Polyamide block copolymer, polyamide block copolymer composition, and molded body

Abstract

A polyamide block copolymer according to the present invention includes a polymer block (A) that contains at least 50 mol% of a structural unit derived from a semi-aromatic polyamide and a polymer block (B) that has a glass transition temperature of no more than 20°C. The polyamide block copolymer has a terminal cap rate of at least 10%.

Description

Polyamide block copolymer, polyamide block copolymer composition, and molded article

[0001] The present invention relates to a polyamide block copolymer having capped molecular ends, a polyamide block copolymer composition, and a molded article.

[0002] Thermoplastic elastomers are melt-moldable and are used in a wide range of fields, including automotive interior and exterior components, electronic device components, and sporting goods. Thermoplastic elastomers contain soft segments that exhibit flexibility and hard segments that exhibit crosslinking points, and are classified into, for example, olefin-based, amide-based, urethane-based, ester-based, acrylic-based, and styrene-based types. Depending on the classification, thermoplastic elastomers can exhibit good physical properties such as mechanical strength, abrasion resistance, heat resistance, and oil resistance, and further improvements are being investigated. For example, Patent Document 1 discloses an amide-based thermoplastic elastomer. Specifically, Patent Document 1 discloses a polyamide block copolymer obtained by polymerizing a dicarboxylic acid, a diamine, and a polyetherdiamine and / or a polyetherdicarboxylic acid, with the aim of exhibiting heat resistance and low-temperature properties superior to those of conventional thermoplastic elastomers.

[0003] Meanwhile, Patent Document 2 discloses a polyamide composed of a dicarboxylic acid component and a diamine component, which has a specific intrinsic viscosity and in which 10% or more of the end groups are blocked. The polyamide, due to its specific intrinsic viscosity and end-capping rate, exhibits excellent properties such as hot water resistance, surface elegance, heat resistance, mechanical properties, low water absorption, and chemical resistance. Techniques for improving various physical properties of polyamide block copolymers by blocking end groups are also known. For example, Patent Document 3 discloses a polyamide resin formed from a mixture containing an acid component containing an aromatic dicarboxylic acid and an amine component, which has improved dispersibility and a lower solution viscosity than conventional polyamides. Example 21 of Patent Document 3 describes the production of a polyamide resin blocked with propionic acid. Patent Document 4 discloses a terminal-modified polyetheramide resin composed of specific structural units and having hydrocarbon groups with 1 to 22 carbon atoms at the terminals. The terminal-modified polyetheramide resin reduces easily extractable low-molecular-weight compounds, generates little low-molecular-weight compounds after molding (after thermal history), and exhibits good thermal stability.

[0004] JP 2000-154248, JP 07-228690, JP 62-164728, JP 03-237131

[0005] The above-mentioned Document 1 discloses that an end-capping agent may be used in the production of polyamide block copolymers, but does not disclose the specific effects thereof. Meanwhile, the above-mentioned Documents 2 to 4 disclose techniques for improving various physical properties by blocking the end groups of polyamide resins. For example, the above-mentioned Patent Document 4 discloses a technique for polyetheramide resins exhibiting good thermal stability. However, even the technique of Patent Document 4 may not provide satisfactory thermal stability depending on the application, and from the viewpoint of molding and processing, polyamide block copolymers with even better thermal stability are desired.

[0006] Therefore, an object of the present invention is to provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article having improved thermal stability. Other objects of the present invention will be apparent to those skilled in the art upon reading this specification.

[0007] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the above problems can be solved.

[0008] [1] A polyamide block copolymer comprising a polymer block (A) containing 50 mol % or more of structural units derived from a semi-aromatic polyamide and a polymer block (B) having a glass transition temperature of 20°C or lower, and having an end-capping rate of 10% or more. [2] The polyamide block copolymer according to [1], wherein the polymer block (B) has a number average molecular weight of 100 or more. [3] The polyamide block copolymer according to [1] or [2], wherein the polymer block (B) contains an oxygen atom in the main chain. [4] The polyamide block copolymer according to any one of [1] to [3], wherein the polymer block (B) contains 50 mol % or more of structural units derived from a polyether polyol, an amine derivative thereof, or a carboxyl derivative thereof. [5] The polyamide block copolymer according to any one of [1] to [4], wherein the tensile elongation at break measured in accordance with JIS K 7161-1:2014 is 30% or more. [6] The polyamide block copolymer according to any one of [1] to [5], wherein the semi-aromatic polyamide comprises a structural unit derived from an aliphatic diamine having 4 or more carbon atoms and a structural unit derived from an aromatic dicarboxylic acid. [7] The polyamide block copolymer according to any one of [1] to [6], wherein the molecular terminals are terminated with at least one selected from the group consisting of an aryl group, an aromatic alkyl group, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 9 or more carbon atoms, an alicyclic alkyl group having 4 or more carbon atoms, and a hydrogen atom. [8] The polyamide block copolymer according to [7], wherein the aryl group is a phenyl group or a naphthyl group. [9] The polyamide block copolymer according to [7], wherein the aromatic alkyl group is a benzyl group.

[10] The polyamide block copolymer according to [7], wherein the alkyl group having 1 to 3 carbon atoms is a methyl group or an ethyl group.

[11] The polyamide block copolymer according to [7], wherein the linear alkyl group having 9 or more carbon atoms is a lauryl group or a stearyl group.

[12] The polyamide block copolymer according to [7], wherein the alicyclic alkyl group is a cyclohexyl group.

[13] A polyamide block copolymer composition comprising the polyamide block copolymer according to any one of [1] to

[12] .

[14] A molded article formed from the polyamide block copolymer according to any one of [1] to

[12] or the polyamide block copolymer composition according to

[13] .

[15] A molded article formed from the polyamide block copolymer composition according to

[13] .

[0009] According to the present invention, it is possible to provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article having improved thermal stability.

[0010] The following describes an embodiment of the present invention. However, the embodiment described below is merely an example for embodying the technical concept of the present invention, and the present invention is not limited to the following description. Furthermore, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. For matters indicated as numerical ranges, when there are several numerical ranges, the lower and upper limits can be selectively combined to form a preferred embodiment. Note that, in this specification, a numerical range such as "XX to YY" means "XX or more and YY or less." Furthermore, in this specification, the term "unit" (where "~" indicates a monomer) means "a structural unit derived from ~." For example, "dicarboxylic acid unit" means "a structural unit derived from dicarboxylic acid," and "diamine unit" means "a structural unit derived from diamine."

[0011] <Polyamide Block Copolymer> The polyamide block copolymer of this embodiment comprises a polymer block (A) containing 50 mol% or more of structural units derived from a semi-aromatic polyamide and a polymer block (B) having a glass transition temperature of 20°C or lower, and is characterized by an end-capping ratio of 10% or more. The end-capping ratio of 10% or more of the polyamide block copolymer of this embodiment can improve thermal stability compared to conventional copolymers. One of the reasons for the improved thermal stability is thought to be that the specific proportion of molecular ends is blocked, thereby suppressing the promotion of thermal degradation due to molecular end motion. Furthermore, in the polyamide block copolymer, the polymer block (A) is a hard segment, and the polymer block (B) is a soft segment. The polyamide block copolymer of this embodiment can fully exhibit the physical properties of the polymer block (A) and the polymer block (B), which can contribute to the development of excellent heat resistance and flexibility. Therefore, the polyamide block copolymer of this embodiment can have improved thermal stability and excellent heat resistance and flexibility.

[0012] <Polymer Block (A)> The polymer block (A) contains 50 mol% or more of structural units derived from a semi-aromatic polyamide. Semi-aromatic polyamide refers to a polyamide containing diamine units primarily composed of structural units derived from an aliphatic diamine and dicarboxylic acid units primarily composed of structural units derived from an aromatic dicarboxylic acid, or a polyamide resin containing dicarboxylic acid units primarily composed of structural units derived from an aliphatic dicarboxylic acid and diamine units primarily composed of structural units derived from an aromatic diamine. Here, "primarily composed" refers to the diamine units or dicarboxylic acid units constituting 50 to 100 mol%, preferably 60 to 100 mol%, of the total units in the diamine units or dicarboxylic acid units. In this embodiment, from the viewpoint of achieving better heat resistance, the semi-aromatic polyamide preferably contains diamine units primarily composed of structural units derived from an aliphatic diamine and dicarboxylic acid units primarily composed of structural units derived from an aromatic dicarboxylic acid.

[0013] [Aliphatic diamine unit] From the viewpoint of advantageously improving physical properties such as heat resistance and flexibility, the carbon number of the aliphatic diamine used in the diamine unit is preferably 4 or more. That is, the semi-aromatic polyamide preferably contains a structural unit derived from an aliphatic diamine having 4 or more carbon atoms and a structural unit derived from an aromatic dicarboxylic acid. The aliphatic diamine used in the diamine unit is preferably an aliphatic diamine having 4 to 18 carbon atoms, more preferably an aliphatic diamine having 4 to 16 carbon atoms, even more preferably an aliphatic diamine having 4 to 12 carbon atoms, even more preferably an aliphatic diamine having 6 to 12 carbon atoms, even more preferably an aliphatic diamine having 6 to 10 carbon atoms, and even more preferably an aliphatic diamine having 7 to 10 carbon atoms. Furthermore, from the viewpoint that the polymerization reaction with dicarboxylic acid proceeds smoothly and is advantageous in improving physical properties such as heat resistance and flexibility, the content of the structural units derived from an aliphatic diamine having 4 to 18 carbon atoms relative to all diamine units is preferably 30 mol% or more, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, still more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and may even be 100 mol%.

[0014] Examples of aliphatic diamines having 4 to 18 carbon atoms include linear aliphatic diamines such as 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, and 1,18-octadecanediamine;1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 2-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-ethyl-1,5-pentanediamine, 2-propyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine amine, 2,4,4-trimethyl-1,6-hexanediamine, 2-ethyl-1,6-hexanediamine, 2-propyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2-ethyl-1,7-heptanediamine, 2-propyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine branched aliphatic diamines such as nonanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 2-ethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 5-methyl-1,9-nonanediamine;Alicyclic diamines such as 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, and bis(aminopropyl)piperazine are examples of such diamines. These may be used alone or in combination of two or more. From the viewpoint of heat resistance, it is preferable to use at least one aliphatic diamine selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines, and it is more preferable to use a combination of linear aliphatic diamines and branched aliphatic diamines.

[0015] When a linear aliphatic diamine and a branched aliphatic diamine are used in combination, the molar ratio of linear aliphatic diamine to branched aliphatic diamine is preferably 99:1 to 1:99, more preferably 95:5 to 5:95, even more preferably 90:10 to 10:90, even more preferably 85:15 to 15:85, even more preferably 80:20 to 20:80, even more preferably 70:30 to 30:70, and particularly preferably 65:35 to 35:65. When the molar ratio of linear aliphatic diamine to branched aliphatic diamine is within the above range, the polymerization reaction with polymer block (B) proceeds smoothly, and the resulting polyamide block copolymer can be expected to have excellent heat resistance and flexibility.

[0016] From the viewpoints of more significantly exhibiting the effects of the present invention and also having excellent raw material availability, the semi-aromatic polyamide preferably contains a structural unit derived from at least one selected from the group consisting of 1,4-butanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 2-propyl-1,6-hexanediamine, 2-ethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine, and more preferably contains a structural unit derived from at least one selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine. Among these, it is more preferable that the semi-aromatic polyamide contains structural units derived from both 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and that it contains structural units derived from both 1,6-hexanediamine and 1,10-decanediamine, and from the viewpoint of easily obtaining moldability and even more excellent heat resistance, it is even more preferable that it contains structural units derived from both 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

[0017] The content of 1,9-nonanediamine units and / or 2-methyl-1,8-octanediamine units in the total amount of diamine units constituting the semi-aromatic polyamide is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 75 to 100 mol%, and even more preferably 90 to 100 mol%. When the content of 1,9-nonanediamine units and / or 2-methyl-1,8-octanediamine units in the total amount of diamine units constituting the semi-aromatic polyamide is within the above range, further improved heat resistance and excellent chemical resistance can also be expected.

[0018] When 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonanediamine:2-methyl-1,8-octanediamine is preferably 99:1 to 1:99, more preferably 95:5 to 5:95, even more preferably 90:10 to 10:90, still more preferably 85:15 to 15:85, even more preferably 80:20 to 20:80, even more preferably 70:30 to 30:70, and particularly preferably 65:35 to 35:65. When the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is within the above range, the polymerization reaction with polymer block (B) proceeds smoothly, and the resulting polyamide block copolymer can be expected to have excellent heat resistance and flexibility.

[0019] Of the total amount of diamine units constituting the semi-aromatic polyamide, the content of 1,6-hexanediamine units and / or 1,10-decanediamine units is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 75 to 100 mol%, and even more preferably 90 to 100 mol%.

[0020] When 1,6-hexanediamine and 1,10-decanediamine are used in combination, the molar ratio of 1,6-hexanediamine:1,10-decanediamine is preferably 99:1 to 1:99, more preferably 95:5 to 5:95, even more preferably 90:10 to 10:90, and still more preferably 85:15 to 15:85.

[0021] Furthermore, the semi-aromatic polyamide may contain, as diamine units, structural units derived from diamines other than aliphatic diamines, such as aromatic diamines, as long as the effects of the present invention are not impaired. These structural units derived from diamines other than aliphatic diamines may be contained in one type only, or in two or more types. The content of the structural units derived from diamines other than aliphatic diamines in the diamine units is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 5 mol% or less.

[0022] [Aromatic Dicarboxylic Acid Unit] Examples of aromatic dicarboxylic acid units include structural units derived from isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, etc. From the viewpoint of smoothly proceeding the polymerization reaction with diamine and advantageously improving physical properties such as heat resistance, the aromatic dicarboxylic acid unit preferably contains a structural unit derived from at least one selected from the group consisting of terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. From the viewpoint of further improving heat resistance, it is more preferable to contain a structural unit derived from at least one selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid. These aromatic dicarboxylic acid units may be used alone or in combination of two or more.

[0023] From the viewpoint of heat resistance and mechanical strength, the content of structural units derived from at least one selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid relative to all dicarboxylic acid units is preferably 30 mol% or more, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, still more preferably 70 to 100 mol%, still more preferably 90 to 100 mol%, and may even be 100 mol%.

[0024] Furthermore, the semi-aromatic polyamide may contain, as dicarboxylic acid units, structural units derived from dicarboxylic acids other than aromatic dicarboxylic acids, such as aliphatic dicarboxylic acids, as long as the effects of the present invention are not impaired. These structural units derived from dicarboxylic acids other than aromatic dicarboxylic acids may be contained alone or in combination of two or more. Examples of aliphatic dicarboxylic acids include linear aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid; branched aliphatic dicarboxylic acids such as 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid; and alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. The content of structural units derived from other than the aromatic dicarboxylic acid in the dicarboxylic acid units is preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and even more preferably 5 mol % or less.

[0025] (Aliphatic diamine unit and aromatic dicarboxylic acid content) The content of structural units derived from aliphatic diamines relative to all structural units constituting the semi-aromatic polyamide is preferably 15 to 55 mol%, more preferably 25 to 55 mol%. The content of structural units derived from aromatic dicarboxylic acids relative to all structural units constituting the semi-aromatic polyamide is preferably 15 to 55 mol%, more preferably 25 to 55 mol%. The total content of structural units derived from aliphatic diamines and aromatic dicarboxylic acids relative to all structural units constituting the semi-aromatic polyamide is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, and may also be 90 to 100 mol%, or even 100 mol%.

[0026] [Other Structural Units] The semi-aromatic polyamide may contain structural units other than diamine units and dicarboxylic acid units, as long as the effects of the present invention are not impaired. Examples of other structural units include polycarboxylic acid units, aminocarboxylic acid units, and lactam units. Examples of polycarboxylic acid units include structural units derived from trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid. These polycarboxylic acid units can be incorporated to the extent that melt molding is possible. Examples of aminocarboxylic acid units include structural units derived from lactams such as caprolactam and lauryllactam; and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. Examples of lactam units include structural units derived from ε-caprolactam, enantholactam, undecanelactam, lauryllactam, α-pyrrolidone, and α-piperidone. The content of other structural units relative to all structural units constituting the semi-aromatic polyamide is preferably 30 mol% or less, more preferably 10 mol% or less.

[0027] [Specific Examples of Semi-Aromatic Polyamides] Representative semi-aromatic polyamides containing diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units include polytetramethylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T), polyhexamethylene terephthalamide / poly(2-methylpentamethyl terephthalamide) ... Poly(2-methyloctamethylene) terephthalamide copolymer (Polyamide 6T / M5T), Polynonamethylene terephthalamide (Polyamide 9T), Poly(2-methyloctamethylene) terephthalamide (Polyamide M8T), Polynonamethylene terephthalamide / Poly(2-methyloctamethylene) terephthalamide copolymer (Polyamide 9T / M8T), Polynonamethylene naphthalene dicarboxamide (Polyamide 9N), Poly(2-methyloctamethylene) naphthalene dicarboxamide (Polyamide M8N), Polynonamethylene naphthalene Dicarboxamide / poly(2-methyloctamethylene)naphthalenedicarboxamide copolymer (Polyamide 9N / M8N), polydecamethylene terephthalamide (Polyamide 10T), polydecamethylene terephthalamide / polypentamethylene terephthalamide copolymer (Polyamide 10T / 5T), polydecamethylene terephthalamide / poly(2-methylpentamethylene) terephthalamide copolymer (Polyamide 10T / M5T), polydecamethylene terephthalamide / poly(2-methyloctamethylene) terephthalamide Phthalamide copolymer (polyamide 10T / M8T), polyhexamethylene isophthalamide (polyamide 6I), copolymer of polyamide 6I and polyamide 6T (polyamide 6I / 6T), copolymer of polyhexamethylene adipamide (polyamide 66) and polyamide 6T (polyamide 66 / polyamide 6T), copolymer of polyamide 66, polyamide 6I and polyamide 6T (polyamide 66 / polyamide 6I / 6T), copolymer of polyamide 6T and polycaprolactam (polyamide 6) (polyamide 6T / 6),Examples include a copolymer of polyamide 6T and polyundecaneamide (polyamide 11) (polyamide 6T / 11), a copolymer of polyamide 6T and polydodecanamide (polyamide 12) (polyamide 6T / 12), polydecamethylene isophthalamide (polyamide 10I), a copolymer of polyamide 10I and polyamide 10T (polyamide 10I / 10T), a copolymer of polyamide 6T and polyamide 10T (polyamide 6T / 10T), a copolymer of polyamide 10T and polyamide 6 (polyamide 10T / 6), a copolymer of polyamide 10T and polyamide 11 (polyamide 10T / 11), and a copolymer of polyamide 10T and polyamide 12 (polyamide 10T / 12).

[0028] [Method for Producing Semi-Aromatic Polyamides] Semi-aromatic polyamides can be produced, for example, by melt polymerization, solid-state polymerization, melt extrusion polymerization, or other methods using dicarboxylic acids and diamines as raw materials. Specifically, semi-aromatic polyamides can be produced as follows. First, a nylon salt is produced by mixing a diamine, a dicarboxylic acid, an end-capping agent (described below), and, if necessary, an aminocarboxylic acid, a lactam, a catalyst, and the like. The resulting nylon salt is then heated to a temperature of 200 to 250°C and thermally polymerized to obtain a semi-aromatic polyamide as a prepolymer. Furthermore, the semi-aromatic polyamide can be adjusted to a desired molecular weight by solid-state polymerizing the prepolymer or by increasing the polymerization degree using a melt extruder. When the high-polymerization step is carried out by solid-state polymerization, it is preferably carried out under reduced pressure or in an inert gas flow. A polymerization temperature within the range of 200 to 280°C provides a high polymerization rate, excellent productivity, and effective suppression of coloration and gelation. When the step of increasing the degree of polymerization is carried out using a melt extruder, the polymerization temperature is preferably 370° C. or less. When polymerization is carried out under such conditions, a semi-aromatic polyamide is obtained with almost no decomposition and little deterioration.

[0029] Examples of catalysts that can be used in producing semi-aromatic polyamides include phosphoric acid, phosphorous acid, hypophosphorous acid, and salts or esters thereof. Examples of the salts or esters include salts of phosphoric acid, phosphorous acid, or hypophosphorous acid with metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony; ammonium salts of phosphoric acid, phosphorous acid, or hypophosphorous acid; and ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, octadecyl esters, decyl esters, stearyl esters, and phenyl esters of phosphoric acid, phosphorous acid, or hypophosphorous acid. The amount of catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the total mass of the raw materials for the semi-aromatic polyamide. The amount of catalyst used is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. Polymerization proceeds more smoothly when the amount of catalyst used is equal to or greater than the lower limit.

[0030] [Terminal Amino Group Content (Before Terminal Conversion)] In this embodiment, the terminals of the semi-aromatic polyamide can be adjusted to a desired functional group or functional group amount by using a terminal functionalizing agent described later. Meanwhile, the terminal amino group content here refers to the terminal amino group content in the polyamide before terminal conversion with the terminal functionalizing agent. The semi-aromatic polyamide before terminal conversion has a terminal amino group content ([NH ２ ]) is preferably 1 to 4,000 μmol / g, more preferably 1 to 3,000 μmol / g, even more preferably 1 to 2,500 μmol / g, still more preferably 1 to 2,000 μmol / g, even more preferably 1 to 1,500 μmol / g, even more preferably 1 to 1,000 μmol / g, and still more preferably 1 to 800 μmol / g. ２

[0043] The terminal carboxyl group content ([COOH]) of the semi-aromatic polyamide before terminal conversion is preferably 1 to 5,000 μmol / g, more preferably 25 to 4,000 μmol / g, even more preferably 50 to 3,000 μmol / g, still more preferably 75 to 2,500 μmol / g, still more preferably 75 to 2,000 μmol / g, still more preferably 75 to 1,500 μmol / g, and still more preferably 75 to 1,000 μmol / g. The terminal carboxyl group content ([COOH]) referred to in this specification refers to the amount of terminal carboxyl groups (unit: μmol) contained in 1 g of a semi-aromatic polyamide, and can be determined by potentiometric titration.

[0031] [Melting Point] The melting point of the semi-aromatic polyamide is preferably 200°C or higher, more preferably 205°C or higher, even more preferably 210°C or higher, even more preferably 230°C or higher, more preferably 240°C or higher, and even more preferably 250°C or higher. If the melting point of the polyamide is 230°C or higher, the heat resistance of the polyamide block copolymer is more likely to be improved. There is no particular upper limit to the melting point of the polyamide, but from the viewpoint of moldability, etc., it is preferably 320°C or lower. That is, the melting point of the semi-aromatic polyamide is preferably 230 to 320°C. In the present invention, the melting point can be determined as the peak temperature of the melting peak that appears when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) analyzer. More specifically, it can be determined by the method described in the Examples below.

[0032] [Semi-aromatic ratio] The semi-aromatic ratio (%) of a polyamide can be determined by methods well known to those skilled in the art. The semi-aromatic ratio of a polyamide refers to the ratio (percentage) of semi-aromatic polyamide repeating units among the repeating units constituting the polyamide. The semi-aromatic ratio of a polyamide can be determined, for example, by using NMR, and in this case, is expressed as a molar ratio. From the viewpoint of obtaining a polyamide block copolymer with excellent heat resistance, the semi-aromatic ratio of a polyamide is preferably 30% or more, more preferably 60% or more, even more preferably 75% or more, even more preferably 80% or more, and even more preferably 85% or more. The upper limit of the semi-aromatic ratio of a polyamide may be 100%. In a preferred aspect of this embodiment, the semi-aromatic ratio of a polyamide is 90% or more, preferably 94% or more. In a specific aspect, the semi-aromatic ratio of a polyamide is 100%.

[0033] The number average molecular weight of the polymer block (A) is preferably 300 to 12,000, more preferably 300 to 11,000, even more preferably 350 to 10,000, still more preferably 400 to 9,500, and still more preferably 500 to 9,000, and may be 600 to 8,500 or 700 to 8,000. Within the above numerical range, the compatibility between the polymer block (A) and the polymer block (B) is excellent, and the heat resistance of the polyamide block copolymer can be further improved. The weight-average molecular weight of polymer block (A) is preferably 1,000 to 50,000, more preferably 1,100 to 45,000, even more preferably 1,200 to 40,000, still more preferably 1,300 to 40,000, and even more preferably 1,400 to 36,000, and may be 1,500 to 30,000, 1,600 to 25,000, or 2,000 to 20,000. Within these numerical ranges, the compatibility between polymer block (A) and polymer block (B) is excellent, and the heat resistance of the polyamide block copolymer can be further improved. In the present invention, the number-average molecular weight and weight-average molecular weight can be measured by gel permeation chromatography, and more specifically, they are values ​​measured by the method described in the Examples.

[0034] [Terminal Functionalizing Agent] In this embodiment, a terminal functionalizing agent can be used to prepare a polymer block (A) in which the terminals of the polymer block (A), preferably the terminals of the semi-aromatic polyamide, are adjusted to the desired functional group or amount of functional groups. For example, the terminals of the polyamide can be converted by reacting the terminal functionalizing agent with the above-mentioned polyamide prepolymer. Alternatively, the terminals of the polyamide can be converted by adding an excess of either the dicarboxylic acid unit or the diamine unit at the stage of charging the raw materials. By adjusting the terminals of the polymer block (A) to the desired functional group or amount of functional groups, the polymer block (A) and the polymer block (B) can be bonded more effectively. The units derived from the terminal functionalizing agent are included in the polymer block (A).

[0035] In addition, when the semi-aromatic polyamide obtained by the above-mentioned method for producing a semi-aromatic polyamide has the desired functional group or functional group amount, a terminal functionalizing agent does not need to be used. That is, in this case, by reacting the polymer constituting the polymer block (A) with the polymer constituting the polymer block (B) without using a terminal functionalizing agent, the polymer block (A) and the polymer block (B) can be bonded well. In addition, the amount of active terminal functional groups of the semi-aromatic polyamide described below can be adjusted, for example, by adjusting the amount of carboxyl groups and amino groups contained in the reaction raw materials in the production of the semi-aromatic polyamide.

[0036] There are no limitations on the terminal functionalizing agent as long as it does not impair the effects of the present invention, and examples include those that can introduce functional groups such as hydroxyl groups, carboxyl groups, amino groups, epoxy groups, mercapto groups, sulfonyl groups, halogen atoms, vinyl groups, and vinylidene groups into the terminals of polyamides.

[0037] In this embodiment, it is preferable to use a compound selected from the group consisting of dicarboxylic acids and diamines as the terminal functionalizing agent. In this case, the polymer block (A) contains structural units derived from the polyamide and structural units derived from a compound selected from the group consisting of dicarboxylic acids and diamines. Dicarboxylic acids that can be used as terminal functionalizing agents include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Examples of aliphatic dicarboxylic acids include linear aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid; branched aliphatic dicarboxylic acids such as 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid; and alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid, and 3,4-furandicarboxylic acid.

[0038] Diamines that can be used as terminal functionalizing agents include aliphatic diamines and aromatic diamines, such as linear aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, and 1,18-octadecanediamine;1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 2-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine hexanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-ethyl-1,5-pentanediamine, 2-propyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6- Hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-ethyl-1,6-hexanediamine, 2-propyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2-ethyl-1,7-heptanediamine, 2-propyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8- branched aliphatic diamines such as octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 2-ethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 5-methyl-1,9-nonanediamine;Alicyclic diamines such as 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, and bis(aminopropyl)piperazine are listed. Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, and 4,4'-methylenedi-2,6-diethylaniline. The above terminal functionalizing agents may be used alone or in combination of two or more.

[0039] (Active Terminal Functional Group Content) In the present invention, the "active terminal functional group content" refers to the content of active terminal functional groups in the polymer block (A) contained in the polyamide block copolymer, and the total content of active terminal functional groups in the semi-aromatic polyamide is the active terminal functional group content of the polymer block (A). The "active terminal functional group" refers to a functional group that exhibits reactivity with the terminal functional group of the polymer block (B), and examples thereof include amino groups and carboxyl groups. When the terminals of a semi-aromatic polyamide are converted using a terminal functionalizing agent, the "active terminal functional group content" refers to the content of the active terminal functional groups after the conversion of the terminal functional groups. For example, when a semi-aromatic polyamide having amino groups at its terminals is converted to carboxyl groups using a terminal functionalizing agent, the total content of the converted terminal carboxyl groups and the unconverted terminal amino groups is the active terminal functional group content of the polymer block (A).

[0040] The content of the active terminal functional group in polymer block (A) may be any content of functional groups that are sufficiently reactive with the terminal functional groups in polymer block (B), and is preferably 5 μmol / g or more or 50 to 5,000 μmol / g, more preferably 75 to 4,500 μmol / g, even more preferably 100 to 4,000 μmol / g, still more preferably 120 to 4,000 μmol / g, still more preferably 150 to 3,000 μmol / g, still more preferably 200 to 2,000 μmol / g, still more preferably 250 to 1,500 μmol / g, and still more preferably 300 to 1,250 μmol / g. When the content of the active terminal functional group is 5 μmol / g or more, the compatibility between polymer block (A) and polymer block (B) is excellent, and the flexibility of the polyamide block copolymer can be further improved. Furthermore, if the active terminal functional group content is 5,000 μmol / g or less, the heat resistance of the polyamide block copolymer can be further improved. The active terminal functional group content as used herein refers to the amount (unit: μmol) of active terminal functional groups contained per gram of polyamide (or the polyamide after conversion when a terminal functionalizing agent is used), and can be determined by neutralization titration and potentiometric titration using an indicator.

[0041] <Polymer Block (B)> The polymer block (B) has a glass transition temperature of 20°C or lower. If the glass transition temperature exceeds 20°C, it becomes difficult for the polyamide block copolymer to have excellent flexibility. The glass transition temperature of the polymer block (B) is preferably 0°C or lower, more preferably -20°C or lower, from the viewpoint of easily exhibiting excellent flexibility at room temperature in the polyamide block copolymer. The lower the glass transition temperature of the polymer block (B), the more preferable it is. However, from the viewpoint of heat resistance, it may be -120°C or higher. That is, the glass transition temperature of the polymer block (B) is preferably -120 to 0°C. In the present invention, the glass transition temperature can be determined as the temperature of the inflection point that appears when the temperature is increased at a rate of 2°C / min using a differential scanning calorimetry (DSC) analyzer. More specifically, it can be determined by the method described in the Examples below. Alternatively, if it is difficult to measure the glass transition temperature by the above method, the glass transition temperature can be determined from literature values ​​or manufacturer measurement results. However, the glass transition temperature determined by the method described in the Examples below is preferentially used.

[0042] [Polymer Units] The polymer block (B) preferably contains an oxygen atom in the main chain. The polymer block (B) effectively exhibits flexibility by containing an oxygen atom, preferably an ether bond, in the main chain. That is, the polymer block (B) preferably contains a structural unit derived from an oxygen atom-containing polymer (hereinafter referred to as an "oxygen atom-containing polymer") that provides the polymer block (B) containing an oxygen atom in the main chain. From the viewpoint of easily achieving excellent flexibility in the polyamide block copolymer, the content of the structural unit derived from the oxygen atom-containing polymer in the polymer block (B) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and may even be 100 mol%. Furthermore, the content of the structural unit derived from the oxygen atom-containing polymer in the polymer block (B) may be 100 mol% or less. That is, the content of the structural unit derived from the oxygen atom-containing polymer in the polymer block (B) is preferably 50 to 100 mol%. In the polymer block (B), the structural units other than the structural unit derived from the oxygen atom-containing polymer are not limited as long as the effects of the present invention can be obtained.

[0043] Examples of oxygen atom-containing polymers include polyethers, polyesters, polycarbonates, and polysiloxanes. Details of polyethers, polyesters, polycarbonates, and polysiloxanes will be described later. Among these, polyethers are preferred as oxygen atom-containing polymers from the viewpoint of easily imparting excellent flexibility.

[0044] <Polyether> In this embodiment, "polyether" refers to polyether polyol and includes derivatives such as amine derivatives and carboxyl derivatives of polyether polyol. One or more polyethers can be used. When the oxygen atom-containing polymer is a polyether polyol, its amine derivative, or its carboxyl derivative, the polymer block (B) contains structural units derived from the polyether polyol, its carboxyl derivative, or its amine derivative. Preferably, the polymer block (B) contains 50 mol% or more structural units derived from the polyether polyol, its amine derivative, or its carboxyl derivative. Examples of polyethers include polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (PO3G), poly(oxybutylene) glycol, polytetramethylene ether glycol (PTMG), poly(3-alkyltetrahydrofuran), particularly poly(3-methyltetrahydrofuran) (poly(3MeTHF)), polypentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, and copolymers thereof. These may be used alone or in combination.

[0045] Examples of polyether amine derivatives and carboxyl derivatives include polyether diamines and polyether dicarboxylic acids. Among these, polyether diamines are preferred because they are expected to impart greater flexibility to polyamide block copolymers containing the polymer block (A) as a hard segment and to exhibit excellent chemical resistance. Examples of polyether diamines include polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (PO3G), poly(oxybutylene) glycol, polytetramethylene ether glycol (PTMG), poly(3-alkyltetrahydrofuran), particularly poly(3-methyltetrahydrofuran) (poly(3MeTHF)), polypentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, and copolymers thereof having amino groups introduced at two terminals. These may be used alone or in combination. Such polyether diamines can be obtained, for example, by cyanoacetylation of polyether diol.

[0046] Examples of polyether dicarboxylic acids include polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (PO3G), poly(oxybutylene) glycol, polytetramethylene ether glycol (PTMG), poly(3-alkyltetrahydrofuran), particularly poly(3-methyltetrahydrofuran) (poly(3MeTHF)), polypentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, and copolymers thereof having carboxyl groups introduced at two terminals. These may be used alone or in combination of two or more.

[0047] <Polyester> In this embodiment, "polyester" refers to polyester polyol and includes derivatives such as amine derivatives and carboxyl derivatives of polyester polyol. One or more types of polyester can be used. When the oxygen atom-containing polymer is a polyester polyol, its amine derivative, or its carboxyl derivative, the polymer block (B) will contain a structural unit derived from the polyester polyol, its amine derivative, or its carboxyl derivative. Examples of polyesters include poly(caprolactone) diol (PCL), poly(methylvalerolactone) diol, poly(ethylene adipate) glycol, poly(butylene-1,4-adipate) glycol (PBA), poly(methylpentanediol adipate) glycol, and poly(butylene-1,4-hexanediol-1,6-adipate) glycol. One or more types of these can be used.

[0048] The polyester can be, for example, one produced by polycondensation of a dicarboxylic acid and a polyhydric alcohol. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as 1,4-cyclohexyldicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; and dimer fatty acids consisting of one or two types selected from unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid. These can be used alone or in combination of two or more types. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, etc. These can be used alone or in combination of two or more.

[0049] Examples of the amine derivatives in polyesters include those in which an amino group has been introduced at the end of a polyester polyol or the like. One or more of these can be used. Examples of the carboxyl derivatives in polyesters include those in which a carboxyl group has been introduced at the end of a polyester polyol or the like. The carboxyl derivatives may have at least one carboxyl group at the end, and may, for example, have carboxyl groups at all ends, or may have both carboxyl groups and hydroxyl groups at the end. One or more of these can be used.

[0050] <Polycarbonate> In this embodiment, "polycarbonate" refers to polycarbonate polyol and includes derivatives such as amine derivatives and carboxyl derivatives of polycarbonate polyol. One or more types of polycarbonate can be used. When the oxygen atom-containing polymer is polycarbonate polyol, its amine derivative, or its carboxyl derivative, the polymer block (B) will contain structural units derived from polycarbonate polyol, its amine derivative, or its carboxyl derivative. Examples of polycarbonates include poly(hexanediol-1,6-carbonate) diol and polytetrahydrofuran carbonate diol (PCD). One or more types of these can be used.

[0051] The polycarbonate may be, for example, one produced by an esterification reaction between a carbonate ester and a polyhydric alcohol, or one produced by an interfacial polycondensation method in which a polyhydric alcohol is reacted with phosgene. Examples of carbonate esters include methyl carbonate, ethyl carbonate, and phenyl carbonate. These may be used alone or in combination of two or more. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in combination of two or more.

[0052] Examples of the amine derivatives in polycarbonate include those in which an amino group has been introduced at the end of a polycarbonate polyol, etc. One or more of these can be used. Examples of the carboxyl derivatives in polycarbonate include those in which a carboxyl group has been introduced at the end of a polycarbonate polyol, etc. The carboxyl derivatives may have at least one carboxyl group at the end, and may, for example, have carboxyl groups at all ends, or may have both carboxyl groups and hydroxyl groups at the end. One or more of these can be used.

[0053] <Polysiloxane> In this embodiment, "polysiloxane" refers to polysiloxane polyol, and also includes derivatives such as amine derivatives and carboxyl derivatives of polysiloxane polyol. One or more polysiloxanes can be used. When the oxygen atom-containing polymer is polysiloxane polyol, its amine derivative, or its carboxyl derivative, the polymer block (B) will contain a structural unit derived from polysiloxane polyol, its amine derivative, or its carboxyl derivative. Examples of polysiloxanes include compounds having hydroxyl groups at the terminals of polyorganosiloxanes having repeating units represented by the following formula (X): Specific examples include polydimethylsiloxanediol, polydiphenylsiloxanediol, polytrifluoropropylmethylsiloxanediol, polyphenylmethylsiloxanediol, polydiethylsiloxanediol, polydivinylsiloxanediol, polyvinylmethylsiloxanediol, and poly(5-hexenyl)methylsiloxanediol.

[0054]

[0055] R and R' in formula (X) are organic groups and may be the same or different. The organic group is not limited as long as it does not impair the effects of the present invention, and examples thereof include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; alkenyl groups having 1 to 5 carbon atoms, such as vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylvinyl, and 1-methylallyl; alicyclic alkyl groups, such as cyclohexyl; and aryl groups, such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.

[0056] Examples of the amine derivatives in polysiloxane include those in which an amino group has been introduced at the end of a polysiloxane polyol, etc. One or more of these can be used. Furthermore, examples of the carboxyl derivatives in polysiloxane include those in which a carboxyl group has been introduced at the end of a polysiloxane polyol, etc. One or more of these can be used.

[0057] [Molecular Weight] The number average molecular weight of polymer block (B) is preferably 100 or more, 150 or more, or 200 or more, more preferably 300 or more or 400 or more. From the viewpoint of obtaining a polyamide block copolymer having excellent flexibility, particularly excellent tensile properties, it may be 500 or more, 700 or more, or 800 or more. Furthermore, the number average molecular weight of polymer block (B) is not limited as long as the polymerization reaction with polymer block (A) proceeds smoothly, but may be, for example, 7,000 or less, 6,000 or less, or 5,000 or less. That is, the number average molecular weight of polymer block (B) is preferably 100 to 7,000, more preferably 200 to 5,000. Within the above numerical range, the polymerization reaction with polymer block (A) proceeds smoothly, and the polyamide block copolymer has excellent flexibility, which tends to further improve tensile properties.

[0058] <Method for Producing Polyamide Block Copolymer> In the method for producing a polyamide block copolymer of this embodiment, it is preferable to use a terminal-capping agent described below and mix and polymerize a polymer constituting the polymer block (A) containing 50 mol% or more of the structural units derived from the semi-aromatic polyamide described above with a polymer constituting the polymer block (B) having a glass transition temperature of 20°C or less. As exemplified below, the terminal-capping agent can be used at any stage of the production process. Furthermore, the method for producing a polyamide block copolymer of this embodiment may also use the terminal functionalizing agent described above. For example, the monomer constituting the polymer block (A) may be mixed with the terminal-capping agent described below and, if necessary, the terminal functionalizing agent, and the mixture may be melt-polymerized to obtain a polymer constituting the polymer block (A) with adjusted terminal functional groups. Subsequently, the polymer constituting the polymer block (B) may be added and melt-polymerized to produce a polyamide block copolymer. As a first specific example, a polyamide block copolymer may be produced by dry-blending a polymer constituting polymer block (A), in which the terminal functional groups have been adjusted by melt polymerization in the presence of a terminal capping agent described below during the polymerization stage of polymer block (A), with a polymer constituting polymer block (B), optionally in the presence of the terminal functionalizing agent, and melt-kneading the resulting mixture. As a second specific example, the polymer constituting polymer block (A) may be reacted with a terminal capping agent described below and, optionally, the terminal functionalizing agent, followed by pulverization to adjust the terminal functional groups of polymer block (A), and then the polymer constituting polymer block (B) may be added and mixed, and the resulting mixture may be melt-polymerized. As a third specific example, the polymer constituting polymer block (A) may be charged into an upper hopper of a melt kneader and, optionally, the terminal capping agent described below and, optionally, the terminal functionalizing agent, and reacted therewith, and then the polymer block (B) may be added through a side feed port downstream of the extruder, thereby carrying out stepwise melt extrusion polymerization.

[0059] As the polymerization method, methods such as melt polymerization, solid-state polymerization, and melt-extrusion polymerization can usually be used. Melt polymerization or melt-extrusion polymerization may be combined with solid-state polymerization. As the melt-extrusion polymerization method, a method of melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like is preferably used. The melt-kneading conditions are not particularly limited, but for example, a method of melt-kneading for about 1 to 120 minutes at a temperature range about 0 to 60°C higher than the melting point of the polyamide is preferred from the viewpoint of more easily achieving the effects of the present invention.

[0060] The polyamide block copolymer of this embodiment can be obtained, for example, by mixing and polymerizing the respective polymers constituting the hard segment and the soft segment. In this way, by mixing and polymerizing a pre-prepared polymer block (A) and a pre-prepared polymer block (B), the polyamide block copolymer of this embodiment contains the intended blocks as the polymer blocks constituting each segment. When the polyamide block copolymer of this embodiment contains the intended blocks as described above, it tends to have excellent heat resistance. In addition, when the polymer blocks constituting each segment are derived from pre-prepared polymers, the properties of each polymer block are more easily exhibited. As a result, the polyamide block copolymer of this embodiment is thought to contribute to improved thermal stability.

[0061] <End-capping ratio> The polyamide block copolymer of this embodiment is characterized by having an end-capping ratio of 10% or more. The "end-capping ratio" refers to the percentage of the ends blocked by an end-capping agent relative to the total number of molecular chain end groups, including those blocked by an end-capping agent, carboxyl group end, and amino group end. The mobility of molecular chain ends, such as carboxyl group end and amino group end, in polyamide block copolymers may accelerate thermal degradation. Furthermore, end groups with high mobility may reduce thermal stability. Therefore, to suppress the acceleration of thermal degradation due to the mobility of the molecular chain end, the functional groups at the molecular chain end can be replaced with other end groups, preferably end groups that maintain the crystallinity of the polyamide block copolymer or end groups with high cohesive strength, using an end-capping agent described below, thereby improving thermal stability.

[0062] The polyamide copolymer of this embodiment has superior thermal stability compared to polyamide block copolymers having a similar configuration but a terminal-capping ratio of less than 10%. From the viewpoint of further improving the thermal stability of the polyamide block copolymer, the terminal-capping ratio is preferably 15% or more, more preferably 20% or more, even more preferably 25% or more, even more preferably 30% or more, and even more preferably 40% or more. Furthermore, since a higher terminal-capping ratio tends to improve thermal stability, the upper limit of the terminal-capping ratio may be 100% from the viewpoint of improving thermal stability. That is, the terminal-capping ratio is preferably 10% to 100%.

[0063] The terminal-capping ratio can be adjusted by adjusting the amount of terminal-capping agent charged relative to the diamine when charging the polymerization raw materials for the semi-aromatic polyamide. Taking into consideration the volatilization of the monomer components during the polymerization, it is desirable to finely adjust the amount of terminal-capping agent charged when charging the polymerization raw materials so that the terminal-capping ratio falls within the above-mentioned numerical range. Furthermore, when polymerizing the polymer constituting polymer block (A) and the polymer constituting polymer block (B), a terminal-capping agent can be charged so that the terminal-capping ratio falls within the above-mentioned numerical range. Furthermore, a terminal-capping agent can be charged to the polymer constituting polymer block (A) together with the above-mentioned terminal functionalizing agent so that the terminal-capping ratio falls within the above-mentioned numerical range.

[0064] To determine the terminal capping rate, the total number of terminal groups and the number of active terminal groups present in the polyamide block copolymer are determined, and the terminal capping rate can be calculated using the following formula (1). Formula (1): Terminal capping rate (%) = [(A - B) ÷ A] × 100 In formula (1), A represents the total number of terminal groups (μmol / g). The total number of terminal groups is usually equal to twice the number of polyamide molecules. B represents the number of active terminal groups (μmol / g). The number of active terminal groups is the total number of active terminal groups, such as carboxyl terminals, amino terminals, and hydroxyl groups. (A - B) represents the number of blocked terminal groups (μmol / g).

[0065] The total number of terminal groups can be calculated by the following method: Total number of terminal groups (µmol / g) = 2,000,000 / Mn (Mn represents the number average molecular weight).

[0066] The number of active terminal groups can also be determined by titration. Here, as an example of how to determine the number of active terminal groups, the methods for determining the number of carboxyl terminal groups and the number of amino terminal groups are shown below. The number of carboxyl terminal groups (μmol / g) can be determined by titrating a cresol solution of a polyamide block copolymer with a 0.1 N potassium hydroxide-ethanol solution. The number of amino terminal groups (μmol / g) can be determined by titrating a phenol solution of a polyamide block copolymer with 0.1 N hydrochloric acid. More specifically, they can be determined by the method described in the Examples below.

[0067] [End-capping agent] As the end-capping agent, a monofunctional compound reactive with a terminal amino group or a terminal carboxyl group can be used. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoints of reactivity and the stability of the blocked end, a monocarboxylic acid is preferred as an end-capping agent for a terminal amino group, and a monoamine is preferred as an end-capping agent for a terminal carboxyl group. From the viewpoint of ease of handling, a monocarboxylic acid is more preferred as an end-capping agent. Only one type of end-capping agent may be used, or two or more types may be used.

[0068] The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it is reactive with amino groups and can at least suppress the mobility of the molecular chain ends of the polyamide block copolymer. From this viewpoint, it is preferable that the monocarboxylic acid has high cohesive strength or maintains the crystallinity of the polyamide block copolymer. Examples of such monocarboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, behenic acid, and pivalic acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, and methylnaphthalenecarboxylic acid; monocarboxylic acids having an aromatic alkyl group such as phenylacetic acid; and any mixtures thereof. Among these, from the viewpoints of reactivity, stability of the blocked terminal, cost, and the like, at least one selected from acetic acid, propionic acid, butyric acid, decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid is preferred, and benzoic acid is even more preferred from the viewpoint of being more likely to achieve even better thermal stability.

[0069] The monoamine used as the end-capping agent is not particularly limited as long as it is reactive with carboxyl groups and can at least suppress the mobility of the molecular chain ends of the polyamide block copolymer. From this viewpoint, it is preferable that the monoamine has high cohesion or maintains the crystallinity of the polyamide block copolymer. Examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, and dipropylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and any mixtures thereof. Among these, at least one selected from methylamine, ethylamine, propylamine, dodecylamine, stearylamine, cyclohexylamine, and aniline is preferred in terms of reactivity, stability of the blocked end, and cost.

[0070] Furthermore, from the viewpoint of facilitating improved thermal stability, the molecular terminals of the polyamide block copolymer are preferably blocked with at least one selected from the group consisting of an aryl group, an aromatic alkyl group, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 9 or more carbon atoms, an alicyclic alkyl group having 4 or more carbon atoms, and a hydrogen atom.

[0071] From the viewpoint of further enhancing thermal stability, it is preferable that the molecular ends of the polyamide block copolymer are blocked with at least one selected from the group consisting of aryl groups, aromatic alkyl groups, alkyl groups having 1 to 3 carbon atoms, alkyl groups having 9 or more carbon atoms, and alicyclic alkyl groups having 4 or more carbon atoms. From the viewpoint of further enhancing thermal stability, it is more preferable that the molecular ends of the polyamide block copolymer are blocked with at least one selected from the group consisting of aryl groups, aromatic alkyl groups, alkyl groups having 9 or more carbon atoms, and alicyclic alkyl groups having 4 or more carbon atoms. From the viewpoint of further enhancing thermal stability, it is even more preferable that the molecular ends of the polyamide block copolymer are blocked with at least one selected from the group consisting of aryl groups, aromatic alkyl groups, and alicyclic alkyl groups having 4 or more carbon atoms. From the viewpoint of further enhancing thermal stability, it is even more preferable that the molecular ends of the polyamide block copolymer are blocked with at least one selected from the group consisting of aryl groups and alicyclic alkyl groups having 4 or more carbon atoms. It is believed that the aryl group and the alicyclic alkyl group having 4 or more carbon atoms contribute to more effectively suppressing the mobility of the molecular end compared to other terminal groups, from the viewpoint of at least one of increasing the cohesive strength of the molecular chain end and maintaining the crystallinity of the polymer.

[0072] Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group. From the viewpoints of reactivity and cost, the aryl group is preferably a phenyl group or a naphthyl group. Examples of end-capping agents capable of introducing an aryl group into a molecular terminal include benzoic acid, α-naphthalenecarboxylic acid, and β-naphthalenecarboxylic acid.

[0073] Examples of the aromatic alkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group. From the viewpoints of reactivity and cost, the aromatic alkyl group is preferably a benzyl group. Examples of end-capping agents capable of introducing an aromatic alkyl group into a molecular terminal include phenylacetic acid.

[0074] Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of the stability of the blocked terminal, the alkyl group having 1 to 3 carbon atoms is preferably a methyl group or an ethyl group. Examples of end-capping agents that can introduce an alkyl group having 1 to 3 carbon atoms into the molecular terminal include acetic acid, propionic acid, and butyric acid. Note that the carbon constituting this alkyl group does not include a carbon bonded to a carbonyl group.

[0075] The alkyl group having 9 or more carbon atoms refers to a linear or branched alkyl group having 9 or more carbon atoms in its main chain. In other words, the number of carbon atoms in the main chain of such an alkyl group does not include the number of carbon atoms in the branched chain. Examples of alkyl groups having 9 or more carbon atoms in their main chain include n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups. The alkyl group having 9 or more carbon atoms in its main chain may further have a branched chain. Examples of such branched chains include alkyl groups similar to the alkyl groups having 1 to 3 carbon atoms described above. From the viewpoints of reactivity, stability of the blocked terminal, and cost, the alkyl group having 9 or more carbon atoms is preferably a linear alkyl group having 9 to 18 carbon atoms, and more preferably a lauryl group or a stearyl group. Examples of end-capping agents that can introduce an alkyl group having 9 or more carbon atoms into the molecular terminal include monocarboxylic acids having 9 or more carbon atoms, such as decanoic acid, lauric acid, and stearic acid, and monoamines having 12 or more carbon atoms, such as dodecylamine and stearylamine. Note that the carbon atoms that make up this alkyl group do not include carbon atoms bonded to a carbonyl group.

[0076] Examples of the alicyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptanyl group, a cyclooctanyl group, a cyclononanyl group, and a cyclodecanyl group. From the standpoints of reactivity, stability of the blocked terminal, and cost, the alicyclic alkyl group is preferably an alicyclic alkyl group having 4 to 10 carbon atoms, and more preferably a cyclohexyl group. Examples of end-capping agents that can introduce an alicyclic alkyl group to the molecular terminal include monocarboxylic acids having 4 or more carbon atoms, such as cyclohexanecarboxylic acid, and monoamines having 4 or more carbon atoms, such as cyclohexylamine. Note that the carbons constituting this alkyl group do not include the carbon to which a carbonyl group is bonded.

[0077] Examples of end-capping agents that can cap molecular ends with hydrogen atoms include formic acid.

[0078] <Mass Ratio (A) / (B)> In the polyamide block copolymer of this embodiment, the mass ratio (A) / (B) of polymer block (A) to polymer block (B) is preferably 1 / 99 to 99 / 1, preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 95 / 5, even more preferably 20 / 80 to 95 / 5, even more preferably 40 / 60 to 90 / 10, even more preferably 50 / 50 to 85 / 15, and even more preferably 60 / 40 to 85 / 15. If the mass ratio (A) / (B) is within the above range, the polyamide block copolymer is more likely to achieve both excellent heat resistance and flexibility, which is preferable.

[0079] <Polymer Block Content> From the viewpoint of obtaining a polyamide block copolymer having excellent thermal stability, the content of polymer block (A) in 100% by mass of the total amount of the polyamide block copolymer is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 46% by mass or more, and even more preferably 49% by mass or more or 50% by mass or more. From the viewpoint of obtaining a polyamide block copolymer having excellent elongation, the content of polymer block (A) in 100% by mass of the total amount of the polyamide block copolymer is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 88% by mass or less or 85% by mass or less. From the viewpoint of obtaining a polyamide block copolymer having excellent elongation, the content of polymer block (B) in 100% by mass of the total amount of the polyamide block copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more or 15% by mass or more, and in some cases may be 20% by mass or more or 25% by mass or more. From the viewpoint of obtaining a polyamide block copolymer having excellent thermal stability, the content of polymer block (B) in 100% by mass of the total amount of the polyamide block copolymer is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 54% by mass or less or 51% by mass or less. The total amount of polymer block (A) and polymer block (B) in 100% by mass of the total amount of the polyamide block copolymer is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more. From the viewpoint of obtaining a polyamide block copolymer having excellent physical properties such as thermal stability and elongation, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more.

[0080] <Molecular Weight of Polyamide Block Copolymer> The number average molecular weight of the polyamide block copolymer is preferably 50,000 or less or 3,000 to 50,000, more preferably 3,000 to 40,000, even more preferably 4,000 to 30,000, even more preferably 4,500 to 25,000, still more preferably 5,000 to 20,000, even more preferably 6,000 to 20,000, and even more preferably 7,000 to 20,000. The higher the molecular weight, the better the heat resistance, but the lower the moldability tends to be. Within the above numerical range, the heat resistance of the polyamide block copolymer can be further improved and good moldability can be expected. The weight-average molecular weight of the polyamide block copolymer is preferably 500,000 or less, or 30,000 to 500,000, more preferably 40,000 to 300,000, more preferably 43,000 to 280,000, even more preferably 45,000 to 250,000, and even more preferably 50,000 to 230,000, and may be 65,000 to 200,000 or 75,000 to 200,000. Within these numerical ranges, the polyamide block copolymer exhibits stronger material properties and is expected to have good molding processability. The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the polyamide block copolymer is preferably 2.0 to 15.0, more preferably 3.0 to 12.0. Within these numerical ranges, the heat resistance of the polyamide block copolymer can be further improved and good molding processability can be expected.

[0081] <Melting Point of Polyamide Block Copolymer> From the viewpoint of excellent heat resistance, the melting point of the polyamide block copolymer is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, even more preferably 235°C or higher, and even more preferably 240°C or higher. A melting point of the polyamide block copolymer of 230°C or higher is preferable because it can impart better heat resistance to molded articles obtained using the polyamide block copolymer. There is no particular upper limit to the melting point of the polyamide block copolymer, but from the viewpoint of moldability, etc., a melting point of 315°C or lower is preferable. That is, the melting point of the polyamide block copolymer is preferably 200°C to 315°C, more preferably 230°C to 315°C. In order to increase the melting point of the polyamide block copolymer and obtain excellent heat resistance, the polymer block (A) preferably contains 50 mol % or more of structural units derived from a semi-aromatic polyamide, more preferably contains less than 50 mol % or less of structural units derived from a non-semi-aromatic polyamide, even more preferably contains 10 mol % or less of structural units derived from a non-semi-aromatic polyamide, and even more preferably contains no structural units derived from a non-semi-aromatic polyamide (i.e., 0 mol %).

[0082] <Weight Loss Rate (Thermal Stability) of Polyamide Block Copolymer> The weight loss rate of the polyamide block copolymer of this embodiment is preferably 3.00% or less, more preferably 2.00% or less, even more preferably 1.50% or less, still more preferably 1.00% or less or less than 1.00%, still more preferably 0.90% or less, less than 0.84% ​​or 0.80% or less, still more preferably 0.75% or less, still more preferably 0.70% or less, and can also be 0.50% or less. In the present invention, the weight loss rate of the polyamide block copolymer can be measured using a thermogravimetric analyzer, and more specifically, it is a value measured by the method described in the examples.

[0083] <Tensile Break Strength and Tensile Break Elongation (Tensile Properties) of Polyamide Block Copolymer> The tensile break strength of the polyamide block copolymer of this embodiment, measured in accordance with JIS K 7161-1:2014, is preferably 5 MPa or more, more preferably 10 MPa or more, even more preferably 20 MPa or more, still more preferably 30 MPa or more, and can be 35 MPa or more. The tensile break elongation of the polyamide block copolymer of this embodiment, measured in accordance with JIS K 7161-1:2014, is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, even more preferably 100% or more, even more preferably 150% or more, even more preferably 200% or more, even more preferably 250% or more, and can even be 300% or more. In this specification, tensile properties are an index of flexibility. The larger the tensile break elongation value, the more excellent the flexibility of the polyamide block copolymer. More specifically, the tensile strength at break and the tensile elongation at break can be determined by the methods described in the examples below.

[0084] <Polyamide Block Copolymer Composition> One embodiment of the present invention may be a polyamide block copolymer composition containing the polyamide block copolymer. The polyamide block copolymer composition is produced by adding components other than the polyamide block copolymer to the polyamide block copolymer. Examples of such components include additives such as antioxidants, antiozonants, weathering stabilizers, UV absorbers, hydrolysis-resistant stabilizers, fillers, nucleating agents, reinforcing agents, carbon black, pigments, inorganic dyes, organic dyes, colorants, color inhibitors, antigelling agents, delustering agents, antistatic agents, plasticizers, lubricants, mold release agents, shrinkage-resistant agents, compatibilizers, flame retardants, flame retardant assistants, and foaming agents. These additives may be present alone or in combination with one or more other additives. The content of the additives is not particularly limited as long as it does not impair the effects of the present invention, but may be from 0.02 to 200 parts by weight per 100 parts by weight of the polyamide block copolymer. Examples of the method for adding the additives include adding them during polymerization of the polyamide block copolymer, and dry blending them with the polyamide block copolymer and melt-kneading them.

[0085] [Method for Producing Polyamide Block Copolymer Composition] The method for producing the polyamide block copolymer composition is not particularly limited, and any method that can uniformly mix the polyamide block copolymer and the above-mentioned additives can be preferably used. Mixing is typically performed by melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like. The melt-kneading conditions are not particularly limited, and examples include melt-kneading for approximately 1 to 120 minutes at a temperature range approximately 0 to 60°C higher than the melting point of the polyamide block copolymer.

[0086]

[0033] <<Molded Article>> In one embodiment of the present invention, a molded article may be formed from the polyamide block copolymer or the polyamide block copolymer composition. The molded article of this embodiment can be used as an electric / electronic part, an automobile part, an industrial part, a fiber, a film, a sheet, a household product, or any other molded article of any shape and for any purpose.

[0087] <Method for producing molded article> The method for producing a molded article is not particularly limited, and examples thereof include various conventional molding methods, such as injection molding, blow molding, press molding, extrusion molding, calendar molding, vacuum molding, pressure molding, bead molding, batch foam molding, etc. Examples of forms of the molded article include pellets, sheets, plates, pipes, tubes, rods, granules, and foams.

[0088] <Applications> The polyamide block copolymer and polyamide block copolymer composition of this embodiment have improved thermal stability compared to conventional products, and can also exhibit excellent heat resistance and flexibility, making them useful in a wide range of fields where these properties are required. For example, the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as materials for various parts, such as electrical and electronic components, automotive parts, industrial material parts, industrial parts, daily necessities, household goods, sports parts, leisure parts, and medical parts. In particular, they can be used to produce complex-shaped parts by injection molding, hollow-molded parts by blow molding, hose- and tubular-shaped parts and films and sheets by extrusion molding, lightweight components and insulating materials by injection and / or extrusion foam molding, and as additives for resin modification. They can also be used as foams by injection molding, blow molding, press molding, extrusion molding, calendar molding, vacuum forming, pressure forming, bead molding, or batch foam molding. More specifically, among electronic and electrical components, they can be used as materials for mobile phone and game console hinges, camera grips, printer tractor belts, electrical wire coatings, and tubes for home appliances. More specifically, among automotive parts, the material can be used as a material for constant velocity joint boot parts, curl cords, airbag doors, hydraulic hoses, shift levers, cable liners, automotive belts, fuel tether caps, door locks, steering switches, seat locks, accelerator pedals, air ducts, airless tires, tire frames, tire inner liners, etc. More specifically, among industrial material parts and / or industrial components, the material can be used as a material for submersible pumps, seal members, bushings, tubes, spiral tubes, diaphragms, mop joints, noiseless gears, mandrels, films, nonwoven fabrics, monofilaments, ball joint sheets, register rods, fire hoses, conveyor belts, pulleys, wire cables, etc. More specifically, among daily necessities and / or household goods, the material can be used as a material for hair dryer brushes, nail polish cases, hot curlers, zipper pulls, bobbin cases, console shutters, corrugated tubes, corrugated hoses, pillow cushioning, mattress cushioning, chair cushioning, etc.More specifically, among sports parts, it can be used as a material for running shoes, spiked shoes, ski boots, etc. More specifically, among medical parts, it can be used as a material for medical catheters, wearable devices, optical products, eye care parts, etc.

[0089] <Foamed Product> One advantageous aspect of the molded product is a foamed product (foam). Foams will now be described. Foam production methods include, for example, (1) extrusion, (2) crosslinking, (3) foaming, (4) expansion process, and (5) molding steps. In the (1) extrusion step, mixing and kneading are performed as necessary. (2) Crosslinking involves at least one of chemical crosslinking and physical crosslinking. In the (3) foaming step, a foaming agent, such as an organic foaming agent, may be used, or a supersaturated gas, preferably an inert gas, may be used, or both a foaming agent and a supersaturated gas may be used. (4) The expansion process may involve free expansion, for example, in an oven, or limited expansion, for example, in a mold. (5) Molding may be performed in a batch system or a continuous system. Examples of molding methods include press molding, vacuum molding, embossing, and overinjection. The foam production method is not limited to the above examples. To produce the foam, any of injection molding, blow molding, extrusion molding, calendar molding, pressure molding, bead molding, batch foam molding, cutting, punching, scraping, and coating (e.g., adhesive coating, extrusion coating) may be used instead of or in addition to the above processes.Applications of the foam include soccer balls, sports glove pads (goalkeeper, boxing, etc. pads), immersion suits, golf club grips, rebound layers for table tennis rackets, ski poles, sports bat grips, snowboard or windsurfing pads, saddles (e.g., bicycle saddles), cushions (e.g., ski lift seat cushions, pillow cushions, mattress cushions, chair cushions, etc.), ski boot components; anti-slip coated tape; underwear (e.g., bra cups); mouse pads, soft keyboards, buttons; equipment trays (e.g., automotive equipment trays); gaskets; flexographic printing rolls; single-sided adhesive coated tape, double-sided adhesive coated tape; orthopedic insoles or inlays, footwear insoles or inner soles, footwear midsoles, footwear linings, waterproof and breathable insoles or midsoles, footwear shafts or heel inserts, forefoot inserts; transdermal pads, transdermal absorption pads, wound healing plasters; sportswear, and apparel linings.

[0090] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0091] <Measurement and Evaluation Methods> Various physical properties were measured or evaluated by the following methods.

[0092] [Molecular Weight] The polyamides produced in the Synthesis Examples, the polyethers used as polymer block (B), and the polyamide block copolymers obtained in the Examples and Comparative Examples were used as samples, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were determined by gel permeation chromatography (GPC) using standard polymethyl methacrylate-equivalent molecular weights. An HFIP solution prepared by dissolving sodium trifluoroacetate at a ratio of 0.85 g per 1 kg of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was used as the eluent. 1.5 mg of the sample, in resin equivalent, was dissolved in 3 mL of the eluent, and the eluent was passed through a 0.4 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows: (Measurement Conditions) Apparatus: HLC-8320GPC (Tosoh Corporation) Column: Two TSK gel Super HM-H (Tosoh Corporation) columns connected in series. Eluent: 0.085% by mass sodium trifluoroacetate / HFIP solution Flow rate: 0.5 mL / min (reference column: 0.25 mL / min) Sample injection volume: 30 μL Column temperature: 40°C Standard polymethyl methacrylate: Shodex Standard M-75 (Showa Denko K.K.), Polymethylmethacrylate molecular weight 1010 and molecular weight 535 (Agilent Technologies Inc.) Detector: UV (254 nm) detector, UV (210 nm) detector

[0093] [Terminal amino group content ([NH ２ Using the polyamide produced in the Synthesis Example as a sample, 1 g of the sample was dissolved in 35 mL of phenol and mixed with 3 mL of methanol to prepare a sample solution. Using thymol blue as an indicator, titration was carried out using a 0.01 or 0.1 N HCl aqueous solution to measure the terminal amino group content ([NH ２ ], unit: μmol / g) was measured.

[0094] [Measurement of Terminal Carboxyl Group Content ([COOH])] Using the polyamide produced in the Synthesis Example as a sample, 0.5 g of the sample was dissolved in 40 mL of ortho-cresol to prepare a sample solution. Using a potentiometric titrator, titration was carried out using a 0.01 or 0.1 N KOH / EtOH solution under the following measurement conditions to measure the terminal carboxyl group content ([COOH], unit: μmol / g). (Measurement Conditions) Measuring device: MCU-710M / S (Kyoto Electronics Manufacturing Co., Ltd.) Measuring unit: AT-710 Main control unit: MCU-710 The terminal carboxyl group contents ([COOH], unit: μmol / g) of adipic acid and terephthalic acid used as terminal functionalizing agents were calculated from the molecular weight based on the fact that each molecule contains two carboxyl groups.

[0095] [Terminal Capping Rate] For the polyamide block copolymers obtained in the examples, the terminal capping rate was calculated from the following formula (2). Formula (2): Terminal capping rate "%" = {(Number of blocked terminal groups) / Total number of terminal groups} x 100 The meanings of the terms in the above formula (2) are as follows: Number of blocked terminal groups (µmol / g) = Total number of terminal groups - (Number of active terminal groups) Total number of terminal groups (µmol / g) = 2,000,000 / Mn Number of active terminal groups (µmol / g) = Concentration of amino terminal groups (µmol / g) + Concentration of carboxyl terminal groups (µmol / g) Mn is the value calculated by GPC as in the above "Molecular weight". The amino terminal concentration and the carboxyl terminal concentration were calculated using the above "Terminal amino group content ([NH ２ The polyamide block copolymers obtained in the examples and comparative examples were used as samples and quantified by the same titration method as in "Measurement of terminal carboxyl group content ([COOH])" and "Measurement of terminal carboxyl group content ([COOH])."

[0096] [Melting Point and Heat of Fusion] The polyamides produced in the Synthesis Examples and the polyamide block copolymers obtained in the Examples and Comparative Examples were used as samples, and their melting points were measured using a differential scanning calorimeter "DSC25" manufactured by TA Instruments. The melting points were measured in accordance with ISO 11357-3 (2011, 2nd edition). Specifically, in a nitrogen atmosphere, the sample was heated from 30°C to 340°C at a rate of 10°C / min, held at 340°C for 5 minutes to completely melt the sample, and then cooled to 50°C at a rate of 10°C / min and held at 50°C for 5 minutes. The peak temperature of the melting peak that appeared when the sample was again heated to 340°C at a rate of 10°C / min was taken as the melting point (°C). If there were multiple melting peaks, the peak temperature of the highest melting peak was taken as the melting point (°C). The area of ​​the melting peak was taken as the heat of fusion (ΔHm), and the heat of fusion was determined by subtracting the baseline from the melting initiation temperature to the melting yield temperature.

[0097] [Weight Loss Rate] The weight loss rate was determined as an index of the thermal stability of the polyamide block copolymers obtained in the Examples and Comparative Examples by the following method. The polyamide block copolymers produced in the Examples and Comparative Examples were used as samples, and a thermogravimetric analyzer "TG / DTA7200" manufactured by SII Nanotechnology, Inc. was used. Specifically, the sample was left to stand in a 120°C dryer for 12 hours, and then heated from 25°C to 120°C at a rate of 80°C / min under a 100 mL nitrogen flow. The sample was then held at 120°C for 15 minutes, and then heated from 120°C to 300°C at a rate of 80°C / min and held at 300°C for 60 minutes. The weight loss rate was determined as the ratio of the weight lost during heating from 120°C to 300°C and holding at 300°C for 60 minutes to the weight after holding at 120°C for 15 minutes. A smaller weight loss rate indicated better thermal stability.

[0098] [Tensile Break Strength and Tensile Break Elongation] The polyamide block copolymers obtained in the examples and comparative examples were melt-kneaded for 3 minutes using a desktop compact kneader / injection molding machine ("Xplore MC15") manufactured by Xplore Instruments at a cylinder temperature 20°C higher than the melting point of the polyamide block copolymer. Then, small Type 1BA test pieces for tensile evaluation (2 mm thick, 75 mm total length, 5 mm parallel section width) were prepared under the conditions of a mold temperature of 140°C in the T-runner mold of the injection molding machine and an injection pressure of 1.0 bar. The obtained small Type 1BA test pieces of the polyamide block copolymer were left to stand in a dryer at 140°C for 6 hours, and then the tensile break strength and tensile break elongation were measured at 23°C using an Instron universal testing machine (Instron "Model 5566"). Specifically, the test speed was 0.25 mm / min in the strain range of 0 to 0.3% with a chuck distance of 50 mm, and then 50 mm / min in the strain range of 0.3% or more. The tensile elongation at break was measured using the nominal strain value according to Method A of JIS K 7161-1:2014.

[0099] <Materials> The materials used in the examples and comparative examples are as follows.

[0100] <Polymer Block (A)> PA-1 to PA-5 produced in the following Synthesis Example were used as components of polymer block (A). PA-6 produced in the following Synthesis Example was used as a component of non-semi-aromatic polyamide-containing polymer block (A'), which is a comparative object of polymer block (A).

[0101] Synthesis Example 1: Production of Semi-Aromatic Polyamide (PA-1) 1017.6 g (6.13 mol) of terephthalic acid, 988.2 g (6.24 mol) of a 50 / 50 molar mixture of 1,9-nonanediamine (C9DA in Table 3) and 2-methyl-1,8-octanediamine (MC8DA in Table 3), 18.2 g (0.15 mol) of benzoic acid as an end-capping agent, 2.0 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 788 mL of distilled water were placed in a 5 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the reaction was allowed to proceed while gradually releasing the water vapor. The reaction was continued for another hour to obtain a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and then pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-1." The semi-aromatic ratio (unit: %) is shown in Table 1.

[0102] Synthesis Example 2: Preparation of Semi-Aromatic Polyamide (PA-2) 983.0 g (5.92 mol) of terephthalic acid, 983.0 g (6.14 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 44.7 g (0.37 mol) of benzoic acid as an end-capping agent, 2.0 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 789 mL of distilled water were placed in a 5 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the water vapor was gradually released to allow the reaction. The reaction was allowed to continue for another hour, yielding a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-2." The semi-aromatic ratio is shown in Table 1.

[0103] Synthesis Example 3: Production of Semi-Aromatic Polyamide (PA-3) 732.7 g (4.41 mol) of terephthalic acid, 730.0 g (4.53 mol) of a mixture of 1,10-decanediamine (DDA in Table 3) and hexamethylenediamine (HMDA in Table 3) (molar ratio 80 / 20), 22.0 g (0.18 mol) of benzoic acid as an end-capping agent, 1.5 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 578 mL of distilled water were placed in a 5 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the water vapor was gradually released to allow the reaction. The reaction was allowed to continue for another 1 hour to obtain a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-3." The semi-aromatic ratio is shown in Table 1.

[0104] Synthesis Example 4: Preparation of Semi-Aromatic Polyamide (PA-4) 203.7 g (1.27 mol) of terephthalic acid, 197.5 g (1.25 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 6.0 g (0.03 mol) of lauric acid as an end-capping agent, 0.4 g (0.1% by mass relative to the total mass of the raw materials) of sodium hypophosphite monohydrate, and 158 mL of distilled water were placed in a 1 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the water vapor was gradually released to allow the reaction. The reaction was allowed to continue for another hour, yielding a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-4." The semi-aromatic ratio is shown in Table 1.

[0105] Synthesis Example 5: Preparation of Semi-Aromatic Polyamide (PA-5) 193.5 g (1.17 mol) of terephthalic acid, 8.96 g (0.06 mol) of adipic acid, 197.5 g (1.25 mol) of a 50 / 50 molar mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, 3.7 g (0.03 mol) of benzoic acid as an end-capping agent, 0.4 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 158 mL of distilled water were placed in a 1 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the water vapor was gradually released to allow the reaction. The reaction was allowed to continue for another hour, yielding a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-5." The semi-aromatic ratio is shown in Table 1.

[0106] Synthesis Example 6: Preparation of Aliphatic Polyamide (PA-6) as Non-Semi-Aromatic Polyamide 254.4 g (1.74 mol) of adipic acid, 280.5 g (1.77 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 5.2 g (0.04 mol) of benzoic acid as an end-capping agent, 0.5 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 210 mL of distilled water were placed in an autoclave with an internal volume of 1 L and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 3 hours. At this time, the pressure inside the autoclave rose to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the water vapor was gradually released to allow the reaction. The reaction was allowed to continue for another hour, yielding a prepolymer. The obtained prepolymer was dried at 120°C under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-6." The semi-aromatic ratio is shown in Table 1.

[0107] [Terminal Functionalizing Agent] The following dicarboxylic acid monomers were used as terminal functionalizing agents as components of polymer block (A) and polymer block (A'). It was confirmed that the terminal amino groups of the semi-aromatic polyamide were quantitatively converted to carboxyl groups by the terminal functionalizing agents (dicarboxylic acid monomers). Terephthalic acid (abbreviated as "TA" in Table 3): manufactured by Tokyo Chemical Industry Co., Ltd. Adipic acid (abbreviated as "AA" in Table 3): manufactured by Tokyo Chemical Industry Co., Ltd.

[0108] The various physical property evaluations described above were carried out for PA-1 to PA-6. The results are shown in Table 1 together with the physical properties of the terminal functionalizing agent. The notations in Table 1 are as follows. In the columns for PA-1, PA-2, and PA-4 to PA-6, "n / i" indicates the molar ratio of 1,9-nonanediamine / 2-methyl-1,8-octanediamine. In the column for PA-3, "n / i" indicates the molar ratio of 1,10-decanediamine / hexamethylenediamine. "[NH ２ ]" indicates the terminal amino group content. "[COOH]" indicates the terminal carboxyl group content.

[0109]

[0110] <Polymer Block (B)> The following oxygen atom-containing polymers were used as the polymer block (B): [Polyether] PE-1: Polyether diamine (diamine of polyethylene glycol and polypropylene glycol copolymer), manufactured by Sigma-Aldrich, Jeffamine (registered trademark) ED-900 PE-2: Polyether diamine (diamine of polyethylene glycol and polypropylene glycol copolymer), manufactured by Sigma-Aldrich, Jeffamine (registered trademark) ED-600 PE-3: Polyether diamine (polyoxytetramethylenediamine), manufactured by Koei Chemical Co., Ltd., PTMGPA-1000

[0111] The physical properties of the polymer block (B) are shown in Table 2. The notations in Table 2 are as follows: ２]" indicates the terminal amino group content. "Tg" indicates the glass transition temperature measured by the [Method for measuring glass transition temperature] described below. Note that "<-70" indicates that the glass transition temperature was below -70°C because an inflection point could not be confirmed in the range of -70°C or higher, which is the measurement limit of the instrument. In addition, the glass transition temperatures (based on literature values) of corresponding polyether diols are also shown in Table 2 as reference values. "-70" indicates a range of -80 to -60°C, and "-85" indicates a range of -95 to -75°C. [Method for measuring glass transition temperature] Each polymer block (B) was used as a sample, and the glass transition temperatures were measured using a differential scanning calorimeter "DSC25" manufactured by TA Instruments. The glass transition temperature (°C) was determined by cooling a sample from 25°C to -90°C at a rate of 2°C / min in a nitrogen atmosphere, holding the sample at -90°C for 10 minutes to completely cool the sample, and then heating the sample to 25°C at a rate of 2°C / min. The temperature at the inflection point that appeared when the sample was cooled was taken as the glass transition temperature.

[0112]

[0113] Example 1 The reaction was carried out using raw materials in the mass proportions shown in Table 3. A 200 mL flask equipped with a vacuum pump and an apparatus capable of distilling off generated volatile components was charged with "PA-1" from Synthesis Example 1 as polymer block (A) and terephthalic acid as a terminal functionalizing agent. The mixture was heated to a resin temperature of 280°C while stirring under a nitrogen stream of 200 mL / min, and maintained at this temperature for 30 minutes. Subsequently, "PE-1" was added as polymer block (B), and the mixture was stirred for an additional hour at a resin temperature of 280°C, after which the distillate was removed. Subsequently, the pressure of the reaction system was reduced to 10 Pa, and the mixture was stirred for an additional hour at a resin temperature of 280°C, after which the polyamide block copolymer was removed. To illustrate the mass ratio (A) / (B) shown in Table 3, in Example 1, 69 parts by mass (e.g., 68.7 g) of polyamide PA-1 functionalized with a terminal functionalizing agent was used relative to 31 parts by mass (e.g., 31.3 g) of polyether PE-1.

[0114] Examples 2 to 4, 6 to 7 The same procedure as in Example 1 was carried out except that the materials and mass ratios were changed as shown in Table 3, to obtain polyamide block copolymers.

[0115] Example 5 A polyamide block copolymer was obtained by the same procedure as in Example 1, except that the materials and mass ratios were changed to those shown in Table 3 and the resin temperature during polymerization was changed to 300°C.

[0116] Comparative Example 1 The reaction was carried out using raw materials in the mass ratios shown in Table 3. 588.6 g (3.54 mol) of terephthalic acid, 488.7 g (0.54 mol) of "PE-1," 285 mL of distilled water, and 1.6 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials) were placed in a 5 L glass beaker and stirred at room temperature until uniform. Subsequently, 474.8 g (3.00 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 50 / 50) and 204 mL of distilled water were added to the mixture, and stirring was continued. A uniform salt was then obtained from the reaction solution. The resulting salt was placed in a 5 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 245°C over 3 hours. At this time, the pressure inside the autoclave rose to 3.0 MPa. Heating was continued for 2 hours, followed by cooling. The reaction product was removed from the autoclave and dried at 120°C under reduced pressure for 24 hours, then pulverized to a particle size of 1 mm or less. 40 g of the pulverized product was transferred to a 200 mL flask and heated to a resin temperature of 300°C while stirring under a nitrogen stream of 200 mL / min. The reaction system was then decompressed to 10 Pa and stirred for 3 hours at a resin temperature of 300°C, after which the polyamide block copolymer was removed.

[0117] Comparative Example 2 A polyamide block copolymer was obtained by the same procedure as in Comparative Example 1, except that the materials and mass ratios were changed as shown in Table 3.

[0118] Comparative Example 3 A polyamide block copolymer was obtained by the same operation as in Example 1, except that the materials and mass ratios were changed to those shown in Table 3. While polymer block (A) was used in Example 1, in Comparative Example 3, a non-semi-aromatic polyamide-containing polymer block (A′) was used in place of polymer block (A).

[0119] The polyamide block copolymers obtained in the above Examples and Comparative Examples were evaluated for various physical properties. The results of the physical property evaluations are shown in Table 3.

[0120]

[0121] The results in Table 3 show that the polyamide block copolymers obtained in Examples 1 to 7 had excellent thermal stability. On the other hand, the polyamide block copolymers obtained in Comparative Examples 1 and 2 had molecular ends that were not blocked with a terminal blocking agent, resulting in inferior thermal stability compared to the Examples. The results in Table 3 show that the polyamide block copolymers obtained in Examples 1 to 7 had superior heat resistance compared to the polyamide block copolymer obtained in Comparative Example 3. It was also confirmed that the polyamide block copolymers obtained in Examples 1 to 7 were more usable under high-temperature conditions than the polyamide block copolymer obtained in Comparative Example 3. These results suggest that blocking the molecular ends of the polyamide block copolymer at a specific terminal blocking rate is important for achieving improved thermal stability.

[0122] The polyamide block copolymer of this embodiment has improved thermal stability compared to conventional polyamide block copolymers, and also has excellent heat resistance and flexibility. Therefore, the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as materials for various parts, such as electrical and electronic components, automotive parts, industrial material parts, industrial parts, daily necessities, clothing, household goods parts, sports parts, leisure parts, and medical parts. In particular, they can be used for complex-shaped parts manufactured by injection molding, hollow-molded parts manufactured by blow molding, hose- and tubular-shaped parts and films and sheets manufactured by extrusion molding, lightweight components and insulating materials manufactured by injection and / or extrusion foam molding, and as additives for modifying resins. They can also be used for foams manufactured by injection molding, blow molding, press molding, extrusion molding, calendar molding, vacuum molding, pressure molding, bead molding, or batch foam molding.

Claims

1. A polyamide block copolymer comprising a polymer block (A) containing 50 mol % or more of structural units derived from a semi-aromatic polyamide and a polymer block (B) having a glass transition temperature of 20°C or less, and having an end-capping rate of 10% or more.

2. The polyamide block copolymer according to claim 1, wherein the number average molecular weight of the polymer block (B) is 100 or more.

3. The polyamide block copolymer according to claim 1, wherein the polymer block (B) contains an oxygen atom in the main chain.

4. The polyamide block copolymer according to claim 3, wherein the polymer block (B) contains 50 mol % or more of structural units derived from a polyether polyol, an amine derivative thereof, or a carboxyl derivative thereof.

5. The polyamide block copolymer according to claim 1, having a tensile elongation at break of 30% or more as measured in accordance with JIS K 7161-1:2014.

6. The polyamide block copolymer according to claim 1, wherein the semi-aromatic polyamide comprises constitutional units derived from an aliphatic diamine having 4 or more carbon atoms and constitutional units derived from an aromatic dicarboxylic acid.

7. The polyamide block copolymer according to claim 1, wherein the molecular terminals are blocked with at least one selected from the group consisting of aryl groups, aromatic alkyl groups, alkyl groups having 1 to 3 carbon atoms, alkyl groups having 9 or more carbon atoms, alicyclic alkyl groups having 4 or more carbon atoms, and hydrogen atoms.

8. The polyamide block copolymer of claim 7, wherein the aryl group is a phenyl group or a naphthyl group.

9. The polyamide block copolymer of claim 7, wherein said aromatic alkyl group is a benzyl group.

10. The polyamide block copolymer according to claim 7, wherein the alkyl group having 1 to 3 carbon atoms is a methyl group or an ethyl group.

11. The polyamide block copolymer according to claim 7, wherein said alkyl group having 9 or more carbon atoms is a lauryl group or a stearyl group.

12. The polyamide block copolymer of claim 7, wherein said alicyclic alkyl group is a cyclohexyl group.

13. A polyamide block copolymer composition comprising the polyamide block copolymer of any one of claims 1 to 12.

14. A molded article formed from the polyamide block copolymer according to any one of claims 1 to 12.

15. A molded article formed from the polyamide block copolymer composition according to claim 13.