Resin composition using a polyester elastomer derived from biomass resources

Abstract

Even if the proportion of the raw material derived from biomass resources is increased, a polyester elastomer resin composition derived from biomass resources that can maintain the excellent mechanical properties, storage stability, elongation retention rate after heat and humidity treatment, extrusion moldability, and water aging resistance of the polyester elastomer derived from fossil fuel resources is provided. A polyester elastomer resin composition containing a polyester elastomer derived from biomass resources in which at least one of the constituent components is derived from biomass resources and a heat stabilizer, wherein the bio-based degree of the polyester elastomer resin composition is 20 to 100%, and the oligomer content having a number average molecular weight of less than 1000 in the polyester elastomer derived from biomass resources is 2.5% by weight or less, and the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN, or the 3% weight loss temperature when the temperature is raised from room temperature to 450 °C at 10 °C / min is 300 °C or higher.

Description

Technical Field

[0001] The present invention relates to a polyester elastomer resin composition derived from biomass resources that can maintain the excellent mechanical properties, storage stability, elongation retention rate after heat and humidity treatment, extrusion moldability, and water aging resistance of polyester elastomers derived from fossil fuel resources, despite using a polyester elastomer derived from biomass resources with a high biomass content.

Background Art

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

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

[0004] In recent years, against the backdrop of concerns about the depletion of fossil fuel resources and global environmental problems such as the increase in carbon dioxide in the atmosphere, the biomass conversion of various polymers has been promoted. Since biomass resources are renewable resources, they are considered to be an important design concept in future polymer development from the perspectives of SDGs and carbon neutrality.

[0005] However, since the raw materials derived from biomass resources contain impurities that cannot be completely removed in the purification process, increasing the proportion of raw materials derived from biomass resources in an attempt to increase the biomass content in the polyester elastomer results in an increase in the amount of impurities. As a result, the reaction is inhibited, the reduced viscosity does not increase, and it has been difficult to maintain the excellent properties of polyester elastomers derived from fossil fuel resources.

[0006] In addition, factors such as impurities introduced from biomass resource-derived raw materials, oligomers generated by the polymerization reaction using the same, by-products, foreign substances, and polymers different from the design make it difficult for polyester elastomers to exhibit the excellent molding design accuracy they inherently possess. For example, in film molding, a resin that is likely to deform in the high-elongation region exiting the die, a resin that is likely to harden with strain rate in terms of extensional viscosity from the perspective of flow characteristics, and on the other hand, a resin that does not generate ductile necking in the low-elongation region after exiting the die result in high molding stability. To obtain such high molding stability, high polymer molecular designability is required to control entanglement and slippage between molecular chains. However, when using a polyester elastomer produced from a biomass resource-derived raw material, in addition to low polymer molecular designability, problems such as low wall thickness accuracy and easy breakage during production are caused by the influence of introduced impurities, foreign substances, etc.

[0007] In response to such problems, it has been proposed to reduce the sulfur atom content and acid end group amount in the polyester using dicarboxylic acid and / or diol from biomass resource-derived raw materials to prevent a decrease in the mechanical properties of the polyester (see Patent Document 1). This biomass resource-derived polyester can prevent a decrease in mechanical properties to a certain extent, but there is a problem of causing coloring of the polyester and deteriorating the appearance of the molded product. Also, excellent properties possessed by polyester derived from fossil fuel resources regarding storage stability, hydrolysis resistance, and heat aging resistance could not be maintained.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention was devised in view of the current state of the prior art, and its object is to maintain the excellent mechanical properties, storage stability, elongation retention rate after wet heat treatment, extrusion moldability, and water aging resistance of polyester elastomers derived from fossil fuel resources, even when increasing the proportion of raw materials derived from biomass resources in the polyester elastomer. The aim is to provide a polyester elastomer resin composition derived from biomass resources that can achieve this.

Means for Solving the Problems

[0010] As a result of intensive studies to achieve this object, the inventor has found that in a polyester elastomer resin composition containing a biomass resource-derived polyester elastomer with a high bio-based content and a heat stabilizer, after 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, by controlling the melt tension of the composition or the 3% weight loss temperature when the temperature of the composition is raised from room temperature to 450°C at 10°C / min within a specific range, it is possible to provide a polyester elastomer resin composition derived from biomass resources that can maintain the excellent mechanical properties, storage stability, elongation retention rate after wet heat treatment, extrusion moldability, and water aging resistance of polyester elastomers derived from fossil fuel resources. This led to the completion of the present invention.

[0011] That is, the present invention is composed of the following (1) to (10). (1) 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-based degree of the polyester elastomer resin composition is 20 to 100%, the oligomer content with a number average molecular weight of less than 1000 in the biomass resource-derived polyester elastomer is 2.5% by weight or less, and the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN. The polyester elastomer resin composition is characterized by these features. (2) A polyester elastomer resin composition containing at least one component derived from biomass resources and a heat stabilizer, wherein the biobased degree of the polyester elastomer resin composition is 20 to 100%, the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN, and 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. A polyester elastomer resin composition characterized by the above. (3) The polyester elastomer resin composition according to (1) or (2), characterized in that the polyester elastomer resin composition further contains a thickener. (4) The polyester elastomer resin composition according to (1) or (2), characterized in that the polyester elastomer resin composition further contains a hydrolysis inhibitor. (5) The polyester elastomer derived from biomass resources is a polyester elastomer in which a hard segment composed of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components and a soft segment composed of an aliphatic polyether are bonded. 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. The polyester elastomer resin composition according to (1) or (2). (6) The polyester elastomer resin composition according to (5), characterized in that the biomass-derived aliphatic polyether of the biomass-derived polyester elastomer is polytetramethylene ether glycol. (7) The polyester elastomer resin composition according to (5), characterized in that the reduced viscosity of the biomass-derived polyester elastomer is 1.2 dl / g or more. (8) A hose formed by extrusion molding the polyester elastomer resin composition according to (1) or (2). (9) A film formed by extrusion molding the polyester elastomer resin composition according to (1) or (2). An electric wire coating material obtained by extrusion molding the polyester elastomer resin composition described in (10)(1) or (2).

Advantages of the Invention

[0012] Even when the proportion of the raw material derived from biomass resources is increased, the polyester elastomer resin composition derived from biomass resources of the present invention can maintain the excellent mechanical properties, storage stability, elongation retention rate after heat and humidity treatment, extrusion moldability, and water aging resistance of the polyester elastomer derived from fossil fuel resources. Therefore, the polyester elastomer resin composition of the present invention can be suitably used for hoses, films, electric wire coating materials, etc. obtained by extrusion molding.

Modes for Carrying Out the Invention

[0013] The polyester elastomer resin composition of the present invention contains a polyester elastomer derived from biomass resources in which at least one of the constituent components is derived from biomass resources and a heat stabilizer, and the bio-based degree of the polyester elastomer resin composition is 20 to 100%, and the oligomer content having a number average molecular weight of less than 1000 in the polyester elastomer derived from biomass resources is 2.5% by weight or less, and the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN, or the 3% weight loss temperature when the temperature is raised from room temperature to 450 °C at 10 °C / min is 300 °C or higher.

[0014] The polyester elastomer derived from biomass resources used in the resin composition of the present invention is preferably a polyester elastomer in which a hard segment composed of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components and a soft segment composed of an aliphatic polyether are bonded, and 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 biomass resources.

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

[0016] In addition, 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 are preferably mainly alkylene glycols having 2 to 8 carbon atoms. Specifically, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, etc. may be mentioned. Among these, either ethylene glycol or 1,4-butanediol is preferably used.

[0017] As components constituting the polyester of the above hard segment, those composed of butylene terephthalate units (units composed of terephthalic acid and 1,4-butanediol) or butylene naphthalate units (units composed of 2,6-naphthalenedicarboxylic acid and 1,4-butanediol) are preferable from the viewpoints of physical properties, moldability, and cost performance.

[0018] Further, when a suitable aromatic polyester as the polyester constituting the hard segment of the polyester elastomer is produced in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained according to the ordinary polyester production method. Further, such a polyester preferably has a number average molecular weight of 10,000 to 40,000.

[0019] As the aliphatic polyether constituting the soft segment of the polyester elastomer, in order to bond to the polyester of the hard segment, it is preferably a glycol compound. Specifically, 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, a copolymer of ethylene oxide and tetrahydrofuran, etc. are mentioned. Among these, from the viewpoint of elastic characteristics, polytetramethylene ether glycol and an ethylene oxide adduct of poly(propylene oxide) glycol are preferable.

[0020] In the present invention, as the aliphatic polyether which is a constituent component of the soft segment, it is preferable to use those derived from biomass resources, particularly polytetramethylene ether glycol (PTMG) derived from biomass resources. As such PTMG, commercially available ones can be obtained and used. For example, BioPTMG1000, BioPTMG2000, etc. manufactured by Mitsubishi Chemical are preferably used.

[0021] The polyester elastomer is preferably a copolymer mainly composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol. Among the dicarboxylic acid components constituting the polyester elastomer, terephthalic acid is preferably 40 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Among 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, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0022] The number average molecular weight of the polytetramethylene ether glycol is preferably 500 to 4000, more preferably 700 to 3000, and still more preferably 800 to 2500. If the number average molecular weight is less than 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 the hard segment component may decrease, and it may be difficult to copolymerize in a block form.

[0023] 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 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 polytetramethylene ether glycol (PTMG).

[0024] The mass ratio of the hard segment to the soft segment of the polyester elastomer is preferably from 5 / 95 to 90 / 10, more preferably from 10 / 90 to 85 / 15, and even more preferably from 15 / 85 to 80 / 20. If the amount of the hard segment is small (the amount of PTMG is large), it may not be possible to obtain a product that satisfies the functions of heat aging resistance and moldability (crystallinity) as a polyester elastomer. On the contrary, if the amount of the hard segment is large (the amount of PTMG is small), the compatibility between the hard segment component and the soft segment component may decrease, and it may be difficult to copolymerize in a block form.

[0025] Also, the melting point of the polyester elastomer is preferably from 150 to 230 °C. If the melting point is lower than 150 °C, it may not be possible to obtain a product that satisfies the functions of heat aging resistance and moldability (crystallinity) as a polyester elastomer. On the contrary, if the melting point exceeds 230 °C, since it contains a large amount of the hard segment, the glass transition temperature (Tg) will increase accordingly, and it may not be possible to obtain a product that satisfies the functions of resilience, flexibility, and low-temperature mechanical properties as a polyester elastomer.

[0026] As the production method of the polyester elastomer, any known method can be adopted. For example, any of the melt polymerization method, solution polymerization method, solid-phase polymerization method, etc. can be appropriately used. In the case of the melt polymerization method, either the transesterification method or the direct polymerization method may be used. For example, a method in which a dicarboxylic acid component and a diol component are reacted to form a prepolymer by the transesterification method, direct esterification method, etc., and then a polycondensation reaction is carried out under reduced pressure can be mentioned. At this time, catalysts for the transesterification reaction, esterification reaction, and polycondensation reaction can be appropriately used. Also, after polymerization, chain extension may be carried out with an isocyanate compound, epoxy compound, etc. In addition, when the solid-phase polymerization method is used, the melt tension can be improved in the polymerization process.

[0027] In order to produce the polyester elastomer of the present invention, it is preferable to make the polycondensation time longer than before. For example, in the polycondensation of a polyester elastomer using butylene terephthalate units as the hard segment constituent and polytetramethylene ether glycol as the soft segment component, usually, the polycondensation time in the production of the polyester elastomer is about 50 to 90 minutes. However, in the present invention, the polycondensation time is preferably 100 to 140 minutes, more preferably 105 to 135 minutes. Also, it is preferable to control the polycondensation temperature within a narrow range. Usually, the polycondensation temperature in the production of the polyester elastomer is about 235 to 260 °C. However, in the present invention, the polycondensation temperature is preferably 235 to 255 °C, more preferably 240 to 250 °C. If the polycondensation time is short or the polycondensation temperature is low, the polymerization reaction may not proceed smoothly, the oligomer content may increase, or the acid value of the system may rise. Also, 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 of the polyester elastomer, or the retention stability may deteriorate. On the contrary, if the polycondensation time is long or the polycondensation temperature is high, coloring of the polyester elastomer may occur due to thermal decomposition, deteriorating the appearance, or promoting the formation of oligomers and gelation. Also, the pressure is gradually reduced from the pressure of the transesterification reaction, but it is preferable to set the final pressure to 0.1 to 3 Torr, or more preferably 0.04 to 0.2 kPa. If this pressure exceeds the upper limit, the reactivity decreases and the reaction time becomes long, and coloring of the polyester elastomer may occur due to thermal decomposition, deteriorating the appearance, or promoting 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 and distillation of the monomer, or delay of the polymerization reaction due to excessive reduction of intermolecular collisions. Note that the above polycondensation conditions need to be appropriately adjusted according to the constituent components.

[0028] When the bio-based content of the polyester elastomer of the present invention is expressed as the bio-based content of the resin composition including components such as heat stabilizers, it is 20 to 100%, preferably 20 to 99.9%, more preferably 20 to 99%, still more preferably 20 to 85%, and particularly preferably 20 to 80%. The bio-based content of the polyester elastomer is preferably 20 to 100%, more preferably 20 to 85%, and still more preferably 20 to 80%. Conventionally, since biomass resource-derived raw materials contain impurities that could not be completely removed in the purification process, when increasing the proportion of biomass raw materials in an attempt to increase the bio-based content, the amount of impurities increases, resulting in problems such as inhibited reactions, no increase in reduced viscosity, longer polymerization times, and coloring. Therefore, it has been difficult to obtain a biomass resource-derived polyester elastomer that can prevent coloring, maintain excellent flexibility, low-temperature mechanical properties, heat aging resistance, and water resistance without reducing production efficiency. In the present invention, as the polymerization raw material of the polyester elastomer, the hard segment uses those derived from fossil fuel resources, and only the soft segment uses aliphatic polyethers as the raw material derived from biomass resources. By adopting appropriate polycondensation reaction times and temperatures, a biomass resource-derived polyester elastomer that has no coloring and can maintain the excellent properties of fossil fuel resource-derived polyester elastomers can be obtained.

[0029] As a characteristic of the polyester elastomer of the present invention, the reduced viscosity (ηsp / c), which is an index of molecular weight, is extremely important. In the present invention, in order to exhibit the long-term durability (heat aging resistance, water resistance) as a polyester elastomer, the reduced viscosity is preferably 1.2 dl / g or more, more preferably 1.4 dl / g or more. Still more preferably, it is 1.8 dl / g or more. When the reduced viscosity (ηsp / c) is low, since the molecular weight is small, it may not be possible to obtain a product that satisfies the functions of long-term durability (heat aging resistance, water resistance) as a polyester elastomer.

[0030] As a characteristic of the polyester elastomer of the present invention, the glass transition temperature (Tg), which is an index of low-temperature mechanical properties, is important. The glass transition temperature changes according to the ratio of the soft segment in the polyester elastomer. In the present invention, the glass transition temperature that exhibits the functions of resilience, flexibility, and low-temperature mechanical properties as a polyester elastomer is preferably -70 to 10 °C, more preferably -65 to 10 °C. If the glass transition temperature is high, it may not be possible to obtain a polyester elastomer that satisfies the functions of resilience, flexibility, and low-temperature mechanical properties.

[0031] As a characteristic of the polyester elastomer of the present invention, the oligomer content of less than 1000 in the biomass resource-derived polyester elastomer is important. The oligomer content of less than 1000 in the biomass resource-derived polyester elastomer changes 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 large, the melt tension of the polyester elastomer composition does not sufficiently increase in the compound during the production of the composition, and high-precision moldability cannot be obtained. In addition, gels are likely to occur when a thickening agent is added, deteriorating the appearance and properties of the molded product. Also, the thermal stability and water resistance of the molten resin deteriorate, resulting in different fluidities at the start and end of molding, impairing stable productivity. Furthermore, in the molded product, it may not be possible to obtain a product that satisfies the functions of resilience, flexibility, and low-temperature mechanical properties.

[0032] As a characteristic of the polyester elastomer of the present invention, it can be mentioned that the Co-b value, which is an index of the appearance of the molded product, can be lowered. The value of Co-b changes depending on impurities in the biomass resource-derived raw material and polymerization conditions. In the present invention, Co-b for obtaining a good appearance is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less. If Co-b is large, the prepared pellets turn yellow, greatly damaging the appearance of the molded product, and thus it may not be possible to obtain a satisfactory product.

[0033] As a method for determining the composition and composition ratio of the polyester elastomer of the present invention, a sample is dissolved in a solvent such as deuterated chloroform and measured. 1 It is also possible to calculate from the proton integration ratio of H-NMR.

[0034] The polyester elastomer resin composition of the present invention contains a heat stabilizer as an essential component in addition to the above polyester elastomer. Further, the polyester elastomer resin composition of the present invention can optionally further contain a thickener and / or a hydrolysis inhibitor.

[0035] The heat stabilizer is used to prevent thermal oxidative decomposition during compounding and molding. As the heat stabilizer, for example, known hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and amine antioxidants can be used. The compounding amount of the heat stabilizer is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and still more preferably 0.2 to 3.5 parts by mass with respect to 100 parts by mass of the polyester elastomer. If the amount of the heat stabilizer is too small, the effect of preventing thermal oxidative decomposition is insufficient, and if it is too large, there is a risk of deterioration of mechanical properties.

[0036] Examples of hindered phenol antioxidants include 3,5-di-t-butyl-4-hydroxy-toluene, 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, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-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, triphenol, 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) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid 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-hydrocinnamide), 3,9-bis [2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, etc.

[0037] Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl stearyl-3,3'-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythrityl-tetra(β-lauryl-thiopropionate) ester, and the like.

[0038] Examples of phosphorus-based antioxidants include tris(mixed, mono and dinonylphenyl) 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-tridecyl phosphite-5-t-butylphenyl) butane, tris(2,4-di-t-butylphenyl) phosphite, bis(2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis(2,4-di-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, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite, and the like.

[0039] Examples of amine antioxidants include amines and their derivatives 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, 4,4'-bis(4-α,α-dimethyl-benzyl)diphenylamine, and reaction products of amines with aldehydes and reaction products of amines with ketones.

[0040] The thickener is a reactive compound having a functional group capable of reacting with the end groups of the polyester elastomer and having a functional group capable of reacting with the hydroxyl group or carboxyl group of the polyester elastomer. The functional group capable of reacting is preferably at least one selected from an epoxy group (glycidyl group), an acid anhydride group, a carbodiimide group, and an isocyanate group, and two or more of these functional groups are contained per molecule. The epoxy group (glycidyl group) is more preferable as the functional group.

[0041] When the thickener is a compound having an epoxy group, it is a polyfunctional epoxy compound having two or more epoxy groups. Specifically, 1,6-dihydroxynaphthalene diglycidyl ether having two epoxy groups, 1,3-bis(oxiranylmethoxy)benzene, 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione having three epoxy groups, diglycerol triglycidyl ether, 1-chloro-2,3-epoxypropane·formaldehyde·2,7-naphthalenediol polycondensate having four epoxy groups, and pentaerythritol polyglycidyl ether can be mentioned. Among them, it is preferably a polyfunctional epoxy compound having heat resistance in the skeleton. In particular, a bifunctional or tetrafunctional epoxy compound having a naphthalene structure in the skeleton, or a trifunctional epoxy compound having a triazine structure in the skeleton is preferable. 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 generation of gelation due to aggregation and solidification of the epoxy itself, a bifunctional or trifunctional epoxy compound is preferable.

[0042] When adding a thickener, its blending amount is preferably 0.1 to 5.0 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.2 to 3.5 parts by mass with respect to 100 parts by mass of the polyester elastomer. If the amount of the thickener is too small, the target molecular chain extension effect is insufficient. If it is too much, the thickening effect becomes excessive, which tends to have an adverse effect on the moldability or the mechanical properties of the molded body. When the thickener is an epoxy compound, if it is too much, unevenness may occur on the surface of the molded body due to aggregation and hardening of the epoxy compound. When the thickener is a carbodiimide compound, if it is too much, hydrolysis of the thermoplastic polyester elastomer may occur due to the basicity of the polycarbodiimide compound, which tends to affect the mechanical properties.

[0043] The hydrolysis inhibitor is added to improve hydrolysis resistance and improve flex fatigue resistance by chain extension. As the hydrolysis inhibitor, for example, a compound having a functional group capable of reacting with the terminal functional group of the polyester elastomer can be used. The terminal functional group of the polyester elastomer is a carboxyl group and / or a hydroxyl group. Further, examples of the functional group capable of reacting with the terminal functional group of the polyester elastomer include a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, a carbodiimide group, an oxazoline group, and the like. Among these, from the viewpoint of the change in melt viscosity during melt residence and the reactivity with the terminal functional group of the polyester elastomer, the functional group is preferably an epoxy group or a carbodiimide group. The hydrolysis inhibitor is preferably an epoxy compound and / or a carbodiimide compound.

[0044] The carbodiimide compound is a compound having at least one carbodiimide group represented by (-N=C=N-) in the molecule and is capable of reacting with the terminal group of the polyester elastomer (A).

[0045] Examples of carbodiimide compounds include diphenylcarbodiimide, dicyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-tolylcarbodiimide, 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-tolylcarbodiimide, N,N’-diphenylcarbodiimide, N,N’-dioctyldecylcarbodiimide, N,N’-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N’-cyclohexylcarbodiimide, N,N’-di-2,6-diisopropylphenylcarbodiimide, N,N’-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N’-phenylcarbodiimide, N,N’-di-p-nitrophenylcarbodiimide, N,N’-di-p-aminophenylcarbodiimide, N,N’-di-p-hydroxyphenylcarbodiimide, N,N’-dicyclohexylcarbodiimide, N,N’-di-p-tolylcarbodiimide, N,N’-benzylcarbodiimide, N-octadecyl-N’-phenylcarbodiimide, N-benzyl-N’-phenylcarbodiimide, N-octadecyl-N’-tolylcarbodiimide, N-cyclohexyl-N’-tolylcarbodiimide, N-phenyl-N’-tolylcarbodiimide, N-benzyl-N’-tolylcarbodiimide, N,N’-di-o-ethylphenylcarbodiimide, N,N’-di-p-ethylphenylcarbodiimide, N,Mono- or dicarbodiimide compounds such as N'-di-o-isopropylphenylcarbodiimide, N,N'-di-p-isopropylphenylcarbodiimide, N,N'-di-o-isobutylphenylcarbodiimide, N,N'-di-p-isobutylphenylcarbodiimide, N,N'-di-2,6-diethylphenylcarbodiimide, N,N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N,N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N,N'-di-2,4,6-trimethylphenylcarbodiimide, N,N'-di-2,4,6-triisopropylphenylcarbodiimide, N,N'-di-2,4,6-triisobutylphenylcarbodiimide; poly(1,6-hexamethylene carbodiimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylene carbodiimide), poly(1,4-cyclohexylene carbodiimide), poly(4,4'-diphenylmethane carbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethane carbodiimide), poly(naphthylene carbodiimide), poly(p-phenylene carbodiimide), poly(m-phenylene carbodiimide), poly(tolyl carbodiimide), poly(diisopropyl carbodiimide), poly(methyl-diisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), etc. Among them, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, and polycarbodiimide are preferred, and more preferably, poly(1,6-hexamethylene carbodiimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylene carbodiimide), poly(1,4-cyclohexylene carbodiimide), poly(4,4'-diphenylmethane carbodiimide), poly(3,3'-dimethyl-4,Polycarbodiimides such as 4'-diphenylmethane carbodiimide, poly(naphthylene carbodiimide), poly(p-phenylene carbodiimide), poly(m-phenylene carbodiimide), poly(tolyl carbodiimide), poly(diisopropyl carbodiimide), poly(methyl-diisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide) and the like can be mentioned. Among these, from the viewpoints of improving heat aging resistance and hydrolysis resistance and reactivity with acid terminals, polycarbodiimide is preferable, and particularly preferably, poly(1,4-cyclohexylene carbodiimide) and poly(triisopropylphenylene carbodiimide).

[0046] When adding a hydrolysis inhibitor, the blending amount is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and still more preferably 0.2 to 3.5 parts by mass with respect to 100 parts by mass of the polyester elastomer. If the hydrolysis inhibitor is too little, the effect is insufficient, while if it is too much, a decrease in flame retardancy or a decrease in mechanical properties due to the foreign matter effect may occur. In addition, when using a high molecular weight polyester elastomer that does not require chain extension or a polyester elastomer with a sufficiently small terminal acid value as the polyester elastomer, the hydrolysis inhibitor may not be added.

[0047] In the polyester elastomer resin composition of the present invention, various additives can be blended according to the purpose in addition to the above components. Examples of the additives include known light stabilizers such as hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, and salicylate-based, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, organic and inorganic pigments, and the like.

[0048] The acid value of the polyester elastomer resin composition of the present invention is preferably 0 to 20 eq / ton. More preferably, it is 0 to 15 eq / ton, and even more preferably 0 to 10 eq / ton. When the acid value is within the above range, the melt viscosity during molding is stable, and in the case of extrusion molding of a tubular molded body such as a cable or a hose, the uniformity of thickness is improved. Also, it has excellent hydrolysis resistance.

[0049] The melt tension of the polyester elastomer resin composition of the present invention is 1.0 to 50 cN. This melt tension is preferably 1.2 to 48 cN, more preferably 1.4 to 47 cN, and even more preferably 1.5 to 45 cN. If it is within the above range, it is excellent in the extrusion moldability of a tubular molded body, the thin film moldability such as a thin film and a film, and the wire and cable coating moldability. For example, in the extrusion molding of a hose or the like, a uniform tubular molded body without thickness unevenness can be obtained, and the mechanical properties such as the bending resistance after molding are also excellent. Also, for example, in the 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. If it is less than the above range, it is difficult to discharge a uniform film thickness in the width direction during discharge from the die, and there is a risk that a uniform thin film cannot be obtained due to pulsation or the like. Also, the appearance may deteriorate such as the occurrence of flow marks. On the other hand, when it is larger than the above range, it is difficult to increase the film forming speed, and there is a risk that wrinkles or surface roughness may occur. The melt tension can be controlled by a conventionally known method, for example, by increasing the reduced viscosity of the polyester elastomer, using a thickening agent, or adjusting the melt kneading conditions during the production of the polyester elastomer resin composition to control it within the above range.

[0050] Here, the melt tension is measured using a Capillograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd., with a capillary: diameter 2.0 mm, length 20 mm, cylinder diameter: 9.55 mm, temperature: melting point + 10 °C, cylinder extrusion speed: 20 mm / min, until the take-up speed reaches 10 m / min, and a take-up acceleration of 40 m / min 2 is the melt tension when measured.

[0051] The manufacturing method of the polyester elastomer resin composition of the present invention is not particularly limited, but it can be manufactured by melt-kneading each component with a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, roll, etc. known to those skilled in the art.

[0052] 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 plasticizing section of the extruder. When melt-kneading each of the above components, in the polymer plasticizing region, the melted components are made to coexist with the molten polymer phase, and the polymer viscosity as the matrix phase is increased, and the melted components are uniformly melted in the polymer phase by shear stress, and it is important to control internal heat generation to suppress polymer deterioration and side reactions. The resin pressure is preferably about 0.1 to 1 MPa.

[0053] Also, the melting temperature of the resin composition during melt-kneading is preferably 160 to 300°C, more preferably 180 to 280°C. If the melting temperature is low, melting is insufficient and unmelted gels are likely to occur frequently. Conversely, if the resin temperature is high, the resin composition is likely to undergo thermal deterioration.

[0054] 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, each component tends to be difficult to melt and react uniformly. Conversely, if it is high, there is a risk of polymer deterioration and side reactions due to shear heat generation. Also, 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 and the kneading becomes non-uniform. Conversely, if it is high, the resin filling rate in the extruder becomes too high and the kneading tends to become non-uniform.

[0055] The melt flow rate (MFR) value of the polyester elastomer resin composition of the present invention, when measured at a melting point + 20°C and a load of 2.16 kg in accordance with the flow test method for thermoplastic plastics specified in JIS K7210, is preferably 1 to 20 g / 10 min, more preferably 2 to 15 g / 10 min. If the MFR value deviates from the above range, there is a risk that extrusion molding cannot be performed. Also, the difference (ΔMFR: MFR35 - MFR5) between the MFR value (MFR35) after 35 minutes and the MFR value (MFR5) after 5 minutes when the resin composition is charged is preferably 0 to 15 g / 10 min, more preferably 0 to 8 g / 10 min. If ΔMFR is greater than the above range, the decrease in melt viscosity during molding is not suppressed and stable extrusion molding cannot be performed, and there is a risk that the thickness becomes uneven when forming cables or hoses. On the other hand, if it is less than the above range, the melt viscosity increases significantly during molding, and there is a risk that stable moldability cannot be obtained in the same way.

[0056] The method for adjusting the MFR value and ΔMFR to the above ranges is not particularly limited, but it is preferable to blend a predetermined amount of a thickening agent in a specific method. Thereby, the acid value of the polyester elastomer resin composition can be controlled within a predetermined range, and the MFR value and ΔMFR can be adjusted to the above ranges. It can be appropriately adjusted according to the thickening characteristics such as the acid value, thickening agent, and reaction group number and molecular weight of the hydrolysis inhibitor of the polyester elastomer, the increase in acid value due to the decomposition reaction of the polyester elastomer due to hydrolysis, and the reactivity with other additives. When an epoxy compound and polycarbodiimide are used in combination as the thickening agent and / or hydrolysis inhibitor, unreacted reactive compounds tend to remain in the resin composition. This unreacted reactive compound has the effect of reacting with the polyester elastomer during residence during molding to increase the molecular weight, contributing to the decrease in MFR and ΔMFR. On the other hand, it may reduce the long-term extrusion moldability, such as increasing the difference between the initial thickness and the final thickness.

[0057] The polyester elastomer resin composition of the present invention preferably has an elongation retention rate at break after heat and humidity treatment at 85°C, 95% RH for 750 hours of 50% or more, and more preferably 70% or more.

[0058] When the temperature of the polyester elastomer resin composition of the present invention is raised from room temperature to 450°C at a rate of 10°C / min, the 3% weight loss temperature is preferably 300°C or higher. If this 3% weight loss temperature is less than 300°C, the residence stability and heat and humidity resistance of the polyester elastomer resin composition may be impaired. The constituent components derived from biomass resources used in the polyester elastomer of the present invention have faster thermal decomposability than the constituent components derived from fossil fuel resources, 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 the ratio in the polyester elastomer, the faster the weight loss tends to be.

[0059] Here, the 3% weight loss temperature was measured using a differential thermal-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 proceeds at a high temperature and the weight becomes 97% of the initial weight is defined as the 3% weight loss temperature.

[0060] Since the polyester elastomer resin composition of the present invention is configured as described above, despite using a polyester elastomer derived from biomass resources with a high biomass content, it is possible to maintain the excellent mechanical properties, storage stability, elongation retention rate after heat and humidity treatment, extrusion moldability, and water aging resistance possessed by polyester elastomers derived from fossil fuel resources. Therefore, it can be used in a wide range of applications such as various parts of electrical products, hoses, tubes, cable coatings, etc. In particular, since the polyester elastomer resin composition of the present invention is excellent in extrusion moldability, it is suitable for applications such as films and sheets. Further, the polyester elastomer resin composition of the present invention can be formed into various shapes by injection molding, transfer molding, blow molding, melt spinning, etc. in addition to extrusion molding.

[0061] Various molded articles produced by the above processing methods can be suitably used for various parts such as automotive parts, electrical and electronic parts, building members, various containers, daily necessities, household sundries, cosmetic parts, sanitary products, and medical (medical and therapeutic) parts.

[0062] More specifically, as automotive parts, there are R&P boots, suspension boots, constant velocity joint boots, dust covers, floats, gears, joint bushes, tire bumper parts, seat belt parts, emblems, slide plates, various switches, various sealing materials, knobs, levers, interior parts such as clips, electrical system parts including meters, connectors, automotive cable covers, wire coating materials, 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 metals represented by 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, air ducts, fuel hoses, emission control hoses, inlet filler hoses, diaphragm parts and other mechanical parts of the fuel system, anti-vibration parts such as engine mounts and in-tank pump mounts, and various tire members such as tire treads, carcasses, sidewalls, inner liners, undertreads, and belt parts can be exemplified.

[0063] As electrical and electronic parts (mechanical parts), there are rubber parts for OA (office automation) equipment such as audio equipment, video equipment, projectors or copiers, facsimiles, personal computers, toys, and telephones, optical and magnetic media parts, etc.

[0064] In addition, it is suitably used for a wide range of life-related parts, cosmetics-related parts, and medical-related parts, such as building materials and piping parts like lighting fixtures, architectural hardware, piping, toilet peripheral equipment parts, fasteners (slide fasteners, snap fasteners, surface fasteners, rail fasteners, etc.), apparel-related materials such as moisture-permeable and waterproof films, footwear applications such as sports shoes, leisure shoes, fashion sandals, leather shoes, ski boots, etc., balls such as golf balls and tennis balls, various brushes such as hairbrushes, combs, hot curlers, daily necessities such as watch bands, stationery, cosmetic containers including lip creams and lipsticks, cleaners, water purifiers, spray nozzles, spray containers, aerosol containers, general containers, food packaging, daily sundry goods packaging, film applications such as stretch tapes used for paper diapers, etc., syringe covers and sealings, office furniture such as office chairs, and cushioning function members for furniture such as cushions and beds.

[0065] It can be used in applications in the fiber and non-woven fabric fields, for example, fibers such as continuous spinning, staple fibers, and monofilaments, hygiene materials such as paper diapers, medical uses such as surgical gowns and gloves, carpets, their linings, ropes, etc. Also, it can be used in applications such as canvas, tent materials, and synthetic leather materials by laminating these non-woven fabrics, monofilaments, knitted fabrics with films or sheets.

[0066] Furthermore, it can be suitably used for various adhesives and adhesives such as hot melt types, various resin modifiers, asphalt blend materials for road paving materials, waterproof sheets, pipe coatings, industrial material packaging, laminations of various rubber products, resin products, fabrics, and leather products, members for industrial machinery such as retainers and conveyor belts, and 3D printer filaments.

Examples

[0067] Examples are given below to demonstrate the effects of the present invention, but the present invention is not limited by these examples. The evaluation of characteristic values was carried out by the following methods. Also, the raw materials used in the examples, unless otherwise specified, are derived from fossil fuel resources.

[0068] (1) Bio-based content The bio-based content of a polyester elastomer is the ratio of monomer components derived from biomass resources, calculated from the mass of monomer components derived from biomass resources to the mass of all monomer components constituting the polyester elastomer. The bio-based content is for all carbon contained in the polyester elastomer and is only contained in raw materials derived from biomass resources 14 C carbon ( 12 Isotope of C carbon) and is consistent with the measured value. The bio-based content (%) of the polyester elastomer was measured by an accelerator mass spectrometer (AMS) based on ASTM D6866. On the other hand, the bio-based content of a polyester elastomer resin composition is the ratio of monomer components derived from biomass resources, calculated from the mass of monomer components derived from biomass resources to the mass of all monomer components constituting the polyester elastomer resin composition. The bio-based content is for all carbon contained in the polyester elastomer resin composition and is only contained in raw materials derived from biomass resources 14 C carbon ( 12 Isotope of C carbon) and is consistent with the measured value. The bio-based content (%) of the polyester elastomer resin composition was measured by an accelerator mass spectrometer (AMS) based on ASTM D6866.

[0069] (2) Reduced viscosity (ηsp / c) 0.05 g of the polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60 / 40), and the reduced viscosity (dl / g) was measured at 30 °C using an Ubbelohde viscometer tube.

[0070] (3) Melting point (Tm) Using a differential scanning calorimeter "DSC220 type" manufactured by Seiko Instruments Inc., 5 mg of the measurement sample was placed in an aluminum pan, covered and sealed, melted at 250 °C for 2 minutes in nitrogen, then cooled to 50 °C at a cooling rate of 20 °C / min, and further heated from 50 °C to 250 °C at 20 °C / min. The endothermic peak due to melting was determined from the obtained thermogram curve and taken as the melting point (°C).

[0071] (4) Glass transition temperature (Tg) As the measurement sample, a 0.4 mm thick sheet was prepared by pressing with a hot plate heated to 200 - 250 °C using an NF type single-action compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.). The measurement was carried out using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) under the conditions of a measurement frequency of 11 Hz and a heating rate of 2 °C / min, and the peak position in the tanδ from -150 °C to 150 °C was taken as Tg (°C).

[0072] (5) Acid value (AV) 0.2 g of the sample was precisely weighed, benzyl alcohol was added, and it was heated and dissolved. It was dissolved in 20 ml of chloroform and titrated with 0.08 N potassium hydroxide (ethanol solution), and the acid value (eq / ton) was determined from the titration amount of potassium hydroxide required for neutralization. A phenol red ethanol solution was used as the indicator.

[0073] (6) Oligomer content The oligomer content in the polyester elastomer (A) was measured as follows. 8 mg of the resin component was weighed and dissolved in 4 ml of HFIP / sodium trifluoroacetate 10 mM. It was filtered through a 0.2 μm membrane filter, and GPC analysis of the obtained sample solution was carried out under the following conditions. The molecular weight was calculated in terms of polymethyl methacrylate (PMMA). In the GPC analysis chart, the ratio (percentage) of the peak area showing a molecular weight of 1000 or less to the total peak area of the polymer was calculated, and the area ratio was taken as the oligomer amount (wt%). Apparatus: TOSOH HLC-8320GPC Column: TOSOH TSKgel SuperHM-H × 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%

[0074] (7) Melt tension The melt tension of the polyester elastomer resin composition was measured using a Capillograph 1D manufactured by Toyo Seiki Seisakusho, Ltd., with a 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 a take-up acceleration of 40 m / min until the take-up speed reached 10 m / min 2 and measured at.

[0075] (8) 3% weight loss temperature It was measured using a differential thermal - thermogravimetric simultaneous measurement device (Shimadzu Corporation, DTG - 60). 50 mg of the polyester elastomer resin composition was placed in a platinum cell, and heated up 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 proceeded at high temperature and the weight became 97% of the initial weight was defined as the 3% weight loss temperature.

[0076] (9) Evaluation of the gelled product Approximately 50 g of the polyester elastomer resin composition was precisely weighed into a glass bottle of about 250 ml (about 4 cm in diameter × 20 cm in height), immersed in a silicone oil bath at 250 °C, stirred while blowing nitrogen from the top (about 30 ml / min), and heat - treated for 4 hours. After the treatment, the content was dissolved in a mixed solvent (500 ml) of tetrachloroethane and phenol (1 / 1 weight ratio) (the glass bottle was also rinsed with a part of the above - mentioned mixed solvent), and then the insoluble matter was separated by a stainless - steel wire mesh of 100 mesh with a known weight (weight V′), observed visually, and evaluated according to the following criteria. ○: No gelled product is observed at all. △: A slight amount of gelled product is observed. ×: A significant amount of gelled product is observed.

[0077] (10) ΔMFR In accordance with the test method (Method A) described in JIS K7210, the melt flow rate (MFR: g / 10 min) of the polyester elastomer resin composition was measured at a temperature of the melting point of the polyester elastomer (A) + 20°C and a load of 2160 g. A composition with a moisture content of 0.1% by mass or less was used for the measurement. The difference (ΔMFR: MFR35 - MFR5) between the MFR value (MFR35) after 35 minutes of composition input and the MFR value (MFR5) after 5 minutes was measured.

[0078] (11) Tensile elongation at break 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. The test specimens were prepared by injection molding a resin dried under reduced pressure at 100°C for 5 hours using an injection molding machine (manufactured by Yamashiro Seiki Co., Ltd., model - SAV) at a cylinder temperature (Tm + 20°C) and a mold temperature of 30°C into a flat plate of 100 mm × 100 mm × 2 mm, and then punching out dumbbell - shaped No. 3 test specimens from the flat plate.

[0079] (12) Hydrolysis resistance (treatment time when the retention rate of tensile elongation at break after wet - heat treatment is 50%) The test specimens were left in an environment of 85°C × 95% RH for 750 hours, then taken out, and the tensile elongation at break was measured by the method described in (11) above. The tensile elongation at break was also measured for the test specimens that had not been subjected to wet - heat treatment, which was taken as the initial tensile elongation at break, and the retention rate of tensile elongation at break after wet - heat treatment (tensile elongation at break retention rate) was calculated as follows. Tensile elongation at break retention rate (%) = (tensile elongation at break after wet - heat treatment / initial tensile elongation at break) × 100

[0080] (13) Extrusion moldability The pellets melt - kneaded by a twin - screw extruder were extruded again through a round die by a single - screw extruder to discharge a strand with a diameter of 3 mm. From that state, the extrusion moldability (fluctuation in discharge amount) was evaluated according to the following criteria. ○: No fluctuation in discharge amount occurs, and the extrudability is stable. ×: There is a fluctuation in discharge amount, and it is impossible to take it up.

[0081] (14) Water aging resistance As the inner tube resin, the polyester elastomer composition (A) obtained in the production example was used. As the reinforcing material, a polyester yarn (1500 d, thickness 1 mm) was used, and a polyether-type urethane elastomer with a surface hardness of 98A was used for the outer tube to produce a resin hose with an outer diameter of 17.5 mm. This hose was cut into 200 mm lengths, immersed in boiling water at 100 °C for 20 days, then taken out, subjected to a bending test with a diameter of 80 mm, and the presence or absence of cracks and breakage was observed and evaluated according to the following criteria. ○: No cracks or breakage are observed. △: There are no cracks or breakage, but the surface is rough and obvious embrittlement is observed. ×: Cracks or breakage are observed.

[0082] [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 polytetramethylene ether glycol derived from biomass resources (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 145 minutes to carry out a transesterification reaction. Next, the pressure inside the can was gradually reduced while further raising the temperature, and an initial condensation reaction was carried out at 250 °C and 1 Torr or less over 70 minutes. Further, at 250 °C and in a state of 1 Torr or less, a polymerization reaction was carried out for 125 minutes, and a polymer with a mass ratio of hard segment / soft segment of 72 / 28 (mass%) was taken out in pellet form. The obtained polymer was designated as polyester elastomer (A1).

[0083] Polymerization example 2 1200 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 800 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1780 parts by mass of polytetramethylene ether glycol derived from biomass resources (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 155 minutes to carry out a transesterification reaction. Then, the pressure inside the can was gradually reduced while the temperature was further raised, and an initial condensation reaction was carried out at 250 °C and 1 Torr or less over 85 minutes. Furthermore, a polymerization reaction was carried out at 250 °C under a condition of 1 Torr or less for 105 minutes, and a polymer having a mass ratio of hard segment / soft segment of 33 / 67 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A2).

[0084] Polymerization Example 3 680 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 430 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 2330 parts by mass of polytetramethylene ether glycol derived from biomass resources (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 charged into an autoclave, and the temperature was raised from room temperature to 205 °C over 190 minutes to carry out a transesterification reaction. Then, the pressure inside the can was gradually reduced while the temperature was further raised, and an initial condensation reaction was carried out at 250 °C and 1 Torr or less over 85 minutes. Furthermore, a polymerization reaction was carried out at 250 °C under a condition of 1 Torr or less for 105 minutes, and a polymer having a mass ratio of hard segment / soft segment of 17 / 83 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A3).

[0085] Polymerization Example 4 2,000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1,360 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 1,000, 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 conduct a transesterification reaction. Next, the pressure inside the can was gradually reduced while further raising the temperature, and an initial condensation reaction was carried out at 250°C and 1 Torr or less over 70 minutes. Furthermore, a polymerization reaction was carried out at 250°C under a condition of 1 Torr or less for 80 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in pellet form. The obtained polymer was designated as polyester elastomer (A4).

[0086] Polymerization Example 5 2,000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1,360 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 parts by mass of polytetramethylene ether glycol derived from biomass resources (BioPTMG1000, number average molecular weight 1,000, 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 145 minutes to conduct a transesterification reaction. Next, the pressure inside the can was gradually reduced while further raising the temperature, and an initial condensation reaction was carried out at 250°C and 1 Torr or less over 70 minutes. Furthermore, a polymerization reaction was carried out at 250°C under a condition of 1 Torr or less for 85 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was taken out in pellet form. The obtained polymer was designated as polyester elastomer (A5).

[0087] Polymerization Example 6 2,000 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1,360 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 parts by mass of polytetramethylene ether glycol derived from biomass resources (BioPTMG1000, number average molecular weight 1,000, 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 145 minutes to carry out a transesterification reaction. Next, the pressure inside the can was gradually reduced and the temperature was further raised, and an initial condensation reaction was carried out at 235°C and 0.7 Torr or less over 60 minutes. Further, at 255°C, a polymerization reaction was carried out for 130 minutes under a state of 0.7 Torr or less, and a polymer having a mass ratio of hard segment / soft segment of 72 / 28 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A6).

[0088] Polymerization Example 7 1,815 parts by mass of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1,665 parts by mass of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 860 parts by mass of dimer acid derived from biomass resources (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 charged into an autoclave, and the temperature was raised from room temperature to 225°C over 115 minutes to carry out a transesterification reaction and an esterification reaction. Next, the pressure inside the can was gradually reduced and the temperature was further raised, and an initial condensation reaction was carried out at 250°C and 1 Torr or less over 70 minutes. Further, at 250°C, a polymerization reaction was carried out for 60 minutes under a state of 1 Torr or less, and a polymer having a mass ratio of hard segment / soft segment of 66 / 34 (mass%) was taken out in the form of pellets. The obtained polymer was designated as polyester elastomer (A7).

[0089] The compositions and evaluation results of polyester elastomers (A1) to (A7) are shown in Table 1.

[0090]

Table 1

[0091] [Heat stabilizer (B)] Hindered phenol antioxidant: Irganox 1010 (manufactured by BASF)

[0092] [Hydrolysis inhibitor (C)] Alicyclic polycarbodiimide: Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Inc.

[0093] [Thickener (D)] Triglycidyl isocyanurate compound: "TEPIC-S", manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent number (average number of epoxy groups per molecule) 3

[0094] [Comparative Examples 1 to 4, 6, 7, Reference Examples 1, 2, Example 4] The components (A) to (D) were weighed at the compounding ratios shown in Table 2, and the components other than the component (C) were premixed with a mixer for 90 seconds, and then supplied to the main supply port provided first from the upstream side of the extruder of a co-rotating twin-screw extruder (STS-50 manufactured by Coperion) with a screw diameter of 51 mm and L / D = 48 (14 barrels). The barrel temperature of the extruder was set at 210°C to 230°C, the screw rotation speed was 180 rpm, and the discharge rate was 50 kg / h. When the component (C) was included, it was charged from the supply port provided in the 9th barrel from the upstream side of the extruder, and melt-kneading was performed. Finally, after pulling it out in a strand shape from the die, it was passed through a water tank for cooling and solidification, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum-dried at 80°C overnight and then subjected to each test.

[0095] [Example 1, Comparative Examples 5, 8, 9, Reference Example 3] The above components (A) to (D) were weighed at the compounding ratios shown in Table 2 and supplied to the main supply port of a co-rotating twin-screw extruder (TEM58BS manufactured by Toshiba Machine Co., Ltd.) with a screw diameter of 58 mm and L / D = 37 (9 barrels). The barrel temperature of the extruder was set at 210°C to 230°C, the screw rotation speed was 200 rpm, and the discharge rate was 120 kg / h, and melt kneading was carried out. Finally, after taking it out in a strand form from the die, it was passed through a water tank for cooling and solidification, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum dried at 80°C overnight and then subjected to each test.

[0096] 〔Examples 2, 3, 5〕 The above components (A) to (D) were weighed at the compounding ratios shown in Table 2, mixed in a mixer for 90 seconds in advance, and then supplied to the main supply port provided first from the upstream of the extruder of a co-rotating twin-screw extruder (STS-50 manufactured by Coperion) with a screw diameter of 51 mm and L / D = 48 (14 barrels). The barrel temperature of the extruder was set at 180°C to 200°C, the screw rotation speed was 180 rpm, and the discharge rate was 50 kg / h, and melt kneading was carried out. Finally, after taking it out in a strand form from the die, it was passed through a water tank for cooling and solidification, and then cut with a pelletizer to obtain polyester elastomer resin composition pellets. The obtained polyester elastomer resin composition pellets were vacuum dried at 80°C overnight and then subjected to each test.

[0097]

Table 2

[0098] As is clear from Table 2, in Examples 1 to 5 in which the oligomer content of the polyester elastomer and the melt tension of the polyester elastomer resin composition are within the ranges specified in the claims, the polyester elastomer resin composition has excellent mechanical properties (tensile elongation at break and tensile strength at break), retention stability (ΔMFR), elongation retention after moist heat treatment (tensile elongation retention at break), extrusion moldability, and water aging resistance, and is suitable for extrusion moldability into hoses, films, electric wire coating materials, etc. Also, as can be seen from a comparison between Comparative Example 1 and Comparative Example 3, in which the oligomer content of the polyester elastomer is outside the specified range, the retention stability is poor and the elongation retention after moist heat treatment is also low. Also, as can be seen from a comparison between Comparative Example 2 and Comparative Example 4 in which a thickener is added, in Comparative Example 4 in which the oligomer content of the polyester elastomer is outside the specified range, the melt tension is difficult to increase even if a thickener is added. This tendency was clearly observed in Comparative Examples 6 to 8. In Comparative Example 9, in which the amount of thickener added was large and the melt tension was outside the upper limit of the specified range, the discharge amount became unstable in the high-speed region during extrusion molding.

[0099] As can be seen from Comparative Examples 1-2, Example 1, and Reference Examples 1-3, in which raw materials derived from biomass resources were used, the effect of the thickener in improving melt tension was lower in Comparative Examples 1-3, in which raw materials derived from fossil fuel resources were used only. From these findings, it can be seen that when raw materials derived from biomass resources are used, in order to satisfy extrusion moldability and hose water aging resistance, not only the use of a thickener but also advanced design in conjunction with melt kneading conditions is required. [Industrial Applicability]

[0100] Despite using a biomass resource-derived polyester elastomer with a high bio-based content, the polyester elastomer resin composition of the present invention can retain the excellent mechanical properties, storage stability, elongation retention rate after heat and humidity treatment, extrusion moldability, and water aging resistance of a fossil fuel resource-derived polyester elastomer, and is suitable for fields that require high-precision moldability such as hoses, films, and wire coating materials. Therefore, the polyester elastomer resin composition of the present invention greatly contributes to solving environmental problems such as the depletion of fossil fuel resources and is extremely useful in the industry.

Claims

Claim 1 A polyester elastomer resin composition containing at least one component derived from biomass resources and a heat stabilizer, wherein the biobased degree of the polyester elastomer resin composition is 20 to 85%, and the oligomer content having a number average molecular weight of less than 1000 in the polyester elastomer derived from biomass resources is 2.5% by weight or less, and the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN, and the polyester elastomer resin composition satisfies any one of the following requirements (i), (ii), and (iii). (i) The polyester elastomer derived from biomass resources is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as components and a soft segment composed of an aliphatic polyether are bonded, and 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. (ii) The polyester elastomer derived from biomass resources is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as components and a soft segment composed of C36 dimer acid are bonded, and the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the C36 dimer acid is derived from biomass resources. (iii) The polyester elastomer derived from biomass resources is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and 1,4-butanediol as components and a soft segment composed of an aliphatic polyether are bonded, and the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and the aliphatic polyether are derived from biomass resources. Claim 2 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 biobased content of the polyester elastomer resin composition is 20 to 85%, the melt tension of the polyester elastomer resin composition is 1.0 to 50 cN, 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 it satisfies any one of the following requirements (i), (ii), and (iii). Polyester elastomer resin composition. (i) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components and a soft segment composed of an aliphatic polyether are bonded, and 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. (ii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components and a soft segment composed of C36 dimer acid are bonded, and the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the C36 dimer acid is derived from a biomass resource. (iii) The biomass resource-derived polyester elastomer is a polyester elastomer in which a hard segment composed of a polyester containing an aromatic dicarboxylic acid and 1,4-butanediol as constituent components and a soft segment composed of an aliphatic polyether are bonded, and the aromatic dicarboxylic acid is derived from fossil fuel resources, and the 1,4-butanediol and the aliphatic polyether are derived from a biomass resource.

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

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

5. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the aliphatic polyether derived from biomass resources in the biomass resource-derived polyester elastomer is polytetramethylene ether glycol.

6. The polyester elastomer resin composition according to claim 1 or 2, characterized in that the reduced viscosity of the biomass resource-derived polyester elastomer is 1.2 dl / g or more.

7. A hose formed by extrusion molding of the polyester elastomer resin composition according to claim 1 or 2.

8. A film formed by extrusion molding of the polyester elastomer resin composition according to claim 1 or 2.

9. An electric wire coating material formed by extrusion molding of the polyester elastomer resin composition according to claim 1 or 2.

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