Resin composition, molded body, and film
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- TOYOBO MC CORP
- Filing Date
- 2025-04-24
- Publication Date
- 2026-07-30
Smart Images
Figure JPOXMLDOC01-APPB-T000001 
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Abstract
Description
Resin composition, molded article, and film
[0001] The present invention relates to a resin composition, a molded article, and a film.
[0002] Polyester elastomers are excellent in injection moldability and extrusion moldability, have high mechanical strength, and are used as materials with excellent rubber-like properties such as elastic recovery, impact resistance, and flexibility, as well as heat resistance and cold resistance, in a wide range of applications such as automotive parts, electrical and electronic parts, fibers, films, and sports parts.
[0003] In addition, since polyester is excellent in heat resistance and mechanical properties, it is used in automotive parts and electrical and electronic parts.
[0004] Patent Document 1 discloses the production of a polyester elastomer with excellent heat resistance by copolymerizing polyester as a hard segment and polytetramethylene ether glycol (PTMG) as a soft segment to impart flexibility.
[0005] However, in the production method of Patent Document 1, the extruded molded article obtained using the polyester elastomer has problems such as insufficient flexibility despite excellent hardness and cracking when bent.
[0006] In addition, when the polyester elastomer is molded at a high processing temperature, bubbles are generated, so molding at a low processing temperature is required. However, in molding at a low processing temperature, if the melting point of the obtained extruded molded article is too high, white contamination derived from highly crystallized substances is likely to occur during extrusion molding, while if the melting point of the extruded molded article is too low, the high-temperature rigidity and high-temperature durability of the extruded molded article are inferior, resulting in problems.
[0007] Patent No. 3270185
[0008] In view of such a situation, the present invention has been devised, and an object thereof is to provide a resin composition containing a polyester elastomer resin that achieves both high hardness and flexibility and is excellent in extrusion moldability, high-temperature rigidity, and high-temperature durability, a molded article formed from the resin composition, and a film.
[0009] In order to solve the above problems, the present invention was developed through diligent research. As a result, a resin composition was found that uses a polyester elastomer resin obtained from specific components and has a glass transition temperature within a specific range, thereby achieving both high hardness and flexibility, and further exhibiting excellent extrusion moldability, high-temperature rigidity, and high-temperature durability. This led to the completion of the present invention.
[0010] That is, the present invention has the following configurations (1) to (8): (1) A resin composition comprising a polyester elastomer resin (A) in which a hard segment formed from a polyester comprising an aromatic dicarboxylic acid component and a glycol component is bonded to a soft segment formed from polytetramethylene ether glycol, wherein the aromatic dicarboxylic acid component contains 86 to 100 mol% terephthalic acid units and 0 to 14 mol% isophthalic acid units, and when the total amount of glycol components contained in the hard segment and the soft segment is 100 mol%, it contains 85 to 97 mol% ethylene glycol units and 3 to 15 mol% polytetramethylene ether glycol units, and the glass transition temperature is 0 to 90°C. (2) The resin composition according to (1), wherein the reduced viscosity of the polyester elastomer resin (A) is 0.7 to 1.8 dl / g. (3) The resin composition according to (1), wherein the melting point of the polyester elastomer resin (A) is 190 to 243°C. (4) The resin composition according to (1), wherein the elongation at break is 200% or more. (5) The resin composition according to (1), wherein the storage modulus at 23°C, as measured by dynamic viscoelasticity, is 100 MPa to 1600 MPa. (6) The resin composition according to (1), which contains 0.01 to 1 part by mass of peroxide decomposing agent (B) per 100 parts by mass of the polyester elastomer resin (A). (7) An extruded sheet molded article formed from the resin composition according to any one of (1) to (6). (8) A film formed from the resin composition according to any one of (1) to (6).
[0011] The resin composition of the present invention uses a polyester elastomer resin obtained from specific components and has a glass transition temperature within a specific range. As a result, the resin composition achieves both high hardness and flexibility, and is also excellent in extrusion moldability, high-temperature rigidity, and high-temperature durability, making it very useful.
[0012] [Polyester elastomer resin (A)] Polyester elastomer resin (A) is composed of a hard segment formed from a polyester comprising an aromatic dicarboxylic acid component and a glycol component, and a soft segment formed from polytetramethylene ether glycol, wherein the aromatic dicarboxylic acid component contains 86 to 100 mol% terephthalic acid units and 0 to 14 mol% isophthalic acid units, and when the total glycol components contained in the hard segment and the soft segment are taken as 100 mol%, they contain 85 to 97 mol% ethylene glycol units and 3 to 15 mol% polytetramethylene ether glycol units.
[0013] (Hard segment) The hard segment is formed from a polyester comprising an aromatic dicarboxylic acid component and a glycol component, wherein the aromatic dicarboxylic acid component of the polyester contains terephthalic acid (TPA) units. The use of terephthalic acid results in a polyester elastomer resin (A) with high crystallinity, high temperature rigidity, and high temperature durability, which is preferable.
[0014] The content of the terephthalic acid units in the aromatic dicarboxylic acid component is 86 to 100 mol%, preferably 88 to 98 mol%, and more preferably 90 to 96 mol%. Using within this range results in a polyester elastomer resin (A) with excellent extrusion moldability, high-temperature rigidity, and high-temperature durability, which is preferable.
[0015] In addition to terephthalic acid, the aforementioned aromatic dicarboxylic acid may also contain isophthalic acid (IPA), and can be used within a range that does not significantly lower the melting point of the polyester elastomer resin (A).
[0016] The content of the isophthalic acid units is 0 to 14 mol%, preferably 2 to 12 mol%, and more preferably 4 to 10 mol%, in the aromatic dicarboxylic acid. If the isophthalic acid content is too high, the crystallinity may be low, and it may not be possible to obtain a product that satisfies the requirements for high-temperature rigidity and high-temperature durability.
[0017] The aforementioned aromatic dicarboxylic acid is used as a raw material for the polyester elastomer resin (A), but an ester of the aromatic dicarboxylic acid may also be used. For example, terephthalic acid can be used as a raw material, but dimethyl terephthalate can also be used.
[0018] The polyester is preferably an aromatic polyester because it uses the aromatic dicarboxylic acid component as a constituent.
[0019] The glycol component, which is a constituent of the polyester, is not particularly limited and can be used, but examples include aliphatic glycols, and among these, from the viewpoint of high crystallinity, ethylene glycol (EG) and 1,4-butanediol can be mentioned, with ethylene glycol being particularly preferred. In other words, the main component constituting the polyester is preferably an ethylene terephthalate unit (a unit formed from terephthalic acid and ethylene glycol).
[0020] (Soft segment) The soft segment is formed from polytetramethylene ether glycol (PTMG). Using polytetramethylene ether glycol results in a polyester elastomer resin (A) with excellent flexibility, which is preferable.
[0021] The number-average molecular weight (Mn) of the PTMG is preferably 500 to 4000, more preferably 700 to 3000, and even more preferably 800 to 2500. If the number-average molecular weight (Mn) is below the above range, the elastomer properties of the polyester elastomer resin (A) may not be easily exhibited. On the other hand, if the number-average molecular weight (Mn) exceeds the above range, the compatibility of the soft segment with the hard segment decreases, and copolymerization in a block-like manner may become difficult.
[0022] The polyester elastomer resin (A) is obtained by bonding the hard segment and the soft segment. Using the hard segment and the soft segment results in a polyester elastomer resin (A) that satisfies high-temperature rigidity, high-temperature durability, flexibility, and low-temperature properties, which is preferable.
[0023] When the total amount of glycol components contained in the hard segment and the soft segment is set to 100 mol%, the content of ethylene glycol (EG) units is 85 to 97 mol%, preferably 86 to 95 mol%, and more preferably 88 to 94 mol%. Within this range, a polyester elastomer resin (A) that satisfies high-temperature rigidity and high-temperature durability is obtained, which is preferable.
[0024] When the total amount of glycol components contained in the hard segment and the soft segment is set to 100 mol%, the content of polytetramethylene ether glycol (PTMG) units is 3 to 15 mol%, preferably 5 to 15 mol%, and more preferably 6 to 13 mol%. Within this range, a polyester elastomer resin (A) that satisfies flexibility and low-temperature properties is obtained, which is preferable.
[0025] The mass ratio of the hard segment to the soft segment in the polyester elastomer resin (A) is preferably 40:60 to 85:15, more preferably 50:50 to 80:20, even more preferably 60:40 to 78:22, and particularly preferably 62:38 to 76:24. If the amount of hard segment is small (the amount of PTMG is large), the crystallinity will be low, and it may not be possible to obtain a product that satisfies the function of high hardness. On the other hand, if the amount of hard segment is large (the amount of PTMG is small), the glass transition temperature (Tg) of the resulting polyester elastomer resin will be high, and it may not be possible to obtain a product that satisfies the functions of rebound elasticity, flexibility, and low-temperature mechanical properties as polyester elastomer resin (A). In addition, the compatibility between the hard segment and the soft segment may decrease, making it difficult to copolymerize them in a block shape.
[0026] [Method for producing polyester elastomer resin (A)] The polyester elastomer resin (A) can be obtained by first synthesizing the aromatic polyester and then copolymerizing it with the polytetramethylene ether glycol (PTMG) that constitutes the soft segment. In this case, the aromatic polyester can be easily synthesized according to a conventional method for producing polyester.
[0027] Furthermore, there are no particular limitations on the method for producing the polyester elastomer resin (A), and known methods can be used. For example, a method may be used in which a lower alcohol diester of a dicarboxylic acid, an excess amount of low molecular weight glycol, and a soft segment component are transesterified in the presence of a catalyst, and the resulting reaction product is polycondensed.
[0028] The reduced viscosity of the polyester elastomer resin (A) is preferably 0.7 to 1.8 dl / g, more preferably 0.8 to 1.7 dl / g, and even more preferably 0.9 to 1.6 dl / g, from the viewpoint of exhibiting flexibility and high-temperature durability. If the reduced viscosity is below the above range, the molecular weight of the polyester elastomer resin (A) is small, which may reduce flexibility and high-temperature durability. If the reduced viscosity exceeds the above range, the machine load may become excessive during extrusion molding, and defects such as melt fractures may easily occur in the molded article.
[0029] The melting point of the polyester elastomer resin (A) is preferably 190 to 243°C, more preferably 206 to 240°C, and even more preferably 210 to 235°C, from the viewpoint of extrusion moldability and high-temperature rigidity. When the melting point is within the above range, the polyester elastomer resin (A) is preferable because it allows for extrusion moldability at low temperatures and has excellent high-temperature rigidity. If the melting point is below the above range, the crystallinity will be low, the storage modulus at 140°C measured by dynamic viscoelasticity will be low, and it may not be possible to obtain a resin that satisfies the function of high-temperature rigidity. Furthermore, if the melting point exceeds the above range, crystallization of the resin will progress in the retention area during extrusion molding, and there is a risk that white contamination originating from highly crystalline material will occur.
[0030] The acid value of the polyester elastomer resin (A) is preferably 1 to 40 eq / ton (eq / t), more preferably 10 to 30 eq / ton, and even more preferably 15 to 25 eq / ton, from the viewpoint of exhibiting hydrolysis resistance of the molded product. It is preferable that the acid value be within the above range, as this reduces the number of carboxyl ends that promote hydrolysis of the polymer constituting the resulting thermoplastic polyester elastomer resin (A), resulting in excellent hydrolysis resistance of the molded product obtained using the thermoplastic polyester elastomer resin (A).
[0031] [Peroxide Decomposing Agent (B)] The resin composition may contain a peroxide decomposing agent (B) from the viewpoint of excellent heat retention stability. The peroxide decomposing agent (B) is a compound that exhibits the ability to decompose peroxides into alcohol, and is different from a simple stabilizer. In the present invention, even if peroxides that cause foaming are generated during molding at high temperatures, they are decomposed into alcohol by the peroxide decomposing agent (B), so foaming during molding is suppressed, and pellets and products of good quality can be efficiently manufactured.
[0032] The content of the peroxide decomposing agent (B) is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 parts by mass, and even more preferably 0.03 to 0.7 parts by mass, per 100 parts by mass of the polyester elastomer resin (A). If the content of the peroxide decomposing agent (B) is below the above range, the foam suppression effect may not be sufficiently obtained. Also, if the content of the peroxide decomposing agent (B) is above the above range, the foam suppression effect will not improve and the color of the molded product may be impaired.
[0033] The peroxide decomposing agent (B) may be, for example, phosphonite (a compound having one carbon-phosphorus bond and two phosphorus-oxygen bonds, R-P-(O-R) ２ ), phosphite (a compound having three phosphorus-oxygen bonds, P-(O-R) ３ ), and hindered amine stabilizers (HALS) are preferred. In the chemical formulas of phosphonite and phosphite, R is a hydrocarbon group, which may be the same or different, and may be linked to each other. The hydrocarbon group may also be a hydrocarbon to which substituents such as hydroxyl groups or halogen groups are bonded. From the viewpoint of the heat resistance of the peroxide decomposing agent (B) itself, it is preferable that R has an aromatic structure, an alicyclic structure, or a linked ring structure. In particular, it is preferable that the peroxide decomposing agent (B) includes at least one of phosphonite and phosphite, which have a great effect in suppressing foaming during molding.
[0034] [Other Additives] In addition to the polyester elastomer resin (A) and the peroxide decomposing agent (B), the resin composition may contain general-purpose antioxidants such as aromatic amines, hindered phenols, and sulfur-based antioxidants. These may be used individually or in combination of two or more.
[0035] Examples of the aromatic amine antioxidants include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 4-isopropoxydiphenylamine.
[0036] While general-purpose compounds can be used as the aforementioned hindered phenol antioxidants, those with a molecular weight of 500 or more, such as N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide) and tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, are preferred because they do not volatilize easily in a high-temperature atmosphere.
[0037] Examples of sulfur-based antioxidants include sulfur-containing compounds such as thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropion esters. Specific examples include dilauryl thiodipropionate, distearyl thiodipropionate, didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite. In particular, thioether-based antioxidants having a thioether structure can be suitably used because they receive oxygen from oxidized substances and reduce them.
[0038] As the content of the antioxidant, from the viewpoint of exhibiting long-term durability (such as heat aging resistance and water resistance), it is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polyester elastomer resin (A).
[0039] As a method for determining the composition and composition ratio of the resin composition, 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.
[0040] Further, when the resin composition requires weather resistance, an ultraviolet absorber and / or a hindered amine compound can be blended. For example, benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicylic-based light stabilizers can be used. The blending amount is preferably 0.1 to 5% based on the mass of the resin composition.
[0041] In the resin composition, as additives other than the above-mentioned other additives, resins, inorganic fillers, stabilizers, and anti-aging agents other than the above can be added within a range that does not impair the characteristics of the present invention. Also, as other additives, coloring pigments, inorganic and organic fillers, coupling agents, tackiness improvers, quenchers, stabilizers such as metal deactivators, and flame retardants can be added. The total blending amount of these various additives is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the polyester elastomer resin (A).
[0042] [Manufacturing method of resin composition] As a manufacturing method of the resin composition, a method of melt-kneading each component using a normal mixer for thermoplastic resins typified by a single-screw or twin-screw screw-type melt-kneader or a kneader-type heater, and then pelletizing by a granulation process can be mentioned.
[0043] [Method for manufacturing a molded body] The method for manufacturing a molded body in the present invention is not particularly limited; for example, the resin composition obtained by the method for manufacturing the resin composition is extruded using a generally used molding machine (extrusion coating, T-die coating, calendar coating, etc.), injection molding, compression molding, blow molding, etc. to perform a molding process such as melt kneading to obtain a molded body. When obtaining a molded body in the form of a sheet or film, it is preferable to use the extrusion molding.
[0044] The melting temperature of the resin composition during the extrusion molding is preferably 160 to 260°C, more preferably 180 to 250°C. If the melting temperature is low, melting will be insufficient and unmelted resin is likely to occur. If the melting temperature is high, the resin composition is likely to undergo thermal degradation, and there is a risk that bubbles will form in the resulting molded body.
[0045] The glass transition temperature (Tg) of the resin composition is 0 to 90°C, preferably 15 to 60°C, and more preferably 35 to 55°C from the viewpoint of exhibiting high rigidity. If the glass transition temperature is less than the above range, it may not be possible to obtain a product that satisfies the mechanical strength. Also, if the glass transition temperature exceeds the above range, it may not be possible to obtain a product that satisfies toughness and flexibility.
[0046] The elongation at break of the resin composition is preferably 200% or more, more preferably 300% or more, and even more preferably 400% or more from the viewpoint of the flexibility of the molded product being exhibited.
[0047] The storage modulus at 23°C when measured by the dynamic viscoelasticity of the resin composition is preferably 100 MPa to 1600 MPa, more preferably 200 MPa to 1500 MPa, and even more preferably 300 MPa to 1000 MPa from the viewpoint of the molded product exhibiting high rigidity.
[0048] The storage modulus at 140°C when measured by the dynamic viscoelasticity of the resin composition is preferably 10 MPa to 150 MPa, more preferably 20 MPa to 140 MPa, and even more preferably 30 MPa to 120 MPa from the viewpoint of excellent high-temperature rigidity being exhibited.
[0049] The difference between the storage modulus at 23°C and the storage modulus at 140°C, as measured by dynamic viscoelasticity of the resin composition, is not particularly limited, but is preferably 200 MPa to 1300 MPa, more preferably 250 MPa to 900 MPa, and even more preferably 300 MPa to 800 MPa, in order to exhibit excellent high-temperature durability. In particular, if the storage modulus at 140°C is low, and the difference between the storage modulus at 23°C and the storage modulus at 140°C becomes large (the difference exceeds 1000), there is a risk that a product that satisfies high-temperature durability cannot be obtained.
[0050] The elongation retention rate at break (140°C) of the resin composition is preferably 30 to 200%, more preferably 40 to 160%, and even more preferably 60 to 120%, from the viewpoint of excellent high-temperature durability.
[0051] The present invention relates to an extruded sheet molded article formed from the aforementioned resin composition. Since the extruded sheet molded article is formed using the aforementioned resin composition, it achieves both high hardness and flexibility, and furthermore, it is a useful sheet with excellent extrudeability, high-temperature rigidity, and high-temperature durability.
[0052] The present invention relates to a film formed from the aforementioned resin composition. Because the film is formed using the aforementioned resin composition, it achieves both high hardness and flexibility, and furthermore, it is a useful film with excellent extrusion moldability, high-temperature rigidity, and high-temperature durability.
[0053] The resin composition of the present invention can be used in a wide range of applications, including covering materials for sheets, films, hoses, tubes, and cables, as well as fibers, elastic yarns, three-dimensional mesh fiber structures, monofilaments, and foamed molded products. Furthermore, it can be developed into various molded products obtained by molding methods such as injection molding, two-color molding, extrusion molding, transfer molding, blow molding, and foam molding.
[0054] The resin composition of the present invention can be used as a modifier for hard resins such as polyester resins and polyamide resins, thereby imparting toughness to the hard resins. In particular, modification to polyester resins is preferred from the viewpoint of compatibility, and modification to polyethylene terephthalate resins is more preferred.
[0055] The extruded sheet molded articles and films of the present invention can be applied to decorative films and biaxially oriented films. Furthermore, by using the extruded sheet molded articles, films, fibers, elastic yarns, and foamed products, they can be applied to sheet laminates, film laminates, fiber laminates, laminates with binder fibers, laminates with nonwoven fabrics, and composites with foamed products. These are useful from the viewpoint of monomaterialization and recyclability in clothing, breathable waterproof films, synthetic leather, hook-and-loop fasteners, mats, shoes, sporting goods, office chairs, cosmetic components, cosmetic containers, brushes, etc. These laminates or composites may also contain polyester-based adhesives.
[0056] Examples are given below to demonstrate the effects of the present invention, but the present invention is not limited in any way by these examples. The evaluation of each measurement value was performed by the following method.
[0057] [Melting Point] The polyester elastomer resin obtained by the synthesis described below was used as the sample for measurement. Using a differential scanning calorimetry analyzer "DSC220" manufactured by Seiko Electronics Industries, Ltd., 5 mg of the sample was placed in an aluminum pan, sealed by pressing down on the lid, and held at 270°C for 5 minutes to completely melt the sample. After that, it was rapidly cooled with liquid nitrogen and then measured from -150°C to 260°C at a heating rate of 20°C / min. From the obtained thermogram curve, the endothermic peak temperature was defined as the melting point (°C).
[0058] [Reduced Viscosity] 0.05 g of the obtained polyester elastomer resin was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60 / 40), and the reduced viscosity (dl / g) was measured at 30°C using an Ubbelohde viscous tube.
[0059] [Acid Value] The acid value (eq / ton) was determined by dissolution titration, in which 200 mg of the obtained polyester elastomer resin, which had been thoroughly dried (100°C, 6 hours), was dissolved in 10 mL of hot benzyl alcohol, the resulting solution was cooled, and then 10 mL of chloroform and phenol red were added, and the solution was titrated with a 1 / 25 N potassium alcohol solution (methanol solution of KOH).
[0060] The components used in the examples are as follows:
[0061] [Polyester Elastomer Resin (A)] (Polyester Elastomer Resin (A-1): IPA content 0 mol%, PTMG content 7 mol%) 46.7 parts by mass of terephthalic acid (TPA, manufactured by Mitsui Chemicals), 33.6 parts by mass of ethylene glycol (EG, manufactured by Nippon Shokubai), and 19.7 parts by mass of polytetramethylene ether glycol (PTMG1000, manufactured by BASF, molecular weight 1000 g / mol) were charged into the reaction vessel. Furthermore, antimony trioxide (Sb) was added as a catalyst to 100 parts by mass of the polymer to be purified. ２ O ３ 0.05 parts by mass of (manufactured by Nippon Seiko) and 0.05 parts by mass of zinc acetate dihydrate (ZnOAc, manufactured by Nacalai Tesque) were charged into a reaction vessel. The temperature was raised from room temperature to 220°C over 130 minutes to carry out the transesterification reaction. Then, the pressure inside the vessel was gradually reduced and the temperature was further raised to 245°C and below 1 Torr over 70 minutes to carry out the initial condensation reaction. A polymerization reaction was then carried out at 250°C and below 1 Torr for 60 minutes. After the polymerization reaction was completed, the polymer was cast and removed as pellets to obtain polyester elastomer resin (A-1) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%). The melting point of this polyester elastomer resin (A-1) was 239°C, the reduced viscosity was 1.09 dl / g, and the acid value was 23 eq / ton.
[0062] (Polyester elastomer resin (A-2): IPA content 5 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-1), the amount of TPA was changed to 44.3 parts by mass, isophthalic acid (IPA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2.3 parts by mass, EG 33.7 parts by mass, and PTMG 1000 19.7 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-2) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. The melting point of this polyester elastomer resin (A-2) was 230°C, the reduced viscosity was 1.10 dl / g, and the acid value was 21 eq / ton.
[0063] (Polyester elastomer resin (A-3): IPA content 10 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 4.7 parts by mass, EG to 33.6 parts by mass, and PTMG 1000 to 19.7 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-3) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. The melting point of this polyester elastomer resin (A-3) was 215°C, the reduced viscosity was 1.10 dl / g, and the acid value was 21 eq / ton.
[0064] (Polyester elastomer resin (A-4): IPA content 10 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-3), the polymerization reaction was changed to 120 minutes under a temperature of 1 Torr or less. The other production methods were the same as for polyester elastomer resin (A-3), and polyester elastomer resin (A-4) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. The melting point of this polyester elastomer resin (A-4) was 215°C, the reduced viscosity was 1.50 dl / g, and the acid value was 19 eq / ton.
[0065] (Polyester elastomer resin (A-5): IPA content 14 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 4.8 parts by mass, EG to 34.3 parts by mass, and PTMG1000 to 20.0 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-5) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. The melting point of this polyester elastomer resin (A-5) was 207°C, the reduced viscosity was 1.10 dl / g, and the acid value was 21 eq / ton.
[0066] (Polyester elastomer resin (A-6): IPA content 10 mol%, PTMG content 9 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 4.5 parts by mass, EG to 31.6 parts by mass, and PTMG1000 to 24.0 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-6) with a hard segment / soft segment ratio of 63 / 37 (mass%) and a PTMG content of 32.5 (mass%) was obtained. The melting point of this polyester elastomer resin (A-6) was 213°C, the reduced viscosity was 1.21 dl / g, and the acid value was 21 eq / ton.
[0067] (Polyester elastomer resin (A-7): IPA content 10 mol%, PTMG content 5 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 4.9 parts by mass, EG to 35.9 parts by mass, and PTMG1000 to 14.8 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-7) with a hard segment / soft segment ratio of 76 / 24 (mass%) and a PTMG content of 20.6 (mass%) was obtained. The melting point of this polyester elastomer resin (A-7) was 224°C, the reduced viscosity was 1.01 dl / g, and the acid value was 24 eq / ton.
[0068] (Polyester elastomer resin (A-8): IPA content 5 mol%, PTMG content 9 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 2.2 parts by mass, EG to 31.7 parts by mass, and PTMG 1000 to 24.0 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-8) with a hard segment / soft segment ratio of 63 / 37 (mass%) and a PTMG content of 32.5 (mass%) was obtained. The melting point of this polyester elastomer resin (A-8) was 224°C, the reduced viscosity was 1.20 dl / g, and the acid value was 21 eq / ton.
[0069] (Polyester elastomer resin (A-9): IPA content 12 mol%, PTMG content 5 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 5.9 parts by mass, EG to 35.9 parts by mass, and PTMG 1000 to 14.8 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-9) with a hard segment / soft segment ratio of 76 / 24 (mass%) and a PTMG content of 20.6 (mass%) was obtained. The melting point of this polyester elastomer resin (A-9) was 222°C, the reduced viscosity was 1.01 dl / g, and the acid value was 24 eq / ton.
[0070] (Polyester elastomer resin (A-10): IPA content 30 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 14.0 parts by mass, EG to 33.6 parts by mass, and PTMG1000 to 19.7 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-10) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. This polyester elastomer resin (A-10) had no melting point, a reduced viscosity of 1.10 dl / g, and an acid value of 21 eq / ton.
[0071] (Polyester elastomer resin (A-11): IPA content 0 mol%, PTMG content 20 mol%) In the method for producing polyester elastomer resin (A-1), the amounts of IPA, EG, and PTMG 1000 were changed to 34.8 parts by mass of TPA, 0 parts by mass of IPA, 23.3 parts by mass of EG, and 41.9 parts by mass of PTMG 1000, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-11) with a hard segment / soft segment ratio of 40 / 60 (mass%) and a PTMG content of 52.7 (mass%) was obtained. The melting point of this polyester elastomer resin (A-11) was 204°C, the reduced viscosity was 1.50 dl / g, and the acid value was 18 eq / ton.
[0072] (Polyester elastomer resin (A-12): IPA content 0 mol%, PTMG content 2.5 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 0 parts by mass, EG to 39.1 parts by mass, and PTMG1000 to 7.9 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-12) with a hard segment / soft segment ratio of 87 / 13 (mass%) and a PTMG content of 11.6 (mass%) was obtained. The melting point of this polyester elastomer resin (A-12) was 244°C, the reduced viscosity was 0.85 dl / g, and the acid value was 23 eq / ton.
[0073] (Polyester elastomer resin (A-13): IPA content 20 mol%, PTMG content 2 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 10.8 parts by mass, EG to 39.7 parts by mass, and PTMG1000 to 6.5 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-13) with a hard segment / soft segment ratio of 89 / 11 (mass%) and a PTMG content of 9.5 (mass%) was obtained. The melting point of this polyester elastomer resin (A-13) was 216°C, the reduced viscosity was 0.81 dl / g, and the acid value was 23 eq / ton.
[0074] (Polyester elastomer resin (A-14): IPA content 15 mol%, PTMG content 7 mol%) In the method for producing polyester elastomer resin (A-1), the amount of IPA was changed to 4.8 parts by mass, EG to 34.5 parts by mass, and PTMG1000 to 20.1 parts by mass, and each was charged into a reaction vessel. The other manufacturing methods were the same as for the method for producing polyester elastomer resin (A-1), and polyester elastomer resin (A-14) with a hard segment / soft segment ratio of 69 / 31 (mass%) and a PTMG content of 27.1 (mass%) was obtained. The melting point of this polyester elastomer resin (A-14) was 205°C, the reduced viscosity was 1.10 dl / g, and the acid value was 21 eq / ton.
[0075] [Peroxide Decomposing Agents (B)] (B-1) Phosphorus-based antioxidant (phosphite), product name: ADEKA Stab PEP-36, manufactured by ADEKA (B-2) Phosphorus-based antioxidant (phosphonite), product name: HOSTANOX P-EPQ, manufactured by Clariant Japan
[0076] Table 1 shows the resin compositions and physical properties of the polyester elastomer resins (A-1) to (A-12) obtained above. In Table 1, the composition in mol% is a value calculated from the raw material charging ratio and the molecular weight of each raw material.
[0077]
[0078] [Examples 1-9 and Comparative Examples 1-5] For Examples 1-9 and Comparative Examples 1-5, pellets obtained from the polyester elastomer resins (A-1) to (A-14) listed in Table 2 were used for evaluation.
[0079] [Examples 10-12] For Examples 10-12, 100 parts by mass of the polyester elastomer resin (A-3) pellets listed in Table 2 were mixed with the peroxide decomposing agent (B) in the respective amounts, and the mixture was kneaded and compounded using a twin-screw extruder to obtain the resin composition pellets of Examples 10-12.
[0080] [Glass Transition Temperature] Using the Rheogel-E4000 dynamic viscoelasticity measuring instrument from UBM Co., Ltd., the temperature dispersion measurement of the dynamic viscoelasticity of strip-shaped test specimens was performed in the range of -100°C to 200°C at a frequency of 11 Hz and a heating rate of 2°C / min. The loss tangent (tanδ) was determined, and the peak top temperature of tanδ was defined as the glass transition temperature (°C). The test specimens were prepared by producing a 200 μmt sheet from a resin composition dried under reduced pressure at 120°C for 8 hours using a 30φ single-screw extruder at a cylinder temperature (Tm + 20°C), and then cutting out strips with a length of 15 mm and a width of 4 mm from the sheet.
[0081] [Elongation at Break] The tensile elongation at break (%) of the resin composition was measured in reference to JIS K6251:2010. Test specimens were prepared by extruding a 200 μmt sheet of the resin composition, which had been dried under reduced pressure at 120°C for 8 hours, using a 30φ single-screw extruder at a cylinder temperature (Tm + 20°C), and punching out a dumbbell-shaped No. 3 test specimen from the sheet.
[0082] [Storage Modulus] Using the Rheogel-E4000 dynamic viscoelasticity measuring instrument from UBM Corporation, the temperature dispersion of dynamic viscoelasticity of strip-shaped test specimens was measured in the range of -100°C to 200°C at a frequency of 11 Hz and a heating rate of 2°C / min, and the storage modulus (MPa) at 23°C and 140°C was determined. The test specimens were prepared by producing a 200 μmt sheet from a resin composition dried under reduced pressure at 120°C for 8 hours using a 30φ single-screw extruder at a cylinder temperature (Tm + 20°C), and then cutting out strips with a length of 15 mm and a width of 4 mm from the sheet.
[0083] [Elongation retention rate at break (140°C, 24hr): Sheet heat resistance] The dumbbell-shaped No. 3 test specimen described above was left in an air environment at 150°C for 24 hours, then removed, and the tensile elongation at break was measured in the same manner as above, referring to JIS K6251:2010. The elongation retention rate at break (%) of the resin composition was calculated using the following formula and used as an indicator of sheet heat resistance. The initial tensile elongation at break is the tensile elongation at break before heat treatment. Elongation retention rate at break (%) = Tensile elongation at break after each treatment / Initial tensile elongation at break × 100
[0084] [Extrudeability (Suppression of White Contamination)] Sheet extrusion molding was performed using a 30φ single-screw extruder at a cylinder temperature of 250°C on pellets of a resin composition dried under reduced pressure at 120°C for 8 hours. Extrudeability was evaluated according to the following criteria based on whether or not white contamination occurred. If white contamination occurred during extrusion molding and the sheet appearance quality was poor, the extrudeability was evaluated as poor. Conversely, if there was no white contamination, or only a small amount of white contamination, and it was possible to secure a sheet with a good appearance, the extrudeability was evaluated as excellent. No white contamination in the extruded sheet: Excellent White contamination in the extruded sheet, but it is possible to secure a good quality sheet: Acceptable Severe white contamination in the extruded sheet, making it impossible to secure a good quality sheet: Poor
[0085] [Thermal Retention Stability (Suppression of Foaming During Extruded Sheet Production)] Pellets of a resin composition dried under reduced pressure at 120°C for 8 hours were extruded into sheets using a 30φ single-screw extruder at a cylinder temperature of 250°C. Thermal retention stability was evaluated based on whether or not foaming occurred according to the following criteria. If foaming occurred during extrusion molding, making it impossible to obtain sheets, the thermal retention stability was evaluated as poor. Conversely, if there was no foaming or only slight foaming, and it was possible to consistently obtain sheets, the thermal retention stability was evaluated as excellent. No foaming during extrusion molding and no air bubbles in the sheet: Excellent No foaming during extrusion molding but air bubbles in the sheet: Acceptable Severe foaming during extrusion molding making it impossible to obtain sheets: Poor
[0086] Table 2 shows the compositions of the resin compositions (including the case of polyester elastomer resin alone) of Examples 1 to 12 and Comparative Examples 1 to 5, and the evaluation results of the resin compositions.
[0087]
[0088] As is clear from the evaluation results in Tables 1 and 2 above, in Examples 1 to 12, by using the desired polyester elastomer resin (A), the melting point and reduced viscosity could be adjusted, and the sheets obtained using the resulting resin compositions exhibited excellent glass transition temperature, elongation at break, storage modulus, and elongation retention at break, achieving both high hardness and flexibility, and furthermore, sheets with excellent extrudeability, high-temperature rigidity, and high-temperature durability were obtained. In particular, in Examples 2 to 12, by adjusting the IPA content and PTMG content in the polyester elastomer resin, it was confirmed that both the storage modulus and elongation at break at 23°C were high, and the melting point did not produce white contamination during extrusion molding at 250°C, while the elongation retention at break at 140°C × 24hr was high, and the high-temperature rigidity and high-temperature durability were excellent. Furthermore, in Examples 10 to 12, it was confirmed that by incorporating an appropriate amount of peroxide decomposing agent (B), the generation of peroxides was suppressed, foaming did not occur during extrusion molding, or the resulting sheet was free of air bubbles, exhibiting excellent heat retention stability, high-temperature rigidity, and high-temperature durability.
[0089] On the other hand, in Comparative Example 1, although high hardness and flexibility could be achieved by adjusting the PTMG content, the high IPA content meant that the polyester elastomer resin had no melting point and fluidized at 140°C (making it impossible to measure the storage modulus at 140°C). The elongation retention rate at break under 140°C × 24hr was also 0, confirming poor high-temperature rigidity and high-temperature durability. In Comparative Example 2, although the elongation at break was high and flexibility was excellent, the high PTMG content in the polyester elastomer resin resulted in a low glass transition temperature of the resin composition and a low storage modulus at 23°C, resulting in poor mechanical rigidity at room temperature, and it was not possible to achieve both high hardness and flexibility. In Comparative Example 3, the high melting point of the polyester elastomer resin resulted in significant white contamination during extrusion molding at 250°C, confirming poor extrusion moldability. Furthermore, it was confirmed that the low PTMG content resulted in poor flexibility due to the low elongation at cleavage of the resin composition, and that the large difference between the storage modulus at 23°C and 140°C of the resin composition resulted in poor high-temperature durability of the sheet in a 140°C environment. In Comparative Example 4, the high IPA content in the polyester elastomer resin resulted in a large difference between the storage modulus at 23°C and 140°C of the resin composition, and that the poor high-temperature durability of the sheet in a 140°C environment. It was also confirmed that the low PTMG content resulted in poor flexibility due to the low elongation at cleavage of the resin composition. In Comparative Example 5, although high hardness and flexibility could be achieved by adjusting the PTMG content, it was confirmed that the low melting point of the polyester elastomer resin and the low storage modulus at 140°C resulted in poor high-temperature rigidity.
[0090] By using a resin composition containing the polyester elastomer resin (A) of the present invention, it is possible to manufacture pellets and extruded products that exhibit both high hardness and flexibility, as well as excellent extrusion moldability, high-temperature rigidity, and high-temperature durability. Furthermore, it can be applied to a wide range of applications, including automotive parts, electrical and electronic components, textiles, films, and sports parts. In addition, for applications other than those listed above, it can be molded into various molded products by injection molding, two-color molding, extrusion molding, transfer molding, blow molding, etc.
Claims
1. A resin composition comprising a polyester elastomer resin (A) in which a hard segment formed from a polyester comprising an aromatic dicarboxylic acid component and a glycol component is bonded to a soft segment formed from polytetramethylene ether glycol, wherein the aromatic dicarboxylic acid component contains 86 to 100 mol% terephthalic acid units and 0 to 14 mol% isophthalic acid units, and when the total glycol components contained in the hard segment and the soft segment are 100 mol%, the resin composition contains 85 to 97 mol% ethylene glycol units and 3 to 15 mol% polytetramethylene ether glycol units, and the glass transition temperature is 0 to 90°C.
2. The resin composition according to claim 1, wherein the reduced viscosity of the polyester elastomer resin (A) is 0.7 to 1.8 dl / g.
3. The resin composition according to claim 1, wherein the melting point of the polyester elastomer resin (A) is 190 to 243°C.
4. The resin composition according to claim 1, wherein the elongation at break is 200% or more.
5. The resin composition according to claim 1, wherein the storage modulus at 23°C, as measured by dynamic viscoelasticity, is 100 MPa to 1600 MPa.
6. The resin composition according to claim 1, comprising 0.01 to 3 parts by mass of a peroxide decomposing agent (B) per 100 parts by mass of the polyester elastomer resin (A).
7. An extruded sheet molded article formed from the resin composition according to any one of claims 1 to 6.
8. A film formed from the resin composition according to any one of claims 1 to 6.