / min Injection volume: 10μl Temperature: 40℃ Detector: RI Concentration: 0.2%

[0176] (20) Breaking strength, breaking elongation Using an Orientec Tensilon™ measuring device, a 100 mm long monofilament was measured at a strain rate of 100% / min under a temperature of 25% and relative humidity of 65%. The fracture strength and fracture elongation were evaluated from the obtained strain-stress curves. The average of five measurements was used for each value.

[0177] (21) Elongation recovery rate after 30% elongation at 23°C, and elongation recovery rate after 20% elongation at 80°C A heating chamber adjusted to a temperature of 23°C or 80°C was placed in the above measuring apparatus, and a monofilament with a sample length of 100 mm was set in it. After heating for 2 minutes, it was stretched to 20% or 30% at a strain rate of 100% / min, and then immediately deformed back to 0% at the same rate. Ten seconds after the deformation returned to normal, it was stretched again to 20% or 30% at the same rate. From the recorded strain-stress curves during this series of measurements, the amount of strain x (%) at which stress begins to occur after the second stretching was determined, and the stretching recovery rate was evaluated using the following formula. Elongation recovery rate (%)=100-x

[0178] (22) Filament processability Six hours of continuous spinning were performed, and yarn breakage was judged according to the following criteria. ○: 0 instances of thread breakage △: Thread breakage occurred 1-2 times. ×: Thread breakage occurred 3 or more times.

[0179] The monofilaments evaluated in (20) to (22) above were manufactured according to the following procedure. The polyester elastomer resin composition was pre-dried for 4 hours under a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried under the same vacuum conditions at 120°C for 12 hours. The resulting dried resin was melted using a spinning machine equipped with a melt extrusion device, and spun by adjusting the extrusion rate to 22.2 g / min per nozzle hole (unit of monofilament). The extruded polymer was cooled by passing it through a water bath of approximately 30°C with a 50 mm air gap, then stretched four times between a Nelson roller and a take-up roller with the surface temperature adjusted to 90°C and the speed to 20 m / min, and subsequently taken up by another pair of Nelson rollers while relaxing by approximately 2% between slit-type heaters at 150°C, and immediately wound up.

[0180] (23) Dv / Dn Photographs of the foamed cross-section of a sample taken with a Hitachi High-Technologies scanning electron microscope SU1510 were processed, and the equivalent circular diameter of at least 100 adjacent bubbles (if bubbles were observed to be elliptical, the average of the major and minor axes was used as the equivalent circular diameter) was defined as the bubble diameter and measured with calipers. The average value of these 100 values ​​was calculated and repeated at three arbitrary locations, and the average of the three values ​​obtained at the three locations was defined as the average bubble diameter. Then, the volume-average bubble diameter Dv and the number-average bubble diameter Dn were calculated using the following formulas, and Dv / Dn was calculated. Dn = Σdi / n Dv = Σ(Vi·di) / Σ(Vi) (Here, n is the total number of bubbles measured, and Vi is the volume of each bubble calculated by di, assuming each bubble is a perfect sphere.)

[0181] (24)Δ(Dv / Dn) Continuous molding is performed, and the Dv / Dn of the foamed molded body obtained after 5 shots from the start of foam molding is set to (Dv / Dn)5, and the Dv / Dn of the foamed molded body obtained after 40 shots from the start of foam molding is set to (Dv / Dn) 40 Let's assume that from these values, Δ(Dv / Dn) = (Dv / Dn) 40 —Calculated using the formula (Dv / Dn)5.

[0182] (25) Dv / Dn change rate It was calculated using the following formula. Δ(Dv / Dn) / (Dv / Dn)×100(%)

[0183] (26) Density (apparent density) The dimensions of the foam molded specimens were measured with calipers, their mass was measured with an electronic balance, and the density was calculated using the following formula. Density (g / cm 3 ) = Mass of the test specimen / Volume of the test specimen

[0184] (27) Rebound modulus The measurements were performed in accordance with the method described in JIS K6400. Using a manual measuring test machine, a steel ball was dropped onto the test specimen from a specified height, and the maximum height of the rebound was read. Three measurements were taken within one minute, and the median value was determined to calculate the rebound modulus.

[0185] (28) 50% constant displacement repeated compression residual strain The sample was cut to a size of 50 mm x 50 mm, and the height of four corners was measured with a caliper. The average value was taken as the initial thickness (a). The sample with the measured thickness was compressed and recovered repeatedly at a cycle of 1 Hz using a pressure plate φ200 mm in a 20°C ± 2°C environment until it reached 50% of the initial thickness. After 80,000 cycles, the sample was left to stand for one day, and the height of four corners was measured with a caliper. The average value was taken as the post-test thickness (b). The residual compression strain under constant displacement cyclic compression at 50% was calculated using the formula {(a)-(b)} / (a)×100.

[0186] (29) Continuous moldability The foamed molded articles obtained using the polyester elastomer resin composition were evaluated as follows. Foaming was performed continuously, and the foamed molded articles from the 5th and 40th shots from the start of foaming were evaluated according to the following criteria. (A: Change in rebound modulus (%), B: Change in residual strain of repeated compression at constant displacement (%)) ◎···A≦1 and B≦1 〇···A≦2 and B≦2 △···A≦3 and B≦3 ×···A≧4 or B≧4

[0187] (30) Specific gravity The specific gravity was measured using an automatic hydrometer D-H100 manufactured by Toyo Seiki Co., Ltd. A flat plate formed in the same manner as in (7) was cut to a size of 10 mm x 10 mm to obtain a sample for specific gravity measurement. The specific gravity was measured using the water displacement method with the prepared sample.

[0188] (31) Tensile elongation retention The dumbbell-shaped test specimens described above were left in an air environment at 100°C for 1000 hours, then removed, and the tensile elongation at break was measured in accordance with JIS K6251, as described above. The tensile elongation retention rate was calculated using the following formula. Tensile elongation retention rate (%) = (Tensile elongation after heat treatment / Initial tensile elongation) × 100

[0189] (32)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 (standard established by Under Writers Laboratories Inc. in the United States), were injection molded at a cylinder temperature (Tm + 20°C). The test specimens obtained using the method described above were evaluated in accordance with the UL-94 flammability test method. Burn time is shown as the sum of the burn times after two flame applications for each of the five samples.

[0190] (33) Variation in flame retardancy (12) The flame retardancy of the test specimens was evaluated 5 minutes, 35 minutes, 65 minutes, 90 minutes, and 125 minutes after the start of injection molding as described above, and the flame retardancy variability was evaluated according to the following criteria. ○: All five test pieces have the same flame retardancy. ×: One or more of the five test specimens have different flame retardancy.

[0191] (Example of the first embodiment) [Polyester elastomer (XA)] Polymerization example X1 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 145 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 70 minutes to 250°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under a state of less than 1 Torr for 125 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA1).

[0192] Polymerization example X2 680 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 430 parts by mass of 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) derived from biomass resources, 2330 parts by mass of polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical Corporation) derived from biomass resources, 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 205°C over 190 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 1 Torr over 85 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under a state of less than 1 Torr for 105 minutes, and a polymer with a hard segment / soft segment mass ratio of 17 / 83 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA2).

[0193] Polymerization example X3 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 parts by mass of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were charged into an autoclave and the temperature was raised from room temperature to 225°C over 145 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 70 minutes to 250°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 250°C and below 1 Torr for 80 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA3).

[0194] Polymerization example X4 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 145 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 70 minutes to 250°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of less than 1 Torr for 85 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA4).

[0195] Polymerization example X5 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 145 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised over 60 minutes to 235°C and below 0.7 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 255°C for 130 minutes under conditions of 0.7 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA5).

[0196] Polymerization example X6 1815 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1665 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 860 parts by mass of biomass resource-derived dimer acid (C36DiCOOH, Propol1009, manufactured by Croda), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and heated from room temperature to 225°C over 115 minutes to carry out transesterification and esterification reactions. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 70 minutes to 250°C and below 1 Torr to carry out the initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C and below 1 Torr for 60 minutes, 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 (XA6).

[0197] Polymerization example X7 550 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 230 parts by mass of 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) derived from biomass resources, 3230 parts by mass of polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical Corporation) derived from biomass resources, 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 210°C over 195 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 85 minutes to 250°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of less than 1 Torr for 110 minutes, and a polymer with a hard segment / soft segment mass ratio of 7 / 93 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (XA7).

[0198] Polymerization example X8 A polymer was obtained in the same manner as in polymerization example X1, except that 1,4-butanediol derived from biomass resources (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) was replaced with 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical). The obtained polymer was designated as a polyester elastomer (XA8).

[0199] Table 1 shows the composition and evaluation results of the polyester elastomers (XA1) to (XA8).

[0200] [Table 1]

[0201] [Heat stabilizer (XB)] Hindered phenol antioxidant: Irganox 1010 (manufactured by BASF)

[0202] [Hydrolysis inhibitor (XC)] Alicyclic polycarbodiimide: Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Co., Ltd.

[0203] [Thickener (XD)] Triglycidyl isocyanurate compound: "TEPIC-S", manufactured by Nissan Chemical Corporation, epoxy valency (average number of epoxy groups per molecule) 3

[0204] The polyester elastomers (XA1) to (XA8) used in the following Examples X1 to X10, Comparative Examples X1 to X7, and Reference Examples X1 to X3 were obtained by vacuum drying at 80°C for 8 hours.

[0205] [Examples X1, X2, X7, X10, Comparative Examples X1, X2, X4, X5, Reference Examples X1, X2] The components (XA) to (XD) listed above were weighed in the proportions shown in Table 2. After mixing all components except (XC) in a mixer for 90 seconds, the mixture was supplied to the first main feed port from the upstream end of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The barrel temperature of the extruder was set to 210°C to 230°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h. If the mixture contained (XC), it was fed in through the feed port on the ninth barrel from the upstream end of the extruder, and melt-kneading was performed. Finally, after the mixture was taken up in strand form from the die, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0206] [Examples X3, X6, Comparative Examples X3, X6, Reference Example X3] The components (XA) to (XD) listed above were weighed in the proportions shown in Table 2 and mixed in a mixer for 90 seconds before being supplied to the first main feed port from the upstream end of a co-rotating twin-screw extruder (Toshiba Machine Co., Ltd. TEM58BS) with a screw diameter of 58 mm and an L / D ratio of 37 (9 barrels). The extruder barrel temperature was set to 210°C to 230°C, the screw rotation speed to 200 rpm, and the discharge rate to 120 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0207] [Examples X4, X5, X9] The components (XA) to (XD) listed above were weighed in the proportions shown in Table 2 and mixed in a mixer for 90 seconds before being supplied to the first main feed port from the upstream end of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 180°C to 200°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0208] [Comparative Example X7] The components (XA) to (XD) listed above were weighed in the proportions shown in Table 2 and mixed in a mixer for 90 seconds before being supplied to the first main feed port from the upstream end of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 230°C to 250°C, the screw rotation speed to 500 rpm, and the discharge rate to 50 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0209] [Example X8] The components (XA) to (XD) listed above were weighed in the proportions shown in Table 2 and mixed in a mixer for 90 seconds before being supplied to the first main feed port from the upstream end of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 100°C to 130°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0210] [Table 2]

[0211] As is clear from Table 2, Examples X1 to X10, which have a low oligomer content in the biomass resource-derived polyester elastomer and a low chemiluminescence emission amount of the polyester elastomer resin composition as defined in the present invention, exhibit excellent mechanical properties (tensile elongation at break and tensile strength at break), retention stability (ΔMFR), and elongation retention rate after moisture-resistant heat treatment (tensile elongation retention rate at break) of the polyester elastomer resin composition. Furthermore, Examples X3 to X5, X7, and X9 have high melt tension and excellent extrusion moldability and water aging resistance, making them suitable for extrusion molding into hoses, films, wire coatings, etc. Furthermore, as can be seen from the comparison between Example X1 and Comparative Example X1, Comparative Example X1, in which the oligomer content of the polyester elastomer was outside the specified range, exhibited poor retention stability and low elongation retention rate after heat treatment for moisture resistance (tensile elongation retention rate at break). In other words, it was suggested that oxidative degradation was more likely to occur in Comparative Example X1, where the chemiluminescence emission value was higher than the specified range of the present invention. Also, as can be seen from the comparison between Example X2, in which a thickener was added, and Comparative Example X2, in which the oligomer content of the polyester elastomer was higher than the specified range of the present invention, the melt tension did not increase easily even with the addition of a thickener. This tendency was particularly evident in Comparative Examples X4 to X6.

[0212] As can be seen from Examples X1-X3 and Reference Examples X1-X3, the effect of thickeners on improving melt tension is lower in Examples X1-X3, which use raw materials derived from biomass resources, compared to Reference Examples X1-X3, which use only raw materials derived from fossil fuel resources. From these findings, it can be seen that when using raw materials derived from biomass resources, in order to satisfy extrusion moldability and hose water aging resistance, not only the use of thickeners but also advanced design in combination with melt kneading conditions is required.

[0213] Furthermore, in Comparative Example X7, it is thought that the high temperature and high shear during the melt-kneading process using a twin-screw extruder led to polymer chain fragmentation and oxidation reactions, resulting in increased chemiluminescence emission and deterioration of ΔMFR and tensile elongation retention at break.

[0214] (Examples containing the flame retardant of the first embodiment) Furthermore, in the first embodiment, to evaluate flame retardancy, the polyester elastomer resin composition was further enriched with flame retardants and flame retardant enhancers for characterization. Details of these examples are shown below.

[0215] [Polyester elastomer (WA)] Polymerization example W1 2750 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1380 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 710 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C, below 1 Torr, to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of less than 1 Torr for 135 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (WA1).

[0216] Polymerization example W2 1550 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1170 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 2140 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 200°C over 180 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 90 minutes to 245°C, below 1 Torr, to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of less than 1 Torr for 115 minutes, and a polymer with a hard segment / soft segment mass ratio of 28 / 72 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (WA2).

[0217] Polymerization example W3 2750 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1380 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 710 parts by mass of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass 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 a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 245°C and below 1 Torr for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (WA3).

[0218] Polymerization example W4 2750 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1380 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 710 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C, below 1 Torr, to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of less than 1 Torr for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (WA4).

[0219] Polymerization example W5 2750 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1380 parts by mass of 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) derived from biomass resources, 710 parts by mass of polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) derived from biomass resources, 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 230°C and below 0.7 Torr over 65 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 255°C for 130 minutes under conditions of 0.7 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (WA5).

[0220] Polymerization example W6 2200g of dimethyl 2,6-naphthalenedicarboxylate (NDC, SK Petrochemical), 1250g of 1,4-butanediol (1,4-BDO, Mitsubishi Chemical), 1390g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, Mitsubishi Chemical), 2.4g of tetrabutyl titanate (TBT, Nacalai Tesque), and 6.0g of AO-330 (ADEKA) were placed in an autoclave and the temperature was raised from room temperature to 220°C over 90 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 90 minutes to 245°C, below 1 Torr, to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 245°C under a temperature below 1 Torr for 110 minutes, 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 (WA6).

[0221] Polymerization example W7 1450 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1720 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1670 parts by mass of biomass resource-derived dimer acid (C36DiCOOH, Propol1009, manufactured by Croda), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and heated from room temperature to 220°C over 120 minutes to carry out transesterification and esterification reactions. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C and below 1 Torr to carry out the initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C and below 1 Torr for 60 minutes, 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 (WA7).

[0222] Table 3 shows the composition and evaluation results of the polyester elastomers (WA1) to (WA7).

[0223] [Table 3]

[0224] [Flame Retardant (WB)] (WB1) Brominated polystyrene: PDBS-80, manufactured by Lanxess Co., Ltd. (WB2) Aluminum diethylphosphinate: EXOLIT OP1230, manufactured by Clariant Co., Ltd.

[0225] [Flame Retardant Auxiliary (WC)] (WC1) Antimony trioxide: Twinkling Star, manufactured by China Kogyo Co., Ltd.

[0226] [Heat Stabilizer (WD)] Hindered phenolic antioxidant: Irganox1010 (manufactured by BASF)

[0227] [Hydrolysis Resistant Agent (WE)] Alicyclic polycarbodiimide: Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Inc.

[0228] [Thickener (WF)] Triglycidyl isocyanurate compound: "TEPIC-S", manufactured by Nissan Chemical Corporation, epoxy value (average number of epoxy groups per molecule)

[0229] The polyester elastomers (WA1) to (WA7) used in the following Examples W1 to W7, Comparative Examples W1 to W9, and Reference Example W1 were vacuum-dried at 80°C for 8 hours before use.

[0230] [Comparative Examples W1 to W3, W8, Reference Example W1] The above components were weighed according to the mixing ratios shown in Table 4, mixed in a mixer for 90 seconds, and then supplied to the first main feed port from the upstream end of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 180°C to 240°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h, and melt-kneading was performed. Finally, after taking the material from the die in strand form, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0231] [Comparative Examples W4, W5] The above components were weighed according to the mixing ratios shown in Table 4 and supplied to the main feed port of a co-direction twin-screw extruder (Toshiba Machine Co., Ltd. TEM58BS) 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 to 360 rpm, and the discharge rate to 100 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0232] [Examples W1-W7, Comparative Examples W6, W7, W9] The above components were weighed according to the mixing ratios shown in Table 4. After mixing all components except the hydrolysis inhibitor in a mixer for 90 seconds, the mixture was supplied to the first main feed port from the upstream end of a co-rotating twin-screw extruder (TEX54αII, manufactured by Japan Steel Works, Ltd.) with a screw diameter of 58 mm and an L / D ratio of 53 (15 barrels). The barrel temperature of the extruder was set to 180°C to 240°C, the screw rotation speed to 160 rpm, and the discharge rate to 200 kg / h. If a hydrolysis inhibitor was included, it was fed in through the feed port on the 10th barrel from the upstream side of the extruder, and melt-kneading was performed. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0233] [Table 4]

[0234] As is clear from Table 4, Examples W1 to W7, in which the specific gravity, tensile elongation at break, and chemiluminescence emission amount of the polyester elastomer resin composition were within the range specified in the present invention, were excellent not only in the mechanical properties of the polyester elastomer resin composition (tensile elongation at break and tensile strength at break), but also in the tensile elongation retention rate, retention stability (ΔMFR), flame retardancy (UL-94: V-2 or higher, with variation), evaluation of gelled products, and extrusion moldability (pulsation, smoothness). Furthermore, as can be seen from the comparison between Comparative Example W1 and Reference Example W1, even when prepared under the same polymerization conditions, composition formulation, and melt-kneading conditions, the polyester elastomer resin composition derived from biomass resources (Comparative Example W1) was inferior to the polyester elastomer resin composition derived from fossil fuel resources (Reference Example W1) in mechanical properties, retention stability, and extrusion moldability (smoothness). Furthermore, in Comparative Example W2, which used a polyester elastomer with low reduced viscosity (WA4), the mechanical properties, retention stability, and extrusion moldability were significantly inferior to those of Comparative Example W1 and Reference Example W1. In addition, in Comparative Example W5, where the screw rotation speed was increased and the kneading was strengthened compared to Comparative Example W1, the mechanical properties and retention stability improved further, but the flame retardant underwent thermal decomposition due to shear heat generation during kneading, resulting in poor extrusion moldability. Moreover, the penetration of the flame retardant into the resin was poor, leading to variations in flame retardant content and poor dispersion. On the other hand, in Example W1, where the screw rotation speed was lowered and the L / D ratio was increased compared to Comparative Example W1, resulting in slower, longer melt kneading conditions, both the viscosity of the polymer and the dispersibility of the flame retardant were significantly improved, and the mechanical properties and extrusion moldability became equivalent to those of Reference Example W1, which uses a polyester elastomer derived from fossil fuel resources. Furthermore, even when the melt-kneading conditions were set in the same way as in Example W1, Comparative Example W6, which used a polyester elastomer (WA4) with low reduced viscosity and high oligomer content, and Comparative Example W7, which used a polyester elastomer (WA5) with equivalent reduced viscosity but high oligomer content, showed significantly inferior mechanical properties and extrusion moldability compared to Reference Example W1. In Comparative Example W9, where the flame retardant content was reduced to less than 1.20 compared to Example W4, V-2 was not achieved.

[0235] In Example W2, which used a polyester elastomer (WA2) with a high soft segment ratio and high reduced viscosity, excellent tensile elongation at break, tensile elongation retention rate, and extrusion moldability were observed despite the absence of a thickening agent. Furthermore, in Comparative Example W1, Comparative Example W8 (in which the polyester elastomer (WA1) in Example W1 was changed to polyester elastomer (WA2)), and Example W3, the tensile elongation at break was further improved. However, in Comparative Example W8, the amount of chemiluminescence emission was greater than the amount specified in the present invention, resulting in inferior tensile elongation retention rate.

[0236] In Example W4, where a hydrolysis inhibitor was added to the composition of Example W1, the retention stability was improved. In Example W5, where the flame retardant (WB1) in the composition of Example W1 was changed to a non-halo flame retardant (WB2), the mechanical properties and extrusion moldability were excellent, but the flame retardancy remained at V-2.

[0237] (Example of the second embodiment) [Polyester elastomer (YA)] Polymerization example Y1 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of 0.9 Torr or less for 125 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA1).

[0238] Polymerization example Y2 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 230°C over 135 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 0.9 Torr over 68 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of 0.9 Torr or less for 115 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA2).

[0239] Polymerization example Y3 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 235°C over 120 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 60 minutes to 255°C and below 0.8 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 255°C for 100 minutes under conditions of 0.8 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA3).

[0240] Polymerization Example Y4 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of 1,4-butanediol derived from biomass resources (Bio 1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO., LTD.), 750 parts by mass of polytetramethylene ether glycol derived from biomass resources (BioPTMG1000, number average molecular weight: 1000, manufactured by Mitsubishi Chemical Corporation), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 235°C over 120 minutes to carry out transesterification. Subsequently, the pressure inside the vessel was gradually reduced while the temperature was further raised, and the temperature and pressure were adjusted to 260°C and 0.7 Torr or less over 60 minutes to carry out an initial condensation reaction. Further, a polymerization reaction was carried out at 260°C under a condition of 0.7 Torr or less for 90 minutes, and a polymer having a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in a pellet form. The obtained polymer was designated as polyester elastomer (YA4).

[0241] Polymerization Example Y5 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 750 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C for 90 minutes under conditions of 0.9 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA5).

[0242] Polymerization example Y6 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 parts by mass of polytetramethylene ether glycol derived from fossil fuel resources (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were charged into an autoclave and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 245°C and below 0.9 Torr 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 as polyester elastomer (YA6).

[0243] Polymerization example Y7 2000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 parts by mass of polytetramethylene ether glycol derived from fossil fuel resources (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and the temperature was raised from room temperature to 235°C over 120 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 60 minutes to 260°C and below 0.7 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 260°C and below 0.7 Torr 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 as polyester elastomer (YA7).

[0244] Polymerization example Y8 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 900 parts by mass of 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) derived from biomass resources, 1190 parts by mass of polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) derived from biomass resources, 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of 0.9 Torr or less for 125 minutes, and a polymer with a hard segment / soft segment mass ratio of 45 / 55 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA8).

[0245] Polymerization example Y9 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 900 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 1190 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 230°C over 135 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 0.9 Torr over 68 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of 0.9 Torr or less for 115 minutes, and a polymer with a hard segment / soft segment mass ratio of 45 / 55 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA9).

[0246] Polymerization example Y10 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 900 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 1190 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 235°C over 120 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 0.8 Torr over 60 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of 0.9 Torr or less for 95 minutes, and a polymer with a hard segment / soft segment mass ratio of 45 / 55 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA10).

[0247] Polymerization example Y11 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 900 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1190 parts by mass of polytetramethylene ether glycol derived from fossil fuel resources (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 245°C and below 0.9 Torr for 80 minutes, and a polymer with a hard segment / soft segment mass ratio of 45 / 55 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (YA11).

[0248] Polymerization example Y12 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 860 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 1430 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 225°C over 150 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C and below 0.9 Torr to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions of 0.9 Torr or less for 125 minutes, and a polymer with a hard segment / soft segment mass ratio of 40 / 60 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (YA12).

[0249] Polymerization example Y13 1815 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1665 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 860 parts by mass of biomass resource-derived dimer acid (C36DiCOOH, Propol1009, manufactured by Croda), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and heated from room temperature to 220°C over 120 minutes to carry out transesterification and esterification reactions. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 75 minutes to 245°C, below 1 Torr, to carry out the initial condensation reaction. Furthermore, the polymerization reaction was carried out at 245°C under conditions below 1 Torr for 60 minutes, 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 (YA13).

[0250] Polymerization example Y14 A polymer was obtained in the same manner as in polymerization example 1, except that 1,4-butanediol derived from biomass resources (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) was replaced with 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical). The obtained polymer was designated as a polyester elastomer (YA14).

[0251] Table 5 shows the composition and evaluation results of the polyester elastomers (YA1) to (YA14).

[0252] [Table 5]

[0253] The polyester elastomers (YA1) to (YA14) used in the following Examples Y1 to Y7, Comparative Examples Y1 to Y6, and Reference Examples Y1 to Y3 were obtained by vacuum drying at 80°C for 8 hours.

[0254] [Resin compositions of Examples Y1, Y2, Y7, Comparative Examples Y1-Y3, and Reference Examples Y1 and Y2] 100 parts by mass of the polyester elastomer shown in Table 6 and 0.1 parts by mass of a heat stabilizer (hindered phenol antioxidant: Irganox 1010 (BASF)) were weighed and supplied to the main feed port of a co-direction twin-screw extruder (Toshiba Machine Co., Ltd. TEM58BS) with a screw diameter of 58 mm and an L / D ratio of 37 (9 barrels). The extruder barrel temperature was set to 210°C to 230°C, the screw rotation speed to 200 rpm, and the discharge rate to 120 kg / h, and melt mixing was performed. Finally, after taking the material from the die in strand form, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum dried overnight at 80°C and then subjected to each test.

[0255] [Resin compositions of Examples Y3-Y5, Comparative Examples Y4, Y5, and Reference Example Y3] 100 parts by mass of the polyester elastomer shown in Table 6 and 0.1 parts by mass of a heat stabilizer (hindered phenol antioxidant: Irganox 1010 (BASF)) were weighed and supplied to the first main feed port from the upstream of a co-screw extruder (Coperion STS-50) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 180°C to 200°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h, and melt mixing was performed. Finally, after taking the material from the die in strand form, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum dried overnight at 80°C and then subjected to each test.

[0256] [Resin composition of Example Y6] Using the YA1 polyester elastomer as the high-melting-point component, polyester elastomer resin composition pellets were obtained in the same manner as in Example 1 above. Furthermore, using the YA8 polyester elastomer as the low-melting-point component, polyester elastomer resin composition pellets were obtained in the same manner as in Example Y3 above.

[0257] [Resin composition of Comparative Example Y6] 100 parts by mass of the polyester elastomer shown in Table 6, 0.1 parts by mass of a thickener (triglycidyl isocyanurate compound: TEPIC-S (manufactured by Nissan Chemical Corporation)), and 0.1 parts by mass of a heat stabilizer (hindered phenol antioxidant: Irganox 1010 (manufactured by BASF)) were weighed and supplied to the first main feed port from the upstream of a co-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 180°C to 200°C, the screw rotation speed to 180 rpm, and the discharge rate to 50 kg / h, and melt mixing was performed. Finally, after taking the material from the die in strand form, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0258] [Monofilaments of Examples Y1-Y5, Y7, Comparative Examples Y1-Y5, and Reference Examples Y1-Y3] Polyester elastomer resin composition pellets were pre-dried for 4 hours under a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried under the same vacuum conditions at 120°C for 12 hours. The resulting dried pellets were melted using a spinning machine equipped with a melt extrusion device, and spinning was performed with the discharge rate adjusted to 22.2 g / min per nozzle hole (unit of monofilament). The extruded resin composition was cooled by passing it through a water bath of approximately 30°C with a 50 mm air gap, and then stretched four times between a Nelson roller and a take-up roller with the surface temperature adjusted to 90°C and the speed adjusted to 20 m / min. Subsequently, it was taken up by another pair of Nelson rollers while being relaxed by approximately 2% between slit-type heaters at 150°C, and immediately wound up. The fineness of the final yarn was approximately 2000 dtex.

[0259] [Monofilament of Example Y6] High-melting-point and low-melting-point polyester elastomer resin composition pellets were pre-dried for 4 hours under a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried under the same vacuum conditions at 120°C for 12 hours. Using a spinning machine with a double-tube composite nozzle and two pairs of melting extrusion devices, the two dried pellets were melted separately. At the meeting point, the low-melting-point component was used as the sheath and the high-melting-point component as the core, and the discharge rate was adjusted so that the cross-sectional area ratio of the sheath to the core was 20:80, and the total discharge rate of both was adjusted to 33.3 g / min per nozzle hole (unit of monofilament). The temperature of the meeting point was set to approximately 10°C higher than the melting point of the resin placed in the core of the high-melting-point component, and spinning was performed. The extruded resin composition was cooled by passing it through a water bath at approximately 30°C with a 50mm air gap. It was then stretched four times between a Nelson-type roller and a take-up roller, with the surface temperature adjusted to 90°C and the speed to 20m / min. Subsequently, it was taken up by another pair of Nelson rollers while being relaxed by approximately 2% between 150°C slit-type heaters, and immediately wound up. The fineness of the final yarn was approximately 2000 dtex.

[0260] [Table 6]

[0261] As is clear from Table 6, Examples Y1 to Y6, in which the Tm-VST and chemiluminescence emission amount of the polyester elastomer resin composition were within the range specified in the present invention, used polyester elastomer derived from biomass resources, but similar to Reference Examples Y1 to Y3, which used polyester elastomer derived from fossil resources, the monofilament elongation at break was 80% or more, the breaking strength was 1.2 cN / dtex or more, the elongation recovery rate after 30% elongation at 23°C was 90% or more, and the elongation recovery rate after 20% elongation at 80°C was 75% or more. The filament processability was also good, and a monofilament with excellent strength, elastic properties, elongation recovery rate, and filament processability was obtained. In Comparative Examples Y1 and Y2, since the Tm-VST was below the lower limit of the range specified in the present invention, the elongation recovery rate decreased, and the filament processability also tended to decrease. In Comparative Examples Y3 and Y6, since the chemiluminescence emission amount exceeded the upper limit of the range specified in the present invention, the mechanical properties decreased overall, and thread breakage occurred frequently. In comparative examples Y4 and Y5, since Tm-VST was above the upper limit of the range specified in the present invention, the strength tended to decrease and the filament processability also tended to decrease. Comparative Example Y3 and Reference Example Y1 differ only in whether or not biomass-derived raw materials were used. However, in Comparative Example Y3, the chemiluminescence emission amount exceeded the range specified in the present invention, suggesting that the use of biomass-derived raw materials makes the material more susceptible to acid value degradation. Comparative Example Y2 and Reference Example Y2 differ only in whether or not biomass-derived raw materials were used. However, Comparative Example Y2 showed a lower Vicat softening point, suggesting that the Vicat softening point tends to vary more when biomass-derived raw materials are used.

[0262] (Example of the third embodiment) [Polyester elastomer (ZA)] Polyester elastomer (ZA1) 2500 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1300 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 1230 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Subsequently, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 1 Torr over 70 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of less than 1 Torr for 130 minutes, and a polymer with a hard segment / soft segment mass ratio of 59 / 41 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (ZA1).

[0263] Polyester elastomer (ZA2) 1600 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1150 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by Mitsubishi Chemical), 2260 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and the temperature was raised from room temperature to 200°C over 165 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 85 minutes to 250°C and below 1 Torr to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 250°C and below 1 Torr for 110 minutes, and a polymer with a hard segment / soft segment mass ratio of 27 / 73 (mass%) was extracted in pellet form. The resulting polymer was designated as polyester elastomer (ZA2).

[0264] Polyester elastomer (ZA3) 2500 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1300 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1230 parts by mass of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass 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 a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 1 Torr over 70 minutes to carry out an initial condensation reaction. Furthermore, a polymerization reaction was carried out at 250°C and below 1 Torr for 85 minutes, and a polymer with a hard segment / soft segment mass ratio of 59 / 41 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (ZA3).

[0265] Polyester elastomer (ZA4) 2500 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1300 parts by mass of 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) derived from biomass resources, 1230 parts by mass of polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) derived from biomass resources, 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 250°C and below 1 Torr over 70 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C under conditions of less than 1 Torr for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 59 / 41 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (ZA4).

[0266] Polyester elastomer (ZA5) 2500 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1300 parts by mass of biomass-derived 1,4-butanediol (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.), 1230 parts by mass of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out a transesterification reaction. Then, the pressure inside the autoclave was gradually reduced and the temperature was further raised to 235°C and below 0.7 Torr over 60 minutes to carry out an initial condensation reaction. Furthermore, the polymerization reaction was carried out at 255°C for 130 minutes under conditions of 0.7 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 59 / 41 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (ZA5).

[0267] Polyester elastomer (ZA6) 2010 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1920 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 990 parts by mass of biomass resource-derived dimer acid (C36DiCOOH, Propol1009, manufactured by Croda), 2.4 parts by mass of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 parts by mass of AO-330 (manufactured by ADEKA) were placed in an autoclave and heated from room temperature to 220°C over 120 minutes to carry out transesterification and esterification reactions. Then, the pressure inside the autoclave was gradually reduced and the temperature was further increased over 70 minutes to 250°C and below 1 Torr to carry out the initial condensation reaction. Furthermore, the polymerization reaction was carried out at 250°C and below 1 Torr for 60 minutes, and a polymer with a hard segment / soft segment mass ratio of 66 / 34 (mass%) was extracted in pellet form. The obtained polymer was designated as polyester elastomer (ZA6).

[0268] Polyester elastomer (ZA7) A polymer was obtained in the same manner as ZA1, except that 1,4-butanediol derived from biomass resources (Bio1,4-BDO, manufactured by ZHEJIANG BOJU NEW MATERIAL CO.,LTD.) was replaced with 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical). The obtained polymer was designated as a polyester elastomer (ZA7).

[0269] Table 7 shows the composition and evaluation results of the polyester elastomers (ZA1) to (ZA7).

[0270] [Table 7]

[0271] [Heat stabilizer ZB] Hindered phenol antioxidant: Irganox 1010 (manufactured by BASF) [Hydrolysis inhibitor ZC] Alicyclic polycarbodiimide: Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Co., Ltd. [Thickener ZD] Triglycidyl isocyanurate compound: "TEPIC-S", manufactured by Nissan Chemical Corporation, epoxy valency (average number of epoxy groups per molecule) 3

[0272] The polyester elastomers (ZA1) to (ZA7) used in the following Examples Z1 to Z8, Comparative Examples Z1 to Z9, and Reference Examples Z1 to Z3 were obtained by vacuum drying at 80°C for 8 hours.

[0273] [Resin compositions of Examples Z1, Z2, Z6-Z8, Comparative Examples Z5, Z8, and Reference Example Z3] The above components were weighed according to the mixing ratios shown in Table 8. After mixing all components except the hydrolysis inhibitor in a mixer for 90 seconds, the mixture was supplied to the main feed port of a co-direction twin-screw extruder (Toshiba Machine Co., Ltd. TEM58SS) with a screw diameter of 58 mm and an L / D ratio of 45 (10 barrels). The extruder barrel temperature was set to 210°C to 230°C, the screw rotation speed to 200 rpm, and the discharge rate to 220 kg / h. When a hydrolysis inhibitor was included, it was fed in through a feed port located on the 7th barrel from the upstream side of the extruder, and melt-kneaded. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0274] [Resin compositions of Examples Z3, Z4, Comparative Examples Z1-Z4, Z6, Z7, Z9, and Reference Examples Z1, Z2] The above components were weighed according to the mixing ratios shown in Table 8 and supplied to the first main feed port from the upstream end of a co-screw extruder (STS-65, manufactured by Coperion) with a screw diameter of 62 mm and an L / D ratio of 48 (13 barrels). The extruder barrel temperature was set to 180°C to 240°C, the screw rotation speed to 120 rpm, and the discharge rate to 150 kg / h, and melt-kneading was performed. Finally, after taking the material from the die in strand form, it was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0275] [Resin composition of Example Z5] The above components were weighed according to the mixing ratios shown in Table 8, mixed in a mixer for 90 seconds, and then supplied to the first main feed port from the upstream end of a co-screwed twin-screw extruder (STS-50, manufactured by Coperion) with a screw diameter of 51 mm and an L / D ratio of 48 (14 barrels). The extruder barrel temperature was set to 180°C to 200°C, the screw rotation speed to 150 rpm, and the discharge rate to 80 kg / h, and melt-kneading was performed. Finally, after being taken up in strand form from the die, the mixture was cooled and solidified in a water bath, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried overnight at 80°C and then subjected to each test.

[0276] Next, a foamed molded body was produced using the polyester elastomer resin composition obtained above by the mold expansion method described above. The mold used was a flat plate production mold consisting of a fixed mold and a movable mold, which could form a cavity with a width of 100 mm, a length of 100 mm, and a thickness of 3 mm when the mold was clamped, and a cavity with the same width and length but a thickness of 3 mm + core back amount (mm) when the core was pushed back in the mold opening direction. Specifically, in the plasticizing region of an electric injection molding machine with a mold clamping force of 1800 kN, a screw diameter of 40 mm, and a screw stroke of 180 mm, supercritical nitrogen was injected, and after injection filling into the mold whose surface temperature was controlled to 50°C, a non-foamed skin layer of 100 to 800 μm was formed by the external injection pressure and internal foaming pressure. At this stage, the movable mold was moved 14 mm in the mold opening direction to expand the cavity volume and obtain a foamed molded body.

[0277] Table 8 shows the composition and physical properties of each resin composition in the examples, comparative examples, and reference examples, as well as the evaluation results of the foamed molded articles obtained therefrom.

[0278] [Table 8]

[0279] As is clear from Table 8, in Examples Z1 to Z8, where the MFR and chemiluminescence emission amount of the polyester elastomer resin composition fall within the range of the present invention, the Dv / Dn is 4 or less, with no or almost no coarse bubbles, the foamed molded body consists of closed cells, and a foamed molded body with a high resilience modulus of elasticity exceeding 60% and excellent compressive recovery force with a 50% constant displacement repeated compressive residual strain of 10% or less is obtained. On the other hand, in Comparative Examples Z1 to Z7 and Reference Example Z1, where the MFR of the polyester elastomer resin composition exceeds the upper limit of the range of the present invention, the Dv / Dn exceeds 4, and the resilience and compressive recovery force of the foamed molded body are inferior. In Comparative Example Z8, where the MFR is below the lower limit, the melt viscosity tends to be too high, making high-magnification foaming difficult, and gel-like material is also more likely to be generated. Furthermore, in Comparative Example Z9, although the MFR of the polyester elastomer resin composition was within the scope of the present invention, the amount of chemiluminescence emission exceeded the scope of the present invention. As a result, the Dv / Dn change rate exceeded 30% due to oxidative degradation, and the continuous moldability was also poor.

[0280] Furthermore, in Comparative Examples Z4, Z5, and Z7, where the chemiluminescence emission amount of the polyester elastomer resin composition exceeded the range of the present invention, the effect of the thickener on reducing MFR was low, suggesting that oxidative degradation occurred in the compound. [Industrial applicability]

[0281] Despite using a highly bio-based polyester elastomer derived from biomass resources, the polyester elastomer resin composition of the present invention exhibits minimal oxidative degradation and retains the excellent properties of fossil fuel-derived polyester elastomers. First, the polyester elastomer resin composition of the present invention maintains mechanical properties, retention stability, elongation retention after humid heat treatment, extrusion moldability, water aging resistance, and flame retardancy, making it suitable for applications requiring high-precision moldability and flame retardancy, such as hoses, tubes, cables, films, and wire coatings. Furthermore, the polyester elastomer resin composition of the present invention also possesses strength, elastic properties, elongation recovery properties, and filament processability, and is resistant to oxidative degradation, making it applicable to a wide range of fields, including textiles and nonwoven fabrics. Moreover, the polyester elastomer resin composition of the present invention also exhibits excellent foam moldability, resulting in foamed molded articles that maintain a uniform foamed state despite high foaming ratios, are lightweight, possess excellent compression recovery, and have a high rebound modulus. Therefore, the polyester elastomer resin composition of the present invention makes 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 in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 86%, the oligomer content in the biomass resource-derived polyester elastomer with a number average molecular weight of less than 1000 is 2.5% by weight or less, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ ５ A polyester elastomer resin composition characterized by being less than or equal to a count and satisfying any one of the following requirements (i), (ii), or (iii). (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising 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 is derived from fossil fuel resources, and the aliphatic and / or alicyclic diol and the aliphatic polyether are derived from biomass resources. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment comprising a dimer acid, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the dimer acid is derived from biomass resources. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising aromatic dicarboxylic acid and 1,4-butanediol is bonded to a soft segment made of aliphatic polyether, wherein the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and aliphatic polyether are derived from biomass resources.

2. A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20-86%, the 3% weight loss temperature when the polyester elastomer resin composition is heated from room temperature to 450°C at 10°C / min is 300°C or higher, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ ５ A polyester elastomer resin composition characterized by being less than or equal to a count and satisfying any one of the following requirements (i), (ii), or (iii). (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising 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 is derived from fossil fuel resources, and the aliphatic and / or alicyclic diol and the aliphatic polyether are derived from biomass resources. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment comprising a dimer acid, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the dimer acid is derived from biomass resources. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising aromatic dicarboxylic acid and 1,4-butanediol is bonded to a soft segment made of aliphatic polyether, wherein the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and aliphatic polyether are derived from biomass resources.

3. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the polyester elastomer resin composition further contains a thickening agent.

4. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN.

5. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the polyester elastomer resin composition further contains a hydrolysis inhibitor.

6. A hose obtained by extruding the polyester elastomer resin composition according to claim 1 or 2.

7. A film obtained by extruding the polyester elastomer resin composition according to claim 1 or 2.

8. A wire and cable covering material obtained by extruding the polyester elastomer resin composition according to claim 1 or 2.

9. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the polyester elastomer resin composition further contains a flame retardant.

10. The polyester elastomer resin composition according to claim 9, characterized in that the flame retardant content is 5 parts by mass or more per 100 parts by mass of polyester elastomer.

11. The polyester elastomer resin composition according to claim 10, characterized in that the specific gravity of the polyester elastomer resin composition is 1.20 or more, and the tensile elongation at break of the polyester elastomer resin composition is 200% or more.

12. The polyester elastomer resin composition according to claim 11, characterized in that, in accordance with the test method (Method A) described in JIS K7210, the difference (ΔMFR: MFR45 - MFR5) between the MFR value 45 minutes after the polyester elastomer resin composition was added (MFR45) and the MFR value 5 minutes after the addition (MFR5) of the melt flow rate (MFR: g / 10 min) of the polyester elastomer resin composition measured at the melting point of the polyester elastomer + 20°C and 2160 g is 25 or less.

13. The polyester elastomer resin composition according to claim 11, characterized in that the temperature at which 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.

14. The polyester elastomer resin composition according to claim 11, characterized in that the flame retardancy rating measured by UL94 is V-2, V-1, or V-0.

15. A wire and cable covering material using the polyester elastomer resin composition described in claim 11.

16. Electronic component using the polyester elastomer resin composition according to claim 11.

17. A monofilament using the polyester elastomer resin composition described in claim 11.

18. A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 85%, the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy 10°C ≤ Tm - VST ≤ 43°C, and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ ５ A polyester elastomer resin composition characterized by being less than or equal to a count and satisfying any one of the following requirements (i), (ii), or (iii). (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising 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 is derived from fossil fuel resources, and the aliphatic and / or alicyclic diol and the aliphatic polyether are derived from biomass resources. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment comprising a dimer acid, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the dimer acid is derived from biomass resources. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising aromatic dicarboxylic acid and 1,4-butanediol is bonded to a soft segment made of aliphatic polyether, wherein the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and aliphatic polyether are derived from biomass resources.

19. A woven fabric, knitted fabric, or nonwoven fabric characterized by containing a monofilament made of the polyester elastomer resin composition described in Claim 18 as a constituent material.

20. A composite monofilament having a core-sheath structure using the polyester elastomer resin composition according to claim 18, comprising two components with different melting points, characterized in that the core portion is formed from a high-melting-point component and the sheath portion from a low-melting-point component.

21. A highly elastic fabric made of a woven, knitted, or nonwoven fabric containing the composite monofilament described in claim 20 as a constituent material, characterized in that the low melting point component of the composite filament is fused at the monofilament intersection.

22. A polyester elastomer resin composition comprising a biomass resource-derived polyester elastomer in which at least one of the constituent components is derived from biomass resources, and a heat stabilizer, wherein the bio-basedness of the polyester elastomer resin composition is 20 to 85%, the MFR value of the polyester elastomer resin composition at a load of 2.16 kg measured in accordance with the flow test method for thermoplastics specified in JIS K7210 is 0.5 to 20 g / 10 min (measurement temperature: melting point + 20°C), and the chemiluminescence emission amount of the polyester elastomer resin composition is 4.0 × 10⁻⁶ ５ A polyester elastomer resin composition for foam molding, characterized in that it is less than or equal to a count and satisfies any one of the following requirements (i), (ii), or (iii). (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising 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 is derived from fossil fuel resources, and the aliphatic and / or alicyclic diol and the aliphatic polyether are derived from biomass resources. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment comprising a dimer acid, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the dimer acid is derived from biomass resources. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment made of polyester comprising aromatic dicarboxylic acid and 1,4-butanediol is bonded to a soft segment made of aliphatic polyether, wherein the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and aliphatic polyether are derived from biomass resources.

23. A footwear component comprising a polyester elastomer foam molded article obtained from the polyester elastomer resin composition described in Claim 22, wherein the polyester elastomer foam molded article has a rebound modulus of 60% or more.

24. The polyester elastomer resin composition according to any one of 1, 2, 18, or 22, characterized in that the aliphatic polyether derived from biomass resources in the biomass resource-derived polyester elastomer is polytetramethylene ether glycol.

25. A polyester elastomer resin composition according to any one of claims 1, 2, 18, or 22, characterized in that the reduced viscosity of the biomass resource-derived polyester elastomer is 1.2 dl / g or more.

26. A method for producing a polyester elastomer resin composition according to any one of claims 1, 2, 18, or 22, wherein the method comprises melt-kneading a biomass resource-derived polyester elastomer and a heat stabilizer using an extruder, and the conditions for melt-kneading satisfy at least one of the following (i) to (v): (i) The melting temperature of the resin composition during melt mixing is 100 to 300°C; (ii) The screw rotation speed of the extruder during melt mixing is 60 to 300 rpm; (iii) Vacuum degassing is performed in the molten kneading section after plasticization is complete; (iv) The ratio of the screw length L (mm) to the diameter D (mm) of the extruder is 20 ≤ (L / D) ≤ 70; (v) The discharge rate Q of the extruder is 30 to 500 kg / hr.

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