Resin composition using polyester elastomer derived from biomass resource

Abstract

Provided is a biomass resource-derived polyester elastomer resin composition combining excellent strength, elastic recovery properties, and filament processability of a fossil fuel resource-derived polyester elastomer even when the proportion of a biomass resource-derived raw material used in a polyester elastomer is increased. This polyester elastomer resin composition contains a heat stabilizer and a biomass resource-derived polyester elastomer in which at least one of constituent components is derived from a biomass resource, the polyester elastomer resin composition being characterized in that the polyester elastomer resin composition has a biobased content of 20%-100%, the polyester elastomer resin composition has a melting point (Tm) and a Vicat softening point (VST) satisfying the expression 10°C ≤ Tm - VST ≤ 43°C; and the polyester elastomer resin composition has a number average molecular weight (Mn) of 9,000 or more.

Description

Resin composition using biomass-derived polyester elastomer

[0001] The present invention relates to a biomass resource-derived polyester elastomer resin composition that uses a biomass resource-derived polyester elastomer with a high bio-based content, yet has the excellent strength, elastic properties, elastic recovery properties, and filament processability that are characteristic of fossil fuel resource-derived polyester elastomers.

[0002] In recent years, concerns about the depletion of fossil fuel resources and the increase in atmospheric carbon dioxide have become global environmental issues, and as a result, efforts are being made to convert various polymers from biomass. As biomass resources are renewable, they are expected to become an important design concept in future polymer development from the perspectives of SDGs and carbon neutrality.

[0003] However, because biomass resource-derived raw materials contain impurities that could not be completely removed during the refining process, increasing the proportion of biomass resource-derived raw materials in an attempt to increase the bio-based content of the polyester elastomer increases the amount of impurities, which in turn inhibits the reaction and prevents the reduced viscosity from increasing, making it difficult to maintain the excellent properties of fossil fuel resource-derived polyester elastomers.

[0004] Furthermore, numerous factors, such as impurities introduced into biomass-derived raw materials, oligomers, side reaction products, foreign matter, and undesigned polymers generated by polymerization reactions using these raw materials, make it difficult for polyester elastomers to demonstrate their inherent excellent molding design precision. For example, in the application of monofilaments, in order to design monofilaments that have sufficient mechanical properties to support static loads as fabric constituent materials and that exhibit minimal deterioration in mechanical properties even when deformed by repeated external forces, fossil fuel-derived polyester elastomers have been proposed that specify the characteristics of the soft segment constituent components in the polyester elastomer and the soft segment content (see Patent Document 1). However, biomass-derived polyester elastomers have problems such as poor polymer molecular designability and the influence of introduced impurities and foreign matter, making it difficult to achieve the desired properties.

[0005] To address this issue, it has been proposed to prevent a decline in the mechanical properties of polyesters made from biomass-derived dicarboxylic acids and / or diols by reducing the sulfur atom content and the amount of acid end groups (see Patent Document 2). While this biomass-derived polyester can prevent a decline in mechanical properties to some extent, it also causes discoloration of the polyester, which leads to poor appearance of molded products. Furthermore, it fails to maintain the excellent properties of fossil-fuel-derived polyesters in terms of elasticity, elastic recovery, and filament processability.

[0006] Patent No. 4018251 Patent No. 5303237

[0007] The present invention was made in view of the current state of the prior art, and its object is to provide a biomass resource-derived polyester elastomer resin composition that has the excellent strength, elastic properties, elastic recovery properties, and filament processability of fossil fuel resource-derived polyester elastomers, even when the proportion of biomass resource-derived raw materials used in the polyester elastomer is increased, and to provide monofilaments, composite monofilaments, and highly elastic fabrics containing the same.

[0008] As a result of extensive research to achieve this object, the present inventors have discovered that, in a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer with a high bio-based content 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 number average molecular weight of the polyester elastomer resin composition to a predetermined value or higher, it is possible to provide a biomass resource-derived polyester elastomer resin composition that combines the excellent strength, elastic properties, elastic recovery properties, and filament processability of polyester elastomers derived from fossil fuel resources, and have completed the present invention.

[0009] That is, the present invention comprises the following (1) to (11): (1) A polyester elastomer resin composition containing a biomass resource-derived polyester elastomer, at least one of whose constituent components is derived from a biomass resource, and a heat stabilizer, wherein the polyester elastomer resin composition has a biobased content of 20 to 100%, the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition satisfy the relationship 10°C≦Tm−VST≦43°C, and the number average molecular weight (Mn) of the polyester elastomer resin composition is 9,000 or more. (2) The polyester elastomer resin composition according to (1), wherein, when the weight average molecular weight (Mw) of the polyester elastomer resin composition is taken as Mw / Mn≦5.0. (3) The polyester elastomer resin composition according to (1), comprising a polyester elastomer having a hard segment / soft segment mass ratio of 40 / 60 to 80 / 20. (4) The polyester elastomer resin composition according to (1), wherein the biomass resource-derived polyester elastomer is a polyester elastomer having hard segments composed of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components, and soft segments composed of an aliphatic polyether as constituent components, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource. (5) The polyester elastomer resin composition according to (4), wherein the biomass resource-derived aliphatic polyether of the biomass resource-derived polyester elastomer is polytetramethylene ether glycol. (6) The polyester elastomer resin composition according to (4), wherein the biomass resource-derived polyester elastomer has a reduced viscosity of 1.2 dl / g or more. (7) A monofilament comprising the polyester elastomer resin composition according to any one of (1) to (6).(8) The monofilament according to (7), characterized in that it has a breaking elongation of 80% or more, a breaking strength of 1.2 cN / dtex or more, an elongation recovery rate after 30% elongation at 23°C of 90% or more, and an elongation recovery rate after 20% elongation at 80°C of 80% or more. (9) A woven fabric, knitted fabric, or nonwoven fabric characterized in that it contains the monofilament according to (7) as a constituent material. (10) A composite monofilament having a core-sheath structure using the polyester elastomer resin composition according to any one of (1) to (6) containing two components with different melting points, the composite monofilament being characterized in that the core is formed from a high-melting-point component and the sheath is formed from a low-melting-point component. (11) A highly elastic fabric consisting of a woven fabric, knitted fabric, or nonwoven fabric containing the composite monofilament according to (10) as a constituent material, characterized in that the low-melting-point components of the composite filament are fused at the intersections of the monofilaments.

[0010] The polyester elastomer resin composition of the present invention, even when using a higher proportion of biomass-derived raw materials, retains the excellent strength, elastic properties, elastic recovery properties, and filament processability of fossil-fuel-derived polyester elastomers. Therefore, the polyester elastomer resin composition of the present invention can be used as a substitute for fossil-fuel-derived polyester elastomers, for example, in reinforcing materials for various membranes, netting, seating materials for office and vehicle use, high-elasticity composite monofilaments, and high-elasticity fabrics made therefrom. Therefore, the biomass-derived polyester elastomer of the present invention can significantly contribute to solving global environmental problems, such as the depletion of fossil fuel resources.

[0011] The polyester elastomer resin composition of the present invention is a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer with a specific high bio-based content and a heat stabilizer, and is characterized in that the relationship between the melting point (Tm) and Vicat softening point (VST) of the polyester elastomer resin composition and the number average molecular weight (Mn) are set within specific ranges.

[0012] The biomass resource-derived polyester elastomer used in the resin composition of the present invention is preferably a polyester elastomer in which a hard segment made of a polyester having as its constituent components an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol is bonded to a soft segment made of an aliphatic polyether. It is preferable that the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource.

[0013] As the aromatic dicarboxylic acid constituting the polyester of the hard segment, 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, and even more preferably 90 mol% or more, of all the dicarboxylic acids constituting the polyester of the hard segment, and may be 100 mol%. Examples of dicarboxylic acid components other than terephthalic acid and naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid, and 5-sodiumsulfoisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride; and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These dicarboxylic acids can be used in a range that does not significantly lower the melting point of the resin, and the amount is preferably 30 mol % or less of the total acid components, more preferably 20 mol % or less, and even more preferably 10 mol % or less, and may be 0 mol %. When these dicarboxylic acids are used as raw materials for polyester elastomers, they may be in the form of esters of the dicarboxylic acids. For example, terephthalic acid and dimethyl terephthalate can also be used as raw materials.

[0014] Furthermore, as the aliphatic or alicyclic diol constituting the polyester of the hard segment, general aliphatic or alicyclic diols are widely used and are not particularly limited, but alkylene glycols mainly having 2 to 8 carbon atoms are preferred. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. Of these, either ethylene glycol or 1,4-butanediol is preferred.

[0015] As the component constituting the polyester of the hard segment, those comprising butylene terephthalate units (units consisting of terephthalic acid and 1,4-butanediol) or butylene naphthalate units (units consisting of 2,6-naphthalenedicarboxylic acid and 1,4-butanediol) are preferred in terms of physical properties, moldability, and cost performance.

[0016] Alternatively, when an aromatic polyester suitable for forming the hard segment of the polyester elastomer is prepared in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained according to a conventional polyester production method. The polyester preferably has a number average molecular weight of 10,000 to 40,000.

[0017] 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. Specific examples include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, polytetramethylene ether glycol, polytrimethylene ether glycol, poly(hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide adduct of poly(propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol and an ethylene oxide adduct of poly(propylene oxide) glycol are preferred from the viewpoint of elastic properties.

[0018] In the present invention, the aliphatic polyether constituting the soft segment is preferably derived from a biomass resource, particularly polytetramethylene ether glycol (PTMG) derived from a biomass resource. Commercially available PTMG can be used, and preferred examples include BioPTMG1000 and BioPTMG2000 manufactured by Mitsubishi Chemical Corporation.

[0019] The polyester elastomer is preferably a copolymer primarily composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol. Of the dicarboxylic acid components constituting the polyester elastomer, terephthalic acid preferably accounts for 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Of the glycol components constituting the polyester elastomer, the total of 1,4-butanediol and polytetramethylene ether glycol is preferably 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

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

[0021] In the present invention, the mass of the hard segment refers to the mass of the component composed of an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol, and the mass of the soft segment refers to the mass of the component composed of an aliphatic dicarboxylic acid and / or an aliphatic polyether. For example, in the case of a polyester elastomer composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol (PTMG), the mass of the hard segment is the mass of butylene terephthalate units (condensation units of terephthalic acid and 1,4-butanediol), and the mass of the soft segment is the mass of polytetramethylene ether glycol (PTMG).

[0022] The melting point of the polyester elastomer is preferably 150 to 230° C. If the melting point is below 150° C., the polyester elastomer may not have satisfactory heat aging resistance and moldability (crystallinity). Conversely, if the melting point is above 230° C., the polyester elastomer may contain a large amount of hard segments, resulting in a correspondingly high glass transition temperature (Tg), and may not have satisfactory impact resilience, flexibility, and low-temperature mechanical properties.

[0023] Any known method can be used to produce a polyester elastomer. For example, melt polymerization, solution polymerization, solid-state polymerization, or the like can be used as appropriate. In the case of melt polymerization, either transesterification or direct polymerization can be used. For example, a method can be used in which a dicarboxylic acid component and a diol component are reacted to form a prepolymer by transesterification, direct esterification, or the like, followed by polycondensation under reduced pressure. In this case, a catalyst for transesterification or esterification, or a catalyst for polycondensation can be used as appropriate. Furthermore, chain extension can be performed after polymerization using an isocyanate compound, an epoxy compound, or the like. Furthermore, solid-state polymerization can improve melt tension during the polymerization process.

[0024] To produce the polyester elastomer of the present invention, it is preferable to extend the polycondensation time compared to conventional methods. For example, in the polycondensation of polyester elastomers using butylene terephthalate units as the hard segment constituent and polytetramethylene ether glycol as the soft segment constituent, the polycondensation time for producing polyester elastomers is typically about 50 to 90 minutes. In the present invention, however, the polycondensation time is preferably 100 to 140 minutes, more preferably 105 to 135 minutes. It is also preferable to control the polycondensation temperature within a narrow range. Typically, the polycondensation temperature for producing polyester elastomers is about 235 to 260°C. In the present invention, however, the polycondensation temperature is preferably 235 to 255°C, more preferably 240 to 250°C. If the polycondensation time is too short or the polycondensation temperature is too low, the polymerization reaction may not proceed smoothly, resulting in a high oligomer content or an increased acid value of the system. Furthermore, the reduced viscosity of the polyester elastomer may not increase, and the elongation at break and tensile strength at break may not satisfy the functions required for a polyester elastomer, and the retention stability may deteriorate. Conversely, if the polycondensation time is long or the polycondensation temperature is high, thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and accelerating the formation of oligomers and gelation. Furthermore, the pressure is gradually reduced from the pressure used for the transesterification reaction, with the final pressure preferably being 0.1 to 3 Torr, and more preferably 0.04 to 0.2 kPa. If the pressure exceeds the upper limit, reactivity may decrease, the reaction time may be prolonged, and thermal decomposition may cause discoloration of the polyester elastomer, worsening its appearance, and accelerating the formation of oligomers and gelation. On the other hand, if the pressure is too low, there is a risk of compositional deviation due to excessive volatilization or distillation of monomers, or a delay in the polymerization reaction due to excessively reduced intermolecular collisions. The polycondensation conditions must be adjusted appropriately depending on the constituent components.

[0025] The biobased content of the polyester elastomer of the present invention, expressed as the biobased content of the resin composition including components such as a heat stabilizer, is 20 to 100%, preferably 20 to 99.9%, more preferably 20 to 99%, even more preferably 20 to 85%, particularly preferably 25 to 80%, and most preferably 25 to 50%. The biobased content of the polyester elastomer is preferably 20 to 100%, more preferably 20 to 85%, even more preferably 25 to 80%, and particularly preferably 25 to 50%. Conventionally, biomass-derived raw materials contain impurities that cannot be completely removed during the purification process. Therefore, increasing the proportion of biomass-derived raw materials in an attempt to increase the biobased content has resulted in problems such as an increase in the amount of impurities, which inhibits the reaction, prevents an increase in reduced viscosity, prolongs the polymerization time, and causes discoloration. Therefore, it has been difficult to obtain a biomass-derived polyester elastomer that can prevent discoloration without reducing production efficiency and maintains excellent flexibility, low-temperature mechanical properties, heat aging resistance, and water resistance. In the present invention, as polymerization raw materials for the polyester elastomer, materials derived from fossil fuel resources are used for the hard segments, and an aliphatic polyether is used as a raw material derived from biomass resources only for the soft segments. By adopting an appropriate polycondensation reaction time and temperature, it is possible to obtain a biomass resource-derived polyester elastomer that is free of coloration and that retains the excellent properties of fossil fuel resource-derived polyester elastomers.

[0026] In the present invention, the reduced viscosity (ηsp / c) of the polyester elastomer is preferably 1.2 dL / g or more, more preferably 1.7 dL / g or more, and even more preferably 1.4 dL / g or more. If the reduced viscosity is low, the molecular weight is small, and the polyester elastomer may not be able to satisfy the long-term durability (heat aging resistance, water resistance) required.

[0027] The composition and composition ratio of the polyester elastomer of the present invention can be determined by dissolving a sample in a solvent such as deuterated chloroform and measuring the composition. １ It can also be calculated from the proton integral ratio of H-NMR.

[0028] 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. The polyester elastomer resin composition of the present invention may also optionally contain a thickener and / or a hydrolysis inhibitor.

[0029] Heat stabilizers are used to prevent thermal oxidative decomposition during compounding and spinning. Examples of heat stabilizers that can be used include known hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. The blending amount of the 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. If the amount of heat stabilizer is too small, the effect of preventing thermal oxidative decomposition will be insufficient, and if the amount is too large, mechanical properties may be reduced.

[0030] 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)butyric acid]glycol ester, tripheno 2,2'-ethylidenebis(4,6-di-t-butylphenol), N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isothiazolinone cyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic amide triester with-1,3,5-tris(2-hydroxyethyl)-S-triazine-2,4,6(1H,3H,5H), N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnaamide), 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like.

[0031] Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodiuropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, dilaurylthiodipropionate, dioctadecyl sulfide, and pentaerythryl-tetra(β-lauryl-thiopropionate) ester.

[0032] Examples of phosphorus-based antioxidants include tris(mixed, mono- and diolylphenyl)phosphite, tris(2,3-di-t-butylphenyl)phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphanite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene diphosphonite, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite, and the like can be mentioned.

[0033] Examples of the amine antioxidant include amines such as N,N-diphenylethylenediamine, N,N-diphenylacetamidine, N,N-diphenylformamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N,N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane, P,P'-dioctyl-diphenylamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, and 4,4'-bis(4-α,α-dimethyl-benzyl)diphenylamine, and derivatives thereof, reaction products of amines and aldehydes, and reaction products of amines and ketones.

[0034] In addition to the above components, the polyester elastomer resin composition of the present invention can contain various additives depending on the purpose, including known light stabilizers such as hindered amines, triazoles, benzophenones, benzoates, nickel, and salicylic acids, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, and organic and inorganic pigments.

[0035] The polyester elastomer resin composition of the present invention may further contain a rigid polyester. By adding the rigid polyester, the strength and processability of the resulting polyester elastomer resin composition can be adjusted.

[0036] Rigid polyesters are obtained by polycondensation of at least one acid component selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, etc., with at least one diol component selected from polyalkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polytetramethylene glycol, etc. Specific 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, etc., as well as copolymer polyesters such as polyethylene isophthalate terephthalate (PET / I) and polybutylene isophthalate isophthalate (PET / I). Of these rigid polyesters, PBT is most preferred from the viewpoint of compatibility with polyester elastomers.

[0037] The amount of hard polyester blended is preferably up to 150 parts by mass, more preferably up to 100 parts by mass, per 100 parts by mass of polyester elastomer. Blending a large amount of hard polyester may result in a decrease in elastic properties and a decrease in elastic recovery.

[0038] The polyester elastomer resin composition of the present invention is characterized in that its melting point (Tm) and Vicat softening point (VST) satisfy the relationship 10°C≦Tm−VST≦43°C. The melting point (Tm) is a value measured in accordance with ASTM D-3418. The Vicat softening point (VST) is a value measured in accordance with ISO 306 (2013) A50 method. Specifically, the VST is the temperature at which a flat-tipped needle penetrates 1 mm into a test specimen when a test load of 10 N is applied perpendicularly to the test specimen while the specimen is heated in an oil bath at a temperature increase rate of 50°C / hr. Tm−VST is preferably in the range of 11 to 42°C, more preferably 12 to 41°C, and particularly preferably 13 to 40°C. By satisfying the above range of Tm−VST, a polyester elastomer resin composition having a good balance between mechanical strength and elastic recovery can be obtained. If Tm-VST is smaller than the above range, the elastic recovery rate tends to decrease, and if it is larger than the above range, the mechanical strength such as tensile strength at break tends to decrease. When the constituent components of a polyester elastomer are the same, the melting point (Tm) tends to be determined by the charge ratio of the hard segment component to the soft segment component during polymerization. On the other hand, the Vicat softening point also depends on the block state and tends to vary depending on the polymerization conditions.

[0039] In order to ensure that the Tm-VST of the polyester elastomer resin composition of the present invention satisfies the above range, it is preferable to take measures such as setting the mass ratio of hard segments to soft segments of the polyester elastomer used to preferably 35 / 65 to 90 / 10, more preferably 38 / 62 to 85 / 15, even more preferably 40 / 60 to 80 / 20, and particularly preferably 42 / 58 to 75 / 25, or extending the polymerization time. By setting the mass ratio within the above range, it becomes easier to satisfy the Tm-VST requirement when adjusting the polymerization conditions, and it becomes easier to obtain a polyester elastomer resin composition with a good balance between mechanical strength and elastic recovery.

[0040] The polyester elastomer resin composition of the present invention is characterized by its number average molecular weight (Mn) of 9,000 or more. Mn is preferably 10,000 or more, 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 more, the mechanical strength, mechanical elongation, elastic recovery, and filament processability are excellent.

[0041] Furthermore, it is preferable that the polyester elastomer resin composition of the present invention satisfy Mw / Mn≦5. This tends to result in a polyester elastomer with a good balance between mechanical strength and elastic recovery. There are no particular limitations on the method for satisfying Mw / Mn≦5. However, since a fast polymerization rate tends to increase Mw / Mn, 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).

[0042] 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 yarn breakage tends to be reduced. In addition, the composition has excellent hydrolysis resistance.

[0043] The method for producing the polyester elastomer resin composition of the present invention is not particularly limited, but it can be produced by melt-kneading each component using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, roll, or the like known to those skilled in the art.

[0044] When using a twin-screw extruder, it is preferable to appropriately select the extruder barrel temperature and screw configuration to control the resin pressure in the extruder plasticization section. When melt-kneading the above components, it is important to allow the molten components to coexist with the molten polymer phase in the polymer plasticization region, increase the polymer viscosity as the matrix phase, and use shear stress to uniformly melt the molten components into the polymer phase, while controlling internal heat generation to suppress polymer degradation and side reactions. The resin pressure is preferably about 0.1 to 1 MPa.

[0045] The melting temperature of the resin composition during melt-kneading is preferably 160 to 300° C., and more preferably 180 to 280° C. If the melting temperature is low, the resin composition will not melt sufficiently and will tend to produce a large number of unmelted gels, whereas if the resin temperature is high, the resin composition will be prone to thermal degradation.

[0046] The screw rotation speed during melt-kneading is preferably 50 to 500 rpm, more preferably 100 to 300 rpm. If the screw rotation speed is low, the components tend not to melt and react uniformly, while if it is high, shear heat generation may occur, which may cause polymer deterioration or side reactions. The discharge rate Q is preferably 5 to 1,000 kg / hr, more preferably 10 to 500 kg / hr. If the discharge rate is low, the resin filling rate in the extruder tends to decrease, resulting in uneven kneading. Conversely, if the discharge rate is high, the resin filling rate in the extruder tends to become too high, resulting in uneven kneading.

[0047] Because the polyester elastomer resin composition of the present invention is configured as described above, it uses a polyester elastomer derived from a biomass resource with a high biomass content, yet possesses the excellent strength, elastic properties, elastic recovery properties, and filament processability of polyester elastomers derived from fossil fuel resources, and is therefore usable for applications in the fields of fibers and nonwoven fabrics, for example, fibers such as continuous spinning, staple fibers, and monofilaments, sanitary materials such as disposable diapers, medical applications such as surgical clothing and gloves, carpets, their linings, ropes, etc. Furthermore, it can be used for applications such as canvas, tent materials, and synthetic leather materials, which are formed by laminating these nonwoven fabrics, monofilaments, or knitted fabrics with films or sheets.

[0048] Specifically, a monofilament can be produced using the polyester elastomer resin composition of the present invention by using a conventional melt spinning apparatus, in which the polyester elastomer resin composition is supplied to a known melt spinning machine, melt-kneaded, and then extruded through a spinneret hole.

[0049] From the viewpoint of spinnability, the number average molecular weight (Mn) of the polyester elastomer resin composition is preferably 9,000 or more. If Mn is low, the strength is insufficient and the composition cannot withstand high-speed spinning, leading to thread breakage. From the same viewpoint, Mw / Mn is preferably less than 5. If Mw / Mn is high, the polyester elastomer resin composition is prone to thermal degradation and breakage, or it often contains gel-like matter that causes breakage. Furthermore, the properties of the resin composition are prone to variation, which can lead to thread breakage.

[0050] The monofilament made of 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 shock-absorbing structure made of the monofilament may be inferior. On the other hand, the diameter of the monofilament is preferably 1.5 mm or less. If a monofilament with a diameter of more than 1.5 mm is used, the processability during processing is likely to be poor.

[0051] The monofilament made from the polyester elastomer resin composition of the present invention can be used to prepare a composite filament using two polyester elastomer resin compositions with different melting points. In this case, the area ratio of the low-melting component in any cross section is preferably 50% or less. In the composite filament made from two polyester elastomer components with different melting points, the melting point of the high-melting component constituting the monofilament is preferably 150°C or higher and lower than 200°C, and the melting point of the low-melting component is preferably 20°C or higher and lower than 50°C.

[0052] The composite monofilament of the present invention is an anisotropic composite of two polymer components, a high-melting point component and a low-melting point component, with respect to the cross-sectional direction of the filament. The two components may be in a core-sheath, side-by-side, or radial configuration, or in a so-called sea-island configuration in which one component has the other component dispersed in the form of several small islands, or even in a configuration in which the two components are joined at a portion of the periphery. The shape and form of the composite monofilament are not particularly limited, but it is preferable that the composite monofilament have a core-sheath structure in which the core is formed from the high-melting point component and the sheath is formed from the low-melting point component.

[0053] 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 highly elastic knitted fabrics, woven fabrics, or nonwoven fabrics that have sufficient mechanical strength to support a load, cushioning properties, and durability against repeated stress, the breaking elongation of the monofilaments is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more. If the breaking elongation is below the above range, the resulting fabric will not have sufficient elastomeric properties.

[0054] The breaking strength of the monofilament is preferably 1.2 cN / dtex or more, more preferably 1.3 cN / dtex or more, and even more preferably 1.4 cN / dtex or more. If the breaking strength is below the above range, the strength of the resulting fabric is insufficient and tends to be insufficient against static load. However, if the fiber strength exceeds 4.0 cN / dtex, the initial load gradient when made into a fabric rises sharply, which is undesirable from the standpoint of fabric design.

[0055] 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. 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 the elongation recovery rate is lower than the above range, the elastic properties will deteriorate with repeated use and the fabric will be more likely to become loose.

[0056] In order to improve the binding force of the composite monofilament of the present invention, it is possible to use the composite monofilament in one or both of the warp and weft directions to form a woven fabric or a nonwoven fabric, and then to form a joining point at the filament intersection by partially melting or fusing the low-melting point component without substantially affecting the high-melting point component of the two components, thereby preventing deformation of the knitted / woven structure during repeated deformation of the fabric and imparting long-term durability, thereby providing a fabric that maintains a high level of elastic recovery for a long period of time.

[0057] The polyester elastomer resin composition of the present invention can be molded into various shapes by extrusion molding, injection molding, transfer molding, blow molding, etc., in addition to being processed into monofilaments.

[0058] The various molded products produced by the above processing method can be suitably used for various parts such as automobile parts, electrical and electronic parts, building materials, various containers, daily necessities, household goods, cosmetic parts, sanitary products, and medical (medical treatment) parts.

[0059] More specifically, examples of automotive parts include 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, interior parts such as knobs, levers, and clips, electrical system parts including meters, connectors, automotive cable covers, wire covering materials, and various cable and hose parts such as corrugated tubes, in-vehicle electrical and electronic parts such as audio equipment and car navigation equipment, parts that come into contact with metal such as window regulator carrier plates, 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 portions.

[0060] Examples of electric and electronic parts (mechanical parts) include rubber parts for OA (office automation) equipment such as audio equipment, video equipment, projectors, copiers, facsimiles, and personal computers, toys, telephones, and optical and magnetic media parts.

[0061] The material is also suitable for use in a wide range of lifestyle, cosmetic, and medical applications, including building materials and piping parts such as lighting fixtures, fittings, piping, and toilet peripheral parts; apparel materials such as fasteners (slide fasteners, snap fasteners, hook-and-loop fasteners, rail fasteners, etc.); sports shoes, leisure shoes, fashion sandals, leather shoes, and ski shoes; balls such as golf balls and tennis balls; various brushes such as hairbrushes; everyday items such as combs, hot curlers, and watch bands; stationery; cosmetic containers including lip balm and lipstick; cleaning devices, water purifiers, spray nozzles, spray containers, aerosol containers; general containers; food packaging; packaging for daily necessities; and film applications such as elastic tape used in disposable diapers; syringe covers and sealing; office furniture such as office chairs; and cushioning functional components for furniture such as cushions and beds.

[0062] Furthermore, it can be suitably used for various adhesives and pressure-sensitive adhesives such as hot melt types, various resin modifiers, road paving materials, waterproof sheets, asphalt blend materials such as pipe coatings, industrial material packaging, laminates for various rubber products, resin products, fabrics, leather products, etc., retainers, conveyor belts, and other industrial machinery components, and 3D printer filaments.

[0063] The following examples are provided to demonstrate the effects of the present invention, but the present invention is not limited to these examples. The property values ​​were evaluated by the following methods. The raw materials used in the examples, and those not otherwise specified, are derived from fossil fuel resources.

[0064] (1) Bio-based Degree The bio-based degree of a polyester elastomer is the ratio of the biomass-derived monomer components to the total mass of the monomer components that make up the polyester elastomer, calculated from the mass of the biomass-derived monomer components. The bio-based degree is the ratio of the amount of carbon that is only contained in the biomass-derived raw materials to the total carbon contained in the polyester elastomer. １４ C carbon ( １２The biobased content (%) of the polyester elastomer was measured using an accelerator mass spectrometer (AMS) in accordance with ASTM D6866. On the other hand, the biobased content of a polyester elastomer resin composition is the proportion of monomer components derived from biomass resources, calculated from the mass of monomer components derived from biomass resources relative to the mass of all monomer components constituting the polyester elastomer resin composition. The biobased content is the ratio of the amount of monomer components derived from biomass resources that are only contained in raw materials derived from biomass resources relative to the total carbon contained in the polyester elastomer resin composition. １４ C carbon ( １２ The biobased content (%) of the polyester elastomer resin composition was measured using an accelerator mass spectrometer (AMS) in accordance with ASTM D6866.

[0065] (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 viscometer.

[0066] (3) Melting Point (Tm) Using a differential scanning calorimeter "DSC220" manufactured by Seiko Instruments Inc., 5 mg of a measurement sample was placed in an aluminum pan, the pan was sealed with a lid, and the sample was melted in nitrogen at 250°C for 2 minutes. The sample was then cooled to 50°C at a rate of 20°C / min, and then heated from 50°C to 250°C at a rate of 20°C / min. The endothermic peak due to melting was determined from the obtained thermogram curve, and this was designated as the melting point (°C).

[0067] (4) Vicat Softening Point (VST) In accordance with the A50 method of ISO 306 (2013), a test specimen was heated in an oil bath at a heating rate of 50°C / hr. A test load of 10 N was applied perpendicularly to the test specimen with a flat-tipped needle. The Vicat softening point (VST) was the temperature at which the needle penetrated 1 mm into the test specimen. The test specimens were prepared as follows. (Test Specimen Preparation Method) 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 100 mm x 100 mm x 2 mm flat plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) at a cylinder temperature of (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.

[0068] (5) Tm-VST: Calculated from the difference between the Tm value and the VST value obtained in (3) and (4).

[0069] (6) Mn, Mw / Mn 8 mg of a 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 molecular weights Mn and Mw were calculated in terms of polymethyl methacrylate (PMMA), and Mw / Mn was calculated from these calculated values. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated by excluding values ​​of Mw < 1000 and Mn < 1000. The molecular weight distribution was also calculated by dividing the weight-average molecular weight by the number-average molecular weight, using the weight-average molecular weight and number-average molecular weight excluding values ​​less than 1000, as described above. Apparatus: TOSOH HLC-8320GPC Column: TOSOH TSKgel SuperHM-H x 2 + TSKgel SuperH2000 Solvent: HFIP / sodium trifluoroacetate 10 mM Flow rate: 0.2 ml / min Injection volume: 10 μl Temperature: 40°C Detector: RI Concentration: 0.2%

[0070] (7) Breaking Strength and Breaking Elongation Using a Tensilon™ measuring device manufactured by Orientec Co., Ltd., a monofilament sample having a length of 100 mm was measured at a strain rate of 100% / min under an atmosphere of 25% temperature and 65% relative humidity, and the breaking strength and breaking elongation were evaluated from the strain-stress curve obtained. The measurements were each taken as an average of five times.

[0071] (8) Elongation recovery rate after 30% elongation at 23°C, elongation recovery rate after 20% elongation at 80°C A heating bath adjusted to a temperature of 23°C or 80°C was placed in the above-mentioned measuring device, and a monofilament sample of 100 mm length was placed in the heating bath. After heating for 2 minutes, the sample was elongated to 20% or 30% at a strain rate of 100% / min and immediately returned to 0% at the same rate. Ten seconds after the return to normal, the sample was again elongated to 20% or 30% at the same rate. From the series of strain-stress curves recorded at this time, the strain amount x (%) at which stress began to be generated by the second elongation was determined, and the elongation recovery rate was evaluated using the following formula: Elongation recovery rate (%) = 100 - x

[0072] (9) Filament Processability Continuous spinning was carried out for 6 hours, and thread breakage was evaluated according to the following criteria: ○: No thread breakage occurred △: 1 to 2 thread breakages occurred ×: 3 or more thread breakages occurred

[0073] The monofilaments used in (7) to (9) above were produced as follows. A polyester elastomer resin composition was pre-dried for 4 hours at a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried for 12 hours at 120°C under the same vacuum conditions. The resulting dried resin was melted using a spinning machine equipped with a melt extrusion device and spun at a discharge rate of 22.2 g / min per nozzle (unit of monofilament). The extruded polymer was cooled by passing it through a water bath at approximately 30°C with a 50 mm air gap. It was then stretched four times its original length between a Nelson roller and a take-up roller, the surface temperature of which was 90°C and the speed was adjusted to 20 m / min. Subsequently, the polymer was relaxed by approximately 2% between a slit-type heater at 150°C, taken up by another pair of Nelson rollers, and immediately wound up.

[0074] [Polyester Elastomer (A)] Polymerization Example 1 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 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 charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised, and the temperature was lowered to 245 ° C. and 0.9 Torr or less over 75 minutes to carry out an initial condensation reaction. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 Torr or less for 125 minutes, and a polymer having a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A1).

[0075] Polymerization Example 2 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1360 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 750 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 230 ° C. over 135 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 250 ° C., 0.9 Torr or less over 68 minutes. The polymerization reaction was further carried out at 250° C. under a pressure of 0.9 Torr or less for 115 minutes, and a polymer having a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A2).

[0076] Polymerization Example 3 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1360 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 750 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 235 ° C. over 120 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 255 ° C. and 0.8 Torr or less over 60 minutes. The polymerization reaction was further carried out at 255°C under a pressure of 0.8 Torr or less for 100 minutes, and a polymer having a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A3).

[0077] Polymerization Example 4 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1360 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 750 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 235 ° C. over 120 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 260 ° C., 0.7 Torr or less over 60 minutes. The polymerization reaction was further carried out at 260°C under a pressure 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 the form of pellets. The obtained polymer was designated as polyester elastomer (A4).

[0078] Polymerization Example 5 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1360 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 750 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C. and 0.9 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 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 the form of pellets. The obtained polymer was designated as polyester elastomer (A5).

[0079] Polymerization Example 6 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 2000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1360 parts by mass, fossil fuel resource-derived polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF) 750 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C. and 0.9 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 Torr or less for 80 minutes, and a polymer having a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A6).

[0080] Polymerization Example 7 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1200 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 1950 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C., 0.9 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 Torr or less for 125 minutes, and a polymer having a hard segment / soft segment mass ratio of 45 / 55 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A7).

[0081] Polymerization Example 8 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1200 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 1950 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 230 ° C. over 135 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 250 ° C., 0.9 Torr or less over 68 minutes. The polymerization reaction was further carried out at 250° C. under a pressure of 0.9 Torr or less for 115 minutes, and a polymer having a hard segment / soft segment mass ratio of 45 / 55 (mass %) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A8).

[0082] Polymerization Example 9 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1200 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 1950 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 235 ° C. over 120 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 250 ° C., 0.8 Torr or less over 60 minutes. The polymerization reaction was further carried out at 250° C. under a pressure of 0.9 Torr or less for 95 minutes, and a polymer having a hard segment / soft segment mass ratio of 45 / 55 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A9).

[0083] Polymerization Example 10 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1000 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1200 parts by mass, fossil fuel resource-derived polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF) 1950 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C. and 0.9 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 Torr or less for 80 minutes, and a polymer having a hard segment / soft segment mass ratio of 45 / 55 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A10).

[0084] Polymerization Example 11 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 680 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1150 parts by mass, biomass resource-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical) 2350 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 225 ° C. over 150 minutes to carry out a transesterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C., 0.9 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 0.9 Torr or less for 125 minutes, and a polymer having a hard segment / soft segment mass ratio of 40 / 60 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A11).

[0085] Polymerization Example 12 Dimethyl terephthalate (DMT, manufactured by SK Petrochemical) 1815 parts by mass, 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical) 1665 parts by mass, biomass resource-derived dimer acid (C36DiCOOH, Croda Propol 1009) 860 parts by mass, tetrabutyl titanate (TBT, manufactured by Nacalai Tesque) 2.4 parts by mass, AO-330 (manufactured by ADEKA) 6.0 parts by mass were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C. over 120 minutes to carry out a transesterification reaction and an esterification reaction. The pressure inside the vessel was then gradually reduced and the temperature was further raised, and the initial condensation reaction was carried out at 245 ° C., 1 Torr or less over 75 minutes. The polymerization reaction was further carried out at 245°C under a pressure of 1 Torr or less for 60 minutes, and a polymer having a hard segment / soft segment mass ratio of 66 / 34 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A12).

[0086] The compositions of the polyester elastomers (A1) to (A12) and the evaluation results are shown in Table 1.

[0087]

[0088] Resin Compositions of Examples 1 and 2, Comparative Examples 1 to 3, and Reference Example 1: 100 parts by mass of the polyester elastomer shown in Table 2 and 0.1 parts by mass of a heat stabilizer (hindered phenol-based antioxidant: Irganox 1010 (BASF)) were weighed out and fed into the main feed port of a 58 mm screw diameter, L / D = 37 (9 barrels) co-rotating twin-screw extruder (TEM58BS, manufactured by Toshiba Machine Co., Ltd.). The extruder barrel temperature was set to 210°C to 230°C, the screw rotation speed was 200 rpm, and the extrusion rate was 120 kg / h, and melt-kneading was performed. Finally, the mixture was taken up in the form of a strand from the die, passed through a water bath to cool and solidify, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The resulting polyester elastomer resin composition pellets were vacuum-dried at 80°C overnight and then subjected to the various tests.

[0089] Resin Compositions of Examples 3 to 5, Comparative Examples 4 and 5, and Reference Example 2: 100 parts by mass of the polyester elastomer shown in Table 2 and 0.1 parts by mass of a heat stabilizer (hindered phenol-based antioxidant: Irganox 1010 (BASF)) were weighed out and fed into the first main feed port from the upstream end of a co-rotating 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 was 180 rpm, and the output rate was 50 kg / h, and melt-kneading was performed. Finally, the mixture was taken up in the form of a strand from the die, passed through a water bath to cool and solidify, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The resulting polyester elastomer resin composition pellets were vacuum-dried at 80°C overnight and then subjected to the various tests.

[0090] Resin Composition of Example 6 Using the polyester elastomer A1 as the high-melting point component, polyester elastomer resin composition pellets were obtained in the same manner as in Example 1. Using the polyester elastomer A7 as the low-melting point component, polyester elastomer resin composition pellets were obtained in the same manner as in Example 3.

[0091] Monofilaments of Examples 1-5, Comparative Examples 1-5, and Reference Examples 1 and 2: Polyester elastomer resin composition pellets were pre-dried for 4 hours at a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried for 12 hours at 120°C under the same vacuum conditions. The resulting dried pellets were melted using a spinning machine equipped with a melt extrusion device and spun at a discharge rate of 22.2 g / min per nozzle (unit of monofilament). The extruded resin composition was cooled by passing it through a water bath at approximately 30°C with a 50 mm air gap. It was then stretched four times between a Nelson roller and a take-up roller, the surface temperature of which was adjusted to 90°C and the speed to 20 m / min. Subsequently, the yarn was relaxed by approximately 2% between a slit-type heater at 150°C, taken up by another pair of Nelson rollers, and immediately wound up. The final yarn had a fineness of approximately 2000 dtex.

[0092] Monofilament of Example 6: Pellets of the polyester elastomer resin composition of the high-melting point component and the low-melting point component were pre-dried for 4 hours at a vacuum of 0.1 mmHg and an ambient temperature of 80°C, and then dried for 12 hours at 120°C under the same vacuum conditions. Using a spinning machine equipped with a double-tube composite nozzle and two pairs of melt extrusion devices, the dried pellets of the two components were separately melted, and at the joining zone, the low-melting point component was used as the sheath and the high-melting point component was used as the core. The extrusion rate was adjusted so that the cross-sectional area ratio of the sheath and core was 20:80, resulting in a total extrusion rate of 33.3 g / min per nozzle hole (unit of monofilament). Spinning was performed at a temperature approximately 10°C higher than the melting point of the resin contained in the core of the high-melting point component. The extruded resin composition was cooled by passing it through a water bath at about 30°C with an air gap of 50 mm provided, and then stretched four times between a Nelson roller and a take-up roller, the surface temperature of which was adjusted to 90°C and the speed to 20 m / min, and subsequently taken up by another pair of Nelson rollers while being relaxed by about 2% between a slit heater at 150°C, and immediately wound up. The final yarn fineness was about 2000 dtex.

[0093]

[0094] As is clear from Table 2, Examples 1 to 6, in which the Tm-VST and number-average molecular weight of the polyester elastomer resin composition were within the ranges specified in the claims, used a biomass-derived polyester elastomer, but similar to Reference Examples 1 and 2, which used a fossil-derived polyester elastomer, exhibited monofilament breaking elongation of 80% or more, breaking strength of 1.2 cN / dtex or more, elongation recovery after 30% elongation at 23°C of 90% or more, and elongation recovery after 20% elongation at 80°C of 80% or more. The filament processability was also excellent, resulting in monofilaments with excellent strength, elastic properties, elastic recovery, and filament processability. In Comparative Examples 1 and 2, the Tm-VST was below the lower limit, which tended to result in reduced elongation recovery and reduced filament processability. In Comparative Example 3, the number-average molecular weight was below the lower limit, which resulted in overall reduced mechanical properties and frequent yarn breakage. In Comparative Examples 4 and 5, since Tm-VST was above the upper limit, the strength decreased and the filament processability also tended to decrease.

[0095] Although the polyester elastomer resin composition of the present invention uses a polyester elastomer derived from biomass resources, it also possesses the excellent strength, elastic properties, elastic recovery properties, and filament processability that are characteristic of polyester elastomers derived from fossil fuel resources, and therefore can be applied to a wide range of fields, including fibers and nonwoven fabrics. Therefore, the polyester elastomer resin composition of the present invention will greatly contribute 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 containing a biomass resource-derived polyester elastomer, at least one of whose constituent components is derived from a biomass resource, and a heat stabilizer, characterized in that the bio-based content 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 the relationship 10°C≦Tm-VST≦43°C, and the number average molecular weight (Mn) of the polyester elastomer resin composition is 9,000 or more.

2. The polyester elastomer resin composition according to claim 1, characterized in that, when the weight average molecular weight (Mw) of the polyester elastomer resin composition is taken as Mw / Mn≦5.

0.

3. The polyester elastomer resin composition according to claim 1, characterized in that it contains a polyester elastomer having a hard segment / soft segment mass ratio of 40 / 60 to 80 / 20.

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

5. The polyester elastomer resin composition according to claim 4, characterized in that the biomass resource-derived aliphatic polyether of the biomass resource-derived polyester elastomer is polytetramethylene ether glycol.

6. The polyester elastomer resin composition according to claim 4, characterized in that the reduced viscosity of the biomass resource-derived polyester elastomer is 1.2 dl / g or more.

7. A monofilament comprising the polyester elastomer resin composition according to any one of claims 1 to 6.

8. A monofilament as described in claim 7, characterized in that it has a breaking elongation of 80% or more, a breaking strength of 1.2 cN / dtex or more, an elongation recovery rate after 30% elongation at 23°C of 90% or more, and an elongation recovery rate after 20% elongation at 80°C of 80% or more.

9. A woven, knitted or nonwoven fabric comprising the monofilament according to claim 7 as a constituent material.

10. A composite monofilament having a core-sheath structure using the polyester elastomer resin composition according to any one of claims 1 to 6, which is made of two components having different melting points, characterized in that the core is formed from a component with a high melting point and the sheath is formed from a component with a low melting point.

11. A highly elastic fabric comprising a woven, knitted or nonwoven fabric containing the composite monofilament according to claim 10 as a constituent material, characterized in that the low melting point component of the composite filament is fused at the intersections of the monofilaments.

Images