Polyalkylene ether glycol copolymer polyester, molded article

Abstract

To provide a copolymerized polyalkylene ether glycol copolyester excellent in thermal stability and flexibility.SOLUTION: A polyalkylene ether glycol copolyester has a structural unit derived from a dicarboxylic acid, a structural unit derived from a diol, and a structural unit derived from a polyalkylene ether glycol represented by the following formula (1). The structural unit derived from the polyalkylene ether glycol has a number average molecular weight of 500-5,000. HO-(R1-O)n-(R2-O)m-H (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyalkylene ether glycol copolymerized polyester obtained by copolymerizing polyalkylene ether glycol, and a molded article containing the copolymerized polyester. [Background technology]

[0002] Polyester resins occupy an important industrial position due to their excellent mechanical and chemical properties. For example, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate (PBT) are resins with excellent heat and chemical resistance, and are widely used in fields such as extrusion molding and injection molding of fibers, films, sheets, bottles, electrical and electronic components, automotive parts, and precision instrument parts due to their ease of molding and cost-effectiveness. However, in recent years, there has been a demand for polyesters that maintain the basic properties of polyester while adding new functions such as flexibility, low-temperature properties, and impact resistance. Furthermore, there is a desire for the efficient production of such polyesters.

[0003] For example, in the case of PBT, numerous copolymerization components have been investigated to improve its physical properties, but the number of cases that have reached practical application has been extremely limited. This is because copolymerization components tend to be randomly incorporated into the PBT chain, causing a decrease in the melting point and crystallization rate of PBT, thus counteracting the advantages of PBT, such as its high melting point and easy moldability. On the other hand, when copolymer components are incorporated into the PBT chain in a block-like manner, the effect of melting point depression corresponding to the introduction ratio is small, so various physical properties can be modified without lowering the melting point of PBT. Polytetramethylene glycol (hereinafter referred to as "PTMG") is known as a typical copolymer component (Patent Document 1). That is, a technique is known in which flexibility can be imparted to PBT by copolymerizing crystalline PBT as a hard segment with soft segment PTMG, and this is now widely used in the film field and other areas. As an example, Patent Document 2 describes an example in which a PTMG copolymer with a PTMG content of 10% by weight is used as one layer of a laminated film (Patent Document 2).

[0004] However, PTMG segments have a drawback: when subjected to heat exceeding the appropriate range, they generate volatile, flammable, and harmful tetrahydrofuran (THF) as a decomposition gas. This characteristic leads to negative consequences in terms of physical properties, such as a decrease in the thermal decomposition temperature of the resin and the generation of decomposition gases. Furthermore, in terms of processing, it causes problems such as the incorporation of THF bubbles into the resin during melt molding.

[0005] Patent Document 3 describes an example of a copolymerized polyalkylene ether glycol copolymerized polyester that does not generate harmful gases even at high temperatures, i.e., exhibits excellent thermal stability, achieved by copolymerizing a polyalkylene ether glycol with a long alkylene chain with a polyester. However, it has been difficult to achieve both thermal stability and mechanical properties such as flexibility, and improvements in practical applications have been needed. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 49-31795 [Patent Document 2] Japanese Patent Publication No. 2007-307708 [Patent Document 3] Japanese Patent Publication No. 2020-147744 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention provides copolymerized polyalkylene ether glycol copolymerized polyesters that exhibit excellent thermal stability and flexibility. [Means for solving the problem]

[0008] As a result of diligent research into the above-mentioned problems, the inventors of the present invention discovered that polyalkylene ether glycol copolymer polyesters having specific structural units possess excellent thermal stability and flexibility, and that these problems can be overcome, thus leading to the present invention. In other words, the gist of this invention is as follows.

[0009] [1] A polyalkylene ether glycol copolymer polyester having structural units derived from a dicarboxylic acid, structural units derived from a diol, and structural units derived from a polyalkylene ether glycol represented by the following formula (1), wherein the number average molecular weight of the structural units derived from the polyalkylene ether glycol is 500 to 5,000. HO-(R 1 -O) n -(R 2 -O) m -H (1) (In the formula, R 1 R is a hydrocarbon group of a dimerized diol containing 36 to 44 carbon atoms, which is normally present in alcohols obtained by reducing cyclic and acyclic dimeric acids obtained by dimerizing unsaturated fatty acids, or an alkylene group consisting of 2 to 6 carbon atoms. 2 represents an alkylene group with 6 to 18 carbon atoms. n and m are values ​​where the number-average molecular weight of the structural unit derived from the polyalkylene ether glycol represented by formula (1) is in the range of 500 to 5,000, and n / (n+m) is 0.1 or greater.

[0010] [2] The content of the structural unit derived from the polyalkylene ether glycol in the polyalkylene ether glycol copolymerized polyester is 10 to 80% by mass, the polyalkylene ether glycol copolymerized polyester according to [1]. [3] The structural unit derived from the dicarboxylic acid includes the structural unit derived from an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid, the polyalkylene ether glycol copolymerized polyester according to [1] or [2]. [4] The structural unit derived from the diol includes the structural unit derived from an aliphatic diol having 2 to 8 carbon atoms, the polyalkylene ether glycol copolymerized polyester according to any one of [1] to [3].

[0011] [5] Having the structural unit derived from the polyalkylene ether glycol component composed of two or more diols, the polyalkylene ether glycol copolymerized polyester according to any one of [1] to [4]. [6] Composed of a polyalkylene ether glycol having the structural unit derived from a diol component having 8 to 15 carbon atoms and the structural unit derived from a diol component having 36 to 44 carbon atoms, the polyalkylene ether glycol copolymerized polyester according to [5]. [7] A molded body including the polyalkylene ether glycol copolymerized polyester according to any one of [1] to [6].

Advantages of the Invention

[0012] According to the present invention, a polyalkylene ether glycol copolymerized polyester excellent in thermal stability and flexibility can be provided.

Modes for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In addition, in this specification, "being the main component" means occupying 70 mol% or more of the said component. For example, "a dicarboxylic acid component containing a terephthalic acid component as the main component" means that 70 mol% or more of all the acid components constituting the polyester is the terephthalic acid component. In addition, "dicarboxylic acid component" is also used in the sense of "a structural unit incorporated into a polyalkylene ether glycol copolymer polyester derived from a dicarboxylic acid component". The same applies to "diol component" and "polyalkylene ether glycol component". In addition, the polyalkylene ether glycol copolymer ester of the present invention may be used as a composition mixed with a polyester not containing a polyalkylene ether glycol component.

[0014] <Polyalkylene ether glycol copolymer polyester> The polyalkylene ether glycol copolymer polyester of the present invention has a structural unit derived from a dicarboxylic acid, a structural unit derived from a diol, and a structural unit derived from a polyalkylene ether glycol represented by the following formula (1). HO-(R 1 -O) n -(R 2 -O) m -H (1) (In the formula, R 1 is a hydrocarbon group of a dimer diol containing 36 to 44 carbon atoms usually present in an alcohol obtained by reducing a cyclic and acyclic dimer acid obtained by dimerizing an unsaturated fatty acid, or an alkylene group consisting of 2 to 6 carbon atoms, and R 2represents an alkylene group with 6 to 18 carbon atoms. n and m are values ​​such that the number-average molecular weight of the structural unit derived from the polyalkylene ether glycol represented by formula (1) is in the range of 500 to 5,000, and n / (n+m) is 0.1 or greater. Note that "R 1 -O" and "R 2 The copolymerization form of "-O" can be either blocky or random.

[0015] (Dicarboxylic acid component) Examples of dicarboxylic acid components used in the present invention include the dicarboxylic acids and their ester-forming derivatives described below. These can also be produced by petrochemical processes and / or by fermentation processes derived from biomass resources. As ester-forming derivatives of dicarboxylic acids, preferred are lower alcohol esters of dicarboxylic acids, as well as ester-forming derivatives such as acid anhydrides and acid chlorides. Here, lower alcohols generally refer to linear or branched alcohols with 1 to 4 carbon atoms in the alkyl group. The dicarboxylic acid components used in the present invention are not particularly limited, but specifically include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, and dodecanedicarboxylic acid, and their ester-forming derivatives; alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives of alicyclic dicarboxylic acids such as dimethyl 1,4-cyclohexanedicarboxylic acid (1,4-DMCD). Conductors include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, as well as ester-forming derivatives of aromatic dicarboxylic acids such as methyl terephthalate (DMT). Furthermore, examples of dicarboxylic acid components include heterocyclic aromatic dicarboxylic acids such as dimethyl frangicarboxylate (FDCM). In addition to the above, other examples of ester-forming derivatives include anhydrides such as succinic anhydride and adipic anhydride. Among these, aromatic dicarboxylic acids such as terephthalic acid, ester-forming derivatives of aromatic dicarboxylic acids such as dimethyl terephthalate (DMT), alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives of alicyclic dicarboxylic acids such as dimethyl 1,4-cyclohexanedicarboxylic acid (1,4-DMCD) are preferred in terms of the physical properties of the resulting polyester, with terephthalic acid, dimethyl terephthalate, 1,4-cyclohexanedicarboxylic acid, and dimethyl 1,4-cyclohexanedicarboxylic acid being particularly preferred. It is preferable that the above-mentioned dicarboxylic acids be included as the main component. These dicarboxylic acid components may be used individually or in combination of two or more.

[0016] (Diol component) The diol components used in the present invention are not particularly limited, but examples include linear aliphatic diols such as ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butylene glycol (1,4-BG), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,8-octanediol; cyclic aliphatic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol (1,4-CHDO), and 1,4-cyclohexanedimethanol (1,4-CHDM); aromatic diols such as xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)sulfone; and plant-derived diols such as isosorbide, isomannide, isoidette, and erythritane. Furthermore, ethylene glycol, 1,3-propanediol, 1,4-BG, etc., can also be derived from biomass resources. Among these, aliphatic diols having 2 to 8 carbon atoms, such as 1,4-BG, 1,4-CHDO, and 1,4-CHDM, are preferred in terms of the physical properties of the resulting polyester, with 1,4-BG and 1,4-CHDM being particularly preferred.

[0017] These diol components may be used individually or in combination of two or more. These diol components, in combination with dicarboxylic acid components, constitute the hard segment of the polyalkylene ether glycol copolymer polyester. The amount of structural units derived from the diol shall be such that the total molar amount of glycol, when combined with the structural units derived from the polyalkylene ether glycol described later, is approximately equal to the molar amount of structural units derived from the dicarboxylic acid. If the polyalkylene ether glycol copolymer polyester contains "other copolymerizable components," this amount shall be taken into consideration when determining the amount of the diol component.

[0018] (Polyalkylene ether glycol component) The polyalkylene ether glycol used in the present invention has a structure represented by the following formula (1). HO-(R 1 -O) n -(R 2 -O) m -H (1) (In the formula, R 1 R is a hydrocarbon group of a dimerized diol containing 36 to 44 carbon atoms, which is normally present in alcohols obtained by reducing cyclic and acyclic dimeric acids obtained by dimerizing unsaturated fatty acids, or an alkylene group consisting of 2 to 6 carbon atoms. 2 represents an alkylene group with 6 to 18 carbon atoms. n and m are values ​​such that the number-average molecular weight of the structural unit derived from the polyalkylene ether glycol represented by formula (1) is in the range of 500 to 5,000, and n / (n+m) is 0.1 or greater. Note that "R 1 -O" and "R 2 The copolymerization form of "-O" can be either blocky or random.

[0019] For example, a manufacturing method described in Japanese Patent Publication No. 2020-147744 can be used. Specifically, a polyalkylene ether glycol having an appropriate number of C1 in the alkylene chain can be produced from one or two alkylenediols having an appropriate number of C1 in the alkylene chain, for example, by using a polycondensation reaction with 1,10-decanediol as a raw material to produce polydecamethylene glycol. If part of the terminal is sulfonic acid, this polyalkylene ether glycol can be hydrolyzed in an acidic or basic aqueous solution by adjusting conditions such as temperature, catalyst type, catalyst amount, reaction temperature, and reaction time to obtain a polyalkylene ether glycol having an appropriate number of C1 in the alkylene chain and an appropriate molecular weight.

[0020] (Characteristics of polyalkylene ether glycol) The polyalkylene ether glycol component according to the present invention constitutes the soft segment of the polyalkylene ether glycol copolymer polyester, and in formula (1), (R 2 The alkylene chain (R) of the polyalkylene ether glycol used as a soft segment is characterized by having 6 or more carbon atoms. 2 By setting the number of carbon atoms in (R) to 6 or more, the number concentration of the easily thermally decomposed ether bond relative to the entire polyalkylene ether glycol copolymer polyester can be reduced, and the generation of stable cyclic ethers during ether bond cleavage can be suppressed, thereby improving thermal stability. In addition, (R) in formula (1) can be reduced. 1 By using a divalent hydrocarbon group derived from a dimeric diol having 36 to 44 carbon atoms, which is a dimer of an unsaturated fatty acid, or an alkylene group consisting of 2 to 6 carbon atoms, the regularity of the polyalkylene ether glycol can be disrupted, lowering its crystallinity and melting point, which is preferable as a soft segment.

[0021] R 2 The number of carbon atoms in the alkylene group has a lower limit of 6 or more, preferably 8 or more, and an upper limit of 18 or less, preferably 15 or less. 1The alkylene group is a divalent hydrocarbon group derived from a dimeric diol having 36 to 44 carbon atoms, or a divalent hydrocarbon group having 6 or fewer carbon atoms, preferably 3 or fewer.

[0022] Specifically, examples of branched dimeric diols obtained by reducing acyclic dimeric acids include compounds represented by the following structural formula (this is merely one embodiment and is not limited to this compound).

[0023] [ka]

[0024] Examples of cyclic dimeric diols obtained by reducing cyclic dimeric acids include compounds represented by the following structural formula (this is merely one embodiment and is not limited to this compound).

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] Furthermore, the number-average molecular weight of the polyalkylene ether glycol component in the present invention is 500 to 5,000, preferably 600 to 4,000, and more preferably 700 to 3,000. When the number-average molecular weight is within this range, the reactivity during copolymerization polyester production is good, the degree of melting point depression due to copolymerization is small, and copolymerized polyesters with good mechanical properties can be obtained.

[0030] The method for measuring the number-average molecular weight of the polyalkylene ether glycol component is as described in the Examples section below. The number-average molecular weight of polyalkylene ether glycol can be controlled by the reaction temperature, reaction time, amount of catalyst, etc., during its production. These polyalkylene ether glycol components may be used individually or in combination of two or more. The content of structural units derived from polyalkylene ether glycol in the polyalkylene ether glycol copolymer polyester, i.e., the copolymerization ratio in the polyalkylene ether glycol copolymer polyester, is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 65% by mass. When the copolymerization ratio of the polyalkylene ether glycol component is within this range, a polyalkylene ether glycol copolymer polyester with excellent thermal stability and a good balance between flexibility and melting point can be obtained.

[0031] In equation (1), n / (n+m) is a value of 0.1 or greater, preferably 0.15 or greater, and more preferably 0.2 or greater. Furthermore, the polyalkylene ether glycol component is preferably composed of two or more diols. In this regard, the upper limit of n / (n+m) is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

[0032] (Other copolymerizable components) The polyalkylene ether glycol copolymer polyester of the present invention may, in addition to the structural units derived from the dicarboxylic acid, the diol, and the polyalkylene ether glycol, optionally contain structural units derived from other copolymerizable compounds. Other copolymerizable compounds that can be used as raw materials for polyester in the present invention include hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-β-hydroxyethoxybenzoic acid; monofunctional carboxylic acids such as stearic acid, behenic acid, benzoic acid, t-butylbenzoic acid, and benzoylbenzoic acid; polyfunctional carboxylic acids with three or more functions such as tricarbaryl acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, and gallic acid; and polyfunctional alcohols with three or more functions such as trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and sugar esters. Other copolymerizable compounds may be used individually or in combination of two or more.

[0033] The content of structural units derived from other copolymerizable compounds in the polyalkylene ether glycol copolymer polyester is preferably less than 10 mol% and more preferably less than 5 mol% relative to the total carboxylic acid component in the case of acids, and less than 5 mol% relative to the total diol component in the case of hydroxyl compounds. By being within this range, it is possible to obtain copolymer polyesters with a small degree of melting point depression due to copolymerization and good mechanical properties.

[0034] <Method for producing polyalkylene ether glycol copolymer polyester> The polyalkylene ether glycol copolymer polyester of the present invention can be produced by a method that uses a dicarboxylic acid, a diol, and a polyalkylene ether glycol, along with other copolymerizable compounds as starting materials, and proceeds through a transesterification and / or esterification reaction step, a polycondensation reaction of the oligomer obtained by this reaction, and a further polycondensation step of solid-phase polycondensation as necessary, to obtain a polyester.

[0035] (Transesterification and / or esterification reactions) In the present invention, as a first step, a transesterification reaction and / or esterification reaction is carried out between a dicarboxylic acid and a diol and a polyalkylene ether glycol. Normally, dicarboxylic acids and polyalkylene ether glycols are not removed by distillation in the polycondensation reaction described later, following the transesterification and / or esterification reaction. However, some diols are removed by distillation in the polycondensation reaction, while others are not. When using a diol that can be removed by distillation in the polycondensation reaction, it is preferable to use a slightly larger molar amount of the total glycol (diol and polyalkylene ether glycol combined) than the molar amount of the dicarboxylic acid, and after reacting all of the dicarboxylic acid in the transesterification and / or esterification reaction, remove any unreacted diol by distillation during the polycondensation reaction. On the other hand, when using a diol that cannot be removed by distillation in the polycondensation reaction, in order to allow the polycondensation reaction to proceed sufficiently, it is best to make the total molar amount of the glycol, which is the sum of the diol and polyalkylene ether glycol used, approximately equal to the molar amount of the dicarboxylic acid.

[0036] In other words, when using a diol that can be removed by distillation in the polycondensation reaction, such as 1,4-BG, the total amount of glycol used, including the diol and polyalkylene ether glycol, is preferably 1.1 to 3.0 moles, and more preferably 1.1 to 1.5 moles, per mole of dicarboxylic acid. If this value is too small, the polycondensation reaction tends not to proceed sufficiently, and if it is too large, for example, the production of THF by the decomposition of 1,4-BG tends to increase. Furthermore, when using a diol that cannot be removed by distillation in the polycondensation reaction, such as 1,4-CHDM, the total amount of glycol used, is preferably 0.9 to 1.1 moles, and more preferably 0.98 to 1.02 moles, per mole of dicarboxylic acid. If this value is too small or too large, the polycondensation reaction tends not to proceed sufficiently.

[0037] Catalysts used in this first step reaction include, for example, antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; titanium compounds such as titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate; dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldisin oxide, cyclohexahexyldisin oxide, didodecyltin oxide, and triethyltin. Examples of catalysts include tin compounds such as hydroxide, triphenyltin hydroxide, triisobutyltin acetate, and dibutyltin diacetate; magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate; and calcium compounds such as calcium acetate, calcium hydroxide, calcium carbonate, calcium oxide, calcium alkoxide, and calcium hydrogen phosphate. These catalysts also include metal compounds containing atoms of Group IIA metals of the periodic table, as well as manganese compounds and zinc compounds. Among these, metal compounds containing titanium atoms and atoms of Group IIA metals of the periodic table are preferred, with titanium compounds and tin compounds being particularly preferred, and tetrabutyl titanate being particularly preferred. These catalysts can be used individually or in combination of two or more.

[0038] These reaction catalysts are preferably added such that the metal concentration derived from the reaction catalyst in the manufactured polyalkylene ether glycol copolymer polyester is within the following range. In the case of transesterification reactions, the amount of these catalysts used is typically 1 to 300 ppm by mass, preferably 5 to 250 ppm by mass, more preferably 10 to 200 ppm by mass, particularly preferably 20 to 175 ppm by mass, and most preferably 25 to 150 ppm by mass, as the metal content in the polyalkylene ether glycol copolymer polyester. In the case of esterification reactions, the amount of these catalysts used is typically 1 to 300 ppm by mass, preferably 5 to 200 ppm by mass, more preferably 1 to 100 ppm by mass, particularly preferably 20 to 90 ppm by mass, and most preferably 30 to 70 ppm by mass, as the metal content in the polyalkylene ether glycol copolymer polyester. If the amount of catalyst added in the transesterification and / or esterification reaction falls within this range of metal content in the polyalkylene ether glycol copolymer polyester, the formation of foreign substances is suppressed, and degradation reactions and gas generation during thermal retention of the resulting polyalkylene ether glycol copolymer polyester are less likely to occur.

[0039] The conditions for the transesterification and / or esterification reaction are arbitrary as long as the reaction can proceed. The reaction temperature is usually 120°C or higher, preferably 150°C or higher, while it is usually 300°C or lower, preferably 270°C or lower, and more preferably 260°C or lower. The reaction time is usually 2 to 8 hours, preferably 2 to 6 hours, and more preferably 2 to 4 hours. The reaction in the first step described above generates an oligomer formed by the reaction of the dicarboxylic acid component, the diol component, and the polyalkylene ether glycol component.

[0040] (Polycondensation reaction) Next, the oligomer produced in the first step is subjected to a polycondensation reaction (the second step reaction). The polycondensation reaction is usually carried out by a melt polycondensation reaction. The conditions in the melt polycondensation reaction are arbitrary as long as the reaction can proceed. The reaction temperature during the polycondensation reaction is preferably 300°C or lower, preferably 260°C or lower, while 200°C or higher is preferable, and more preferably 240°C or higher. If the reaction temperature is below the above upper limit, the thermal decomposition reaction during manufacturing is suppressed, and the color tends to improve. If the reaction temperature is above the above lower limit, the polycondensation reaction can proceed more efficiently. As the catalyst for the polycondensation reaction, the catalyst species described for the transesterification and / or esterification reactions can be used. The catalyst used for the transesterification and / or esterification reactions may be used as is as the catalyst for the polycondensation reaction, or a catalyst may be added further. Preferably, the amount added is such that the metal equivalent content of the polycondensation reaction catalyst in the polyalkylene ether glycol copolymer polyester is within the following range.

[0041] When polycondensation follows a transesterification reaction, the amount of catalyst added is typically 5 to 300 ppm by mass, preferably 10 to 200 ppm by mass, more preferably 15 to 150 ppm by mass, particularly preferably 20 to 100 ppm by mass, and most preferably 30 to 50 ppm by mass, in terms of metal content in the polyalkylene ether glycol copolymer polyester. When polycondensation follows the esterification reaction, the amount of catalyst added is typically 0.5 to 300 ppm by mass, preferably 1 to 200 ppm by mass, more preferably 3 to 100 ppm by mass, particularly preferably 5 to 50 ppm by mass, and most preferably 10 to 40 ppm by mass, in terms of metal content in the polyalkylene ether glycol copolymer polyester. If the amount of catalyst added in the polycondensation reaction falls within this range as the metal equivalent content in the polyalkylene ether glycol copolymer polyester, the formation of foreign substances is suppressed, and degradation reactions and gas generation during thermal retention of the resulting polyalkylene ether glycol copolymer polyester are less likely to occur.

[0042] The lower the pressure inside the reaction vessel during the polycondensation reaction, the easier the reaction proceeds. In the final stage, the pressure is usually 27 kPa or less, preferably 20 kPa or less, more preferably 13 kPa or less, and in at least one polycondensation reaction vessel, it is preferable to maintain a state of 0.4 kPa or less. The time required for the polycondensation reaction is adjusted by measuring the intrinsic viscosity of the resulting polyalkylene ether glycol copolymer polyester and keeping that range constant, but it is usually 2 to 12 hours, preferably 2 to 10 hours. When the polycondensation reaction is carried out in a continuous manner, the average residence time in the polycondensation reaction vessel is considered to be the time required for the polycondensation reaction.

[0043] In this invention, the timing of adding polyalkylene ether glycol to the reaction system is from the start of the transesterification reaction and / or esterification reaction until the completion of the polycondensation reaction. By adding polyalkylene ether glycol during this period, it is possible to obtain a polyalkylene ether glycol copolymer polyester with a high melting point that easily maintains the blocking properties of the copolymer component. The preferred timing for addition, from the standpoint of the addition operation and ensuring blocking properties, is between the start of the transesterification and / or esterification reaction and the start of the polycondensation reaction.

[0044] After the polycondensation reaction is complete, the resulting polymer is removed from the reaction vessel in strand form, cooled in water, or cut after water cooling to form pellets. The pellets can be further polymerized to a higher degree by solid-phase polycondensation as needed. Solid-phase polycondensation reactions are carried out under an inert gas atmosphere such as nitrogen, under reduced pressure, or under an inert gas flow. The reaction temperature is usually 180°C or higher, preferably 190°C or higher, while it is usually 210°C or lower, preferably 200°C or lower. The solid-phase polycondensation reaction is carried out for a relatively long time until the desired intrinsic viscosity is reached. The reaction time for solid-phase polycondensation is usually 5 to 20 hours, preferably 6 to 15 hours. Solid-phase polycondensation can be carried out in batch or continuous manner.

[0045] <Physical properties of polyalkylene ether glycol copolymer polyesters> The following lists the preferred physical properties of the polyalkylene ether glycol copolymer polyester of the present invention. The methods for measuring each physical property are described in the Examples section below.

[0046] (Reduced viscosity) The reduced viscosity (ηsp / C) of the polyalkylene ether glycol copolymer polyester of the present invention is preferably 0.48 dL / g or higher, more preferably 0.5 dL / g or higher, even more preferably 0.6 dL / g or higher, particularly preferably 0.7 dL / g or higher, and most preferably 0.8 dL / g or higher. The upper limit of the reduced viscosity is 3.0 dL / g or lower, preferably 2.5 dL / g or lower, and most preferably 2.0 dL / g or lower. If the reduced viscosity is less than 0.48 dL / g, it may not be possible to mold films or injection-molded articles, or even if molding is possible, the strength may be insufficient and the product may not be suitable for use. Furthermore, if the reduced viscosity is greater than 3.0 dL / g, molding becomes difficult and is undesirable. In this invention, the reduced viscosity (ηsp / C) of the polyester resin was determined from the solution viscosity measured at 30°C in a phenol / tetrachloroethane (1:1 weight ratio) solution with a polyester resin concentration of 0.5 g / dL.

[0047] (Terminal acid value) Furthermore, the terminal acid value of the polyalkylene ether glycol copolymer polyester of the present invention is less than 200 μeq / g, preferably less than 150 μeq / g, more preferably less than 100 μeq / g, and most preferably less than 50 μeq / g. A terminal acid value greater than 200 μeq / g is undesirable due to a significant decrease in physical properties. The lower limit of the terminal acid value is preferably 0.

[0048] (Melting point (Tm2 in later examples)) The melting point of the polyalkylene ether glycol copolymer polyester of the present invention is preferably 100 to 280°C, and more preferably 150 to 270°C. A melting point within this range provides excellent heat resistance for use at high temperatures, excellent thermal stability, and prevents the generation of harmful gases even at high temperatures.

[0049] (pyrolysis temperature) The higher the thermal decomposition temperature (Td5) of the polyalkylene ether glycol copolymer polyester of the present invention when the weight decreases by 5%, the less susceptible it is to thermal decomposition. The thermal decomposition temperature (Td5) is usually around 375 to 400°C, and a higher value is preferable as it indicates better thermal stability.

[0050] (Heat of fusion ΔH) The heat of fusion of the soft segment of the polyalkylene ether glycol copolymer polyester of the present invention (corresponding to ΔHm1 in later examples) is typically around 0 to 50 J / g, and a smaller value indicates better flexibility of the soft segment component, which is preferable. Furthermore, the heat of fusion of the polyalkylene ether glycol copolymer polyester of the present invention (corresponding to ΔHm2 in later examples) is typically around 0 to 40 J / g, and a smaller value indicates lower crystallinity of the hard segment and improved flexibility, which is preferable.

[0051] <Composition / molded object> The polyalkylene ether glycol copolymer polyester of the present invention can be compounded with various additives such as stabilizers, antioxidants, fillers, antistatic agents, mold release agents, and flame retardants, or with PBT or other resins, as needed, to form a polyester composition. Furthermore, the polyalkylene ether glycol copolymer polyester of the present invention, or a composition containing the copolymer polyester, can be molded to form a molded article. The content of the polyalkylene ether glycol copolymer polyester of the present invention in the composition is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0052] (Blending method) The method of blending the various additives and resins mentioned above is not particularly limited. The various additives can be blended during or after the production of the polyalkylene ether glycol copolymer polyester, and PBT and other resins can be blended after the production of the polyalkylene ether glycol copolymer polyester. When blending after the production of the polyalkylene ether glycol copolymer polyester, it is preferable to use a single-screw or twin-screw extruder equipped with a vent for evaporation as the kneader. Each component can be supplied to the kneader sequentially or all at once. In addition, two or more components selected from each component may be mixed in advance.

[0053] (Molding method) The polyalkylene ether glycol copolymer polyester and compositions containing the same of the present invention can be molded into various molded articles, including filaments, fibers, sheets, films, etc., by molding methods commonly used for thermoplastic resins, namely injection molding, hollow molding, extrusion molding, press molding, stretch molding, and inflation molding. Furthermore, the resulting molded article can have moderate flexibility, for example, a flexural modulus of 150 to 600 MPa, making it suitable for applications where flexibility is required. [Examples]

[0054] <Measurement and Evaluation Methods> The measurement methods for the physical properties and evaluation items used in the following examples are as follows: (Synthesis material for polyalkylene ether glycol) 1,3-Propanediol: Tokyo Chemical Industry Co., Ltd. (3 carbon atoms) 1,10-Decanediol: Tokyo Chemical Industry Co., Ltd. or Toyokuni Oil Co., Ltd. (10 carbon atoms) Dimergol: Croda Japan Co., Ltd. Product name "Pripol 2033" (36 carbon atoms) Trifluoromethanesulfonic acid: Tokyo Chemical Industry Co., Ltd. p-Toluene sulfonic acid monohydrate: Fujifilm Wako Pure Chemical Corporation

[0055] (Dicarboxylic acid) Dimethyl terephthalic acid (DMT): Tokyo Chemical Industry Co., Ltd. Dimethyl flavonoid carboxylate (FDCM): Tokyo Chemical Industry Co., Ltd. (Diol) 1,4-Butanediol (1,4-BG): Tokyo Chemical Industry Co., Ltd. Cyclohexanedimethanol (CHDM): Tokyo Chemical Industry Co., Ltd.

[0056] ( 1 H-NMR analysis) Using deuterated chloroform as the solvent, measurements were taken using a JEOL Ltd. "ECZ-400" at a resonance frequency of 400 MHz, a flip angle of 45°, and a measurement temperature of room temperature. 1 1H-NMR was measured.

[0057] (GPC (Gel Permeation Chromatography) measurement) Columns: TSKgel GMHHR-N (Tosoh, 7.8-300mm, 9mm) 2 pieces, Column oven temperature: 40℃ Mobile phase: THF 1mL / min Analysis time: 30min Detection: RI detector Sample: 20-50 μL injection Calibration method: Polystyrene equivalent Calibration curve approximation formula: cubic equation

[0058] (Calculation methods for hydroxyl group count, terminal esterification rate, terminal olefination rate, degree of polymerization, and dimergol content) The terminal hydroxyl groups of polyalkylene ether glycols react with the added acid to form esters, and also undergo intramolecular dehydration to become unsaturated groups. As a result, 1In 1H-NMR analysis, signals originating from methylene groups bonded to primary hydroxyl groups are observed at around 3.6 ppm, signals originating from methylene groups bonded to ester groups are observed at around 4.0 ppm, and signals originating from terminal unsaturated groups (CH2=CH-) are observed in multiple concentrations around 5.0-6.0 ppm (solvent: deuterated chloroform). Signals originating from methylene groups bonded to ether groups generated by the desired dehydration condensation reaction are observed at around 3.4 ppm. The number of hydroxyl groups, terminal olefinization rate, and terminal esterification rate were calculated using the following formulas. Number of hydroxyl groups=[(A / 2) / (A / 2+B / 2+C / 3)]×2 Terminal esterification rate = [(B / 2) / (A / 2+B / 2+C / 3)] × 100 End-olefinization rate = [(C / 3) / (A / 2+B / 2+C / 3)] × 100 Degree of polymerization=D / A+1

[0059] Dimerol content in 1,10-decanediol and dimerol copolymerized polyalkylene ether glycol = [(E / 6) / (A / 4+D / 4)] × 100 (However, in the formula, A is the integral value of the signal originating from a methylene group bonded with a primary hydroxyl group at around 3.6 ppm; B is the integral value of the signal originating from a methylene group bonded with an ester group at around 4.0 ppm.) C is the integral value of the signal originating from terminal unsaturated groups (CH2=CH-) around 5.0-6.0 ppm. D is the integral value of the signal originating from the methylene group bonded to the ether group at around 3.4 ppm. E is the integral of the signal originating from the terminal methyl group of the dimer ol at around 0.88 ppm.

[0060] The carbon (C) of the polyalkylene ether glycol containing the dimerized diol was corrected for the amount of olefin in the starting material using the following formula: C = C' - Cp / Ap × (A + D) × C' - Cp / Ap * (A + D) × (Dimerized diol content in the 1,10-decanediol and dimerized diol copolymerized polyalkylene ether glycol) (where C' is the integral value of the signal originating from the terminal unsaturated group (CH2=CH-) around 5.0-6.0 ppm in the product, Cp is the integral value of the signal originating from the terminal unsaturated group (CH2=CH-) around 5.0-6.0 ppm in the starting material dimerized diol, and Ap is the integral value of the signal originating from the methylene group to which a primary hydroxyl group is attached around 3.6 ppm in the starting material dimerized diol.)

[0061] (Toluene concentration measurement) Deuterated chloroform was used as the solvent. 1 The result was calculated from the integral value of the signal originating from the methyl group observed at around 2.36 ppm (using 1,1,2,2-tetrachloroethane as an internal standard) in 1H-NMR analysis.

[0062] (moisture concentration measurement) The moisture content was measured using a Karl Fischer moisture analyzer (CA-200, manufactured by Mitsubishi Chemical Analytec Co., Ltd.) with Aquamicron® AKX and Aquamicron® CXU (both manufactured by Mitsubishi Chemical Corporation) by coulometric titration.

[0063] (Method for measuring hydroxyl value and calculating number-average molecular weight) The hydroxyl value of polyalkylene ether glycol was measured using an automatic titrator (GT-200, manufactured by Mitsubishi Chemical Analytec Co., Ltd.) in accordance with ASTM E-1899-16. The number-average molecular weight (Mn) was determined from the measured hydroxyl value using the following formula (I). Number-average molecular weight = 2 × 56.1 / (hydroxyl value × 10⁻³) …(I)

[0064] (DSC) The melting point (Tm) was measured using a differential scanning calorimeter "DSC7000x" manufactured by Hitachi High-Tech Science. The heating rate was set to 10°C / min. The lower of the two maximum peaks was defined as Tm1 (melting point derived from the soft segment), and the higher peak as Tm2 (melting point of the polymer). The respective peak areas were defined as the heat of fusion ΔHm1 and ΔHm2 (J / g). A smaller value of ΔHm indicates lower crystallinity.

[0065] (TG-DTA, measurement of 5% weight loss temperature) Using the Hitachi High-Tech Science STA200RV simultaneous thermogravimetric analyzer, approximately 7 mg of sample was placed in an aluminum container, and its mass was measured from 30°C to 500°C under a nitrogen atmosphere (nitrogen flow rate 200 ml / min) at a heating rate of 10°C / min. The temperature at which a 5% weight loss occurred was defined as the 5% weight loss temperature Td5 (unit: °C). The 5% weight loss temperature is an indicator of heat resistance; a higher value indicates higher heat resistance.

[0066] (Reduced viscosity (ηsp / C)) The viscosity of the polyester resins obtained in the examples and comparative examples was determined from a solution prepared in phenol / 1,1,2,2-tetrachloroethane (1:1 weight ratio) at a concentration of 0.5 g / dl, measured at 30°C.

[0067] <Method for producing polyalkylene ether glycol> (Example of preparation of 110-decanediol / prepol 2033 (75 / 25) Mn927 (copolymer polyol 1)) 128 g (0.736 mol) of 1,10-decanediol and 132 g (0.245 mol) of dimergol (Prepol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked flask equipped with a distillation tube, nitrogen inlet tube, thermocouple, and stirrer. After heating and melting in an oil bath, the reactor was degassed under reduced pressure and purged with nitrogen. The flask was immersed in the oil bath and heated while supplying nitrogen at 0.20 NL / min. When the temperature exceeded 160°C, 5.73 g (30.1 mmol) of p-toluenesulfonic acid monohydrate was slowly added. The reaction was started when the temperature of the liquid in the flask reached 170°C, and thereafter the temperature was maintained at 170-171°C for 13 hours. The water produced by the reaction was removed by distillation accompanied by nitrogen. 37 g of 10 wt% sodium hydroxide aqueous solution was added to the reaction mixture, which had been allowed to cool to around 90°C, and the mixture was heated under reflux at 110°C for 15 hours to hydrolyze the ester. The reaction mixture was heated to approximately 90°C, and 500g of deionized water was added. The mixture was stirred at 90°C for approximately 15-30 minutes, then allowed to stand for 1-2 hours to confirm separation into an oil layer and an aqueous layer. The aqueous layer was then removed. The conductivity of the aqueous layer was measured, and the addition of deionized water and the separation of oil and water were repeated a total of eight times until the conductivity reached 0-10 μS / cm. After removing the oil layer, 100mL of toluene was added, and azeotropic dehydration was performed by distilling off the toluene under reduced pressure at 100°C and 20 torr. The water content was measured, and azeotropic dehydration was repeated a total of five times until the water concentration reached 300 ppm or less. The oil bath was heated to 120°C, and defoliation was performed under reduced pressure for 1 hour using an oil rotary vacuum pump until the toluene concentration reached 0.1 wt% or less, yielding the target polyalkylene ether glycol. The degree of polymerization determined by NMR was 3.71, the dimerol content in the polyalkylene ether glycol was 26.6 mol%, the terminal olefinization rate was 0.67 mol%, and the terminal esterification rate was below the NMR detection limit. The number-average molecular weight determined by GPC was 956, the mass-average molecular weight was 2001, the molecular weight distribution was 2.09, and the hydroxyl value was 121.0. The number-average molecular weight calculated from these values ​​was 927. The 5% weight loss temperature was 284.9°C.

[0068] (Example of preparation of 110-decanediol / prepol 2033 (75 / 25) Mn893 (copolymer polyol 2)) 246.7 g (1.416 mol) of 1,10-decanediol and 253 g (0.472 mol) of dimergol (Prepol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked flask equipped with a distillation tube, nitrogen inlet tube, thermocouple, and stirrer. After heating and melting in an oil bath, the reactor was degassed under reduced pressure and purged with nitrogen. The flask was immersed in the oil bath and heated while supplying nitrogen at 1.0 NL / min. When the temperature exceeded 148°C, a mixture of 5.04 g (33.5 mmol) of trifluoromethanesulfonic acid and 2.48 g of deionized water was slowly added to initiate the reaction. The reaction was then carried out for 4 hours while maintaining the liquid temperature at 149-151°C. After cooling to room temperature, the temperature was raised again and the reaction was carried out for 3 hours while maintaining the liquid temperature at 130-131°C. The water produced by the reaction was removed by distillation accompanied by nitrogen. The reaction mixture was allowed to cool to around 90°C, and 100g of deionized water was added. The mixture was stirred at 90°C for 30 minutes, then allowed to stand for 1 hour to confirm separation into oil and water layers, after which the water layer was removed. Next, 300g of deionized water was added, the mixture was stirred at 90°C for approximately 15-30 minutes, and then allowed to stand for 0.5-1 hour to confirm separation into oil and water layers, after which the water layer was removed. The conductivity of the water layer was measured, and the addition of deionized water and oil-water separation were repeated a total of 8 times (and a further 25 times) until the conductivity reached 0-10 μS / cm. After removing the oil layer, 300mL of toluene was added, and azeotropic dehydration was performed by distilling off the toluene under reduced pressure at 100°C and 20 torr. Next, 200 mL of toluene was added, and azeotropic dehydration was performed at 100°C and 10 torr. Thereafter, 100 mL of toluene was added, the water content was measured, and azeotropic dehydration was repeated a total of five times until the water concentration reached 300 ppm or less. The oil bath was heated to 120°C, and defolatation was performed under reduced pressure for 2 hours using an oil rotary vacuum pump until the toluene concentration reached 0.1 wt% or less, to obtain the target polyalkylene ether glycol. The degree of polymerization determined by NMR was 3.67, the dimerol content in the polyalkylene ether glycol was 25.6 mol%, the terminal olefinization rate was 0.68 mol%, and the terminal esterification rate was below the detection limit of NMR. The number-average molecular weight determined by GPC was 970, the mass-average molecular weight was 1996, the molecular weight distribution was 2.06, and the hydroxyl value was 125.6. The number-average molecular weight calculated from these values ​​was 893.

[0069] (Example of production of 110-decanediol / 13-propanediol (50 / 50)Mn1040 (copolymer polyol 3)) 370 g (2.123 mol) of 1,10-decanediol and 161 g (2.123 mol) of 1,3-propanediol were placed in a four-necked flask equipped with a distillation tube, nitrogen inlet tube, thermocouple, and stirrer. The mixture was heated to 70°C in an oil bath, and then the reactor was degassed under reduced pressure and purged with nitrogen. While supplying nitrogen at 0.20 NL / min and maintaining the temperature at 70°C, a mixture of 5.33 g (35.5 mmol) of trifluoromethanesulfonic acid and 2.65 g of deionized water was slowly added. This flask was immersed in an oil bath and heated until the temperature inside the flask reached 150°C in about 0.5-1 hours. The reaction started when the temperature inside the flask reached 150°C, and thereafter the temperature was maintained at 148-152°C for 15 hours. The water produced by the reaction was removed by distillation accompanied by nitrogen. The reaction mixture was allowed to cool to around 120°C, and 200g of deionized water was added. The mixture was stirred at 90°C for 30 minutes, then allowed to stand for 1 hour to confirm separation into oil and water layers, after which the water layer was removed. Next, 250-300g of deionized water was added, the mixture was stirred at 90°C for approximately 15-2 hours, then allowed to stand for 0.5-1 hour to confirm separation into oil and water layers, after which the water layer was removed. The conductivity of the water layer was measured, and the addition of deionized water and oil-water separation were repeated a total of 6 times until the conductivity reached 0-10 μS / cm. After removing the oil layer, 100-150mL of toluene was added, and azeotropic dehydration was performed by distilling off the toluene under reduced pressure at 84°C and 70 torr. The water content was measured, and azeotropic dehydration was repeated a total of 3 times until the water concentration reached 300 ppm or less. The oil bath was heated to 120°C, and defoliation was carried out under reduced pressure for 3.5 hours using an oil rotary vacuum pump until the toluene concentration reached 0.1 wt% or less, thereby obtaining the target polyether polyol. The degree of polymerization determined by NMR was 8.95, the decanediol content in the polyether polyol was 52.4 mol%, and the terminal olefinization rate was 0.92 mol%. The number-average molecular weight determined by GPC was 1080, the mass-average molecular weight was 2844, the molecular weight distribution was 2.63, and the hydroxyl value was 107.9. The number-average molecular weight calculated from these values ​​was 1040.

[0070] <Method for producing polyalkylene ether glycol copolymer polyester> (Example 1) In a reaction vessel equipped with a stirrer, nitrogen inlet, heating device, thermometer, and vacuum port, the following raw materials were charged: 26.45 parts by weight of dimethyl terephthalic acid, 9.18 parts by weight of 1,4-butanediol, 70.00 parts by weight of polyalkylene ether glycol (copolymer polyol 1), and 0.71 parts by weight of a 1,4-butanediol solution in which titanium tetrabutyrate was pre-dissolved at 6.0% by weight. While stirring the contents of the container, nitrogen gas was introduced into the container, and the system was subjected to a nitrogen atmosphere by vacuum displacement. Next, the system was heated to 150°C for 1 hour while stirring, then increased to 210°C over 1 hour and 45 minutes, and the reaction was carried out at this temperature for 15 minutes. Then, 0.36 parts by weight of a 1,4-butanediol solution in which titanium tetrabutyrate had been pre-dissolved at 6.0 wt% was added, and then 0.05 × 10⁻¹⁶ was added over 1 hour and 30 minutes.3 The pressure was reduced to below Pa. Fifteen minutes after the start of the reduced pressure, the temperature was raised to 240°C over 45 minutes. Polymerization was continued for 4 hours and 15 minutes while maintaining the heated and reduced pressure state at 240°C, after which the polymerization was terminated to obtain a polyester resin (terephthalic acid / butanediol / polyalkylene ether glycol copolymer polyester). The reduced viscosity of the obtained copolymer polyester was 1.464 dL / g. Furthermore, the Tm1 of this copolymer polyester was 16°C.

[0071] (Examples 2-7) The process was carried out in the same manner as in Example 1, except that the raw materials and catalyst were charged and the polycondensation reaction was performed, and the reaction was stopped when the target viscosity was reached. In addition, the dicarboxylic acid component, diol component, and polyalkylene ether glycol component shown in Table 1 were used in each example. The reduced viscosity, Tm1, Tm2, ​​ΔHm1, ΔHm2, and T of the obtained polyester resin were determined. d5 The thermal decomposition temperatures are shown in Table 1.

[0072] (Comparative Example 1) In Example 1, the polycondensation reaction was carried out in the same manner as in Example 1, except that 70.00 parts by weight of polydecamethylene glycol (PDMG) was used instead of 70.00 parts by weight of polyalkylene ether glycol (copolymer polyol 1). The reduced viscosity of the obtained polyester resin, Tm1, Tm2, ​​ΔHm1, ΔHm2, and T d5 The thermal decomposition temperatures are shown in Table 1.

[0073] (Comparative Example 2) In Example 1, the polycondensation reaction was carried out in the same manner as in Example 1, except that 70.00 parts by weight of polytetramethylene glycol (PTMG) was used instead of 70.00 parts by weight of polyalkylene ether glycol (copolymer polyol 1). The reduced viscosity of the obtained polyester resin, Tm1, Tm2, ​​ΔHm1, ΔHm2, and T d5 The thermal decomposition temperatures are shown in Table 1.

[0074] (Comparative Example 3) In Example 1, the polycondensation reaction was carried out in the same manner as in Example 1, except that 10.00 parts by weight of polydecamethylene glycol (PDMG) was used instead of 70.00 parts by weight of polyalkylene ether glycol (copolymer polyol 1). The melt viscosity, Tm1, Tm2, ​​ΔHm1, ΔHm2, and T of the obtained polyester resin were determined. d5 The thermal decomposition temperatures are shown in Table 1.

[0075] [Table 1]

[0076] The effects of the present invention can be determined by comparing resins with the same polyalkylene ether glycol content. For example, when comparing Example 1, Example 5, and Comparative Example 1, all of which have a polyalkylene glycol content of 70% by mass, Comparative Example 1 has a large ΔHm1 value and a high Tm1, while Examples 1 and 5 have a small ΔHm1 value and a lower Tm1, and also exhibit a small decrease in thermal decomposition temperature, indicating that they possess both thermal stability and flexibility. [Industrial applicability]

[0077] The polyalkylene ether glycol copolymer polyester of the present invention can be suitably used in various molded articles, including filaments, fibers, sheets, and films, in applications where it is desired to achieve both thermal stability and mechanical properties such as flexibility.

Claims

1. It has structural units derived from dicarboxylic acids, structural units derived from diols, and structural units derived from polyalkylene ether glycol represented by the following formula (1), The structural unit derived from the polyalkylene ether glycol represented by the following formula (1) has a structural unit derived from a polyalkylene ether glycol component consisting of two or more diols, A polyalkylene ether glycol copolymer polyester having a number-average molecular weight of 500 to 5,000 for structural units derived from the polyalkylene ether glycol. HO-(R １ -O) n -(R ２ -O) ｍ -+ (1) (In the formula, R １ R is a hydrocarbon group of a dimerized diol containing 36 to 44 carbon atoms, which is normally present in alcohols obtained by reducing cyclic and acyclic dimeric acids obtained by dimerizing unsaturated fatty acids, or an alkylene group consisting of 2 to 6 carbon atoms. ２ represents an alkylene group having 6 to 18 carbon atoms. n and m are derived from the polyalkylene ether glycol represented by formula (1), where the number-average molecular weight of the structural unit is in the range of 500 to 5,000, and n / (n+m) is between 0.1 and 0.

7.

2. The polyalkylene ether glycol copolymer polyester according to claim 1, wherein the content of structural units derived from the polyalkylene ether glycol in the polyalkylene ether glycol copolymer polyester is 10 to 80% by mass.

3. The polyalkylene ether glycol copolymer polyester according to claim 1 or 2, wherein the structural units derived from the dicarboxylic acid include structural units derived from an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid.

4. The polyalkylene ether glycol copolymer polyester according to any one of claims 1 to 3, wherein the structural unit derived from the diol includes a structural unit derived from an aliphatic diol having 2 to 8 carbon atoms.

5. The polyalkylene ether glycol copolymer polyester according to any one of claims 1 to 4, wherein the polyalkylene ether glycol component comprising two or more diols comprises a polyalkylene ether glycol having structural units derived from a diol component having 8 to 15 carbon atoms and structural units derived from a diol component having 36 to 44 carbon atoms.

6. A molded article comprising a polyalkylene ether glycol copolymer polyester according to any one of claims 1 to 5.

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