Polyamide block copolymer

Abstract

To provide a polyamide block copolymer with excellent heat resistance and flexibility.SOLUTION: Provided is a polyamide block copolymer containing: a polymer block (A) that contains at least 50 mol% of a structural unit derived from a polyamide; and a polymer block (B) that contains at least 50 mol% of a structural unit derived from at least one selected from the group consisting of polyethers and polyesters, wherein the polymer block (B) has a glass transition temperature of 20°C or lower and a melting point of 230°C or higher.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide block copolymer. [Background technology]

[0002] Thermoplastic elastomers can be melt-molded and are used in a wide range of fields, such as automobile interior and exterior parts, electronic equipment parts, 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 physical properties such as good mechanical strength, abrasion resistance, heat resistance, and oil resistance. For example, amide-based, urethane-based, and ester-based thermoplastic elastomers tend to exhibit relatively good heat resistance. However, in various fields, further improvements in physical properties depending on the application are required, and in order to meet this demand, efforts are being made to improve the physical properties of thermoplastic elastomers.

[0003] For example, Patent Document 1 discloses a polyamide block copolymer obtained by polymerizing dicarboxylic acid, diamine, and polyetherdiamine and / or polyetherdicarboxylic acid, with the aim of exhibiting excellent heat resistance and low-temperature properties. Patent Document 2 also discloses a polyether polyamide elastomer, in which the diamine structural units are derived from a polyetherdiamine compound (A-1) having a specific structure and xylylenediamine (A-2), and the dicarboxylic acid structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, with the aim of exhibiting excellent heat resistance, melt moldability, crystallinity, and flexibility. Patent Document 3 also discloses a copolymer of a hard polyamide block and a flexible polyether block or polyester block, with the aim of exhibiting excellent optical and mechanical properties. Patent Document 3 discloses that the polyamide block is semi-crystalline and consists of an X.X' / YZ type copolyamide, where (i) X.X' is an aliphatic diamine-diacid pair, (ii) Y is an alicyclic diamine, and (iii) Z is an aliphatic and / or aromatic dicarboxylic acid. Patent Document 4 also discloses a molding material containing a polyetheramide based on a linear aliphatic diamine having 6 to 12 carbon atoms, a linear aliphatic or aromatic dicarboxylic acid having 6 to 12 carbon atoms, and a polyetherdiamine, for the purpose of exhibiting thermoforming stability and hydrolysis stability. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-154248 [Patent Document 2] International Publication No. 2012 / 111636 [Patent Document 3] Special Publication No. 2020-519719 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-246926 Summary of the Invention [Problem to be solved by the invention]

[0005] The techniques disclosed in the above patent documents have some degree of excellent heat resistance, but are not satisfactory depending on the application, and there is room for improvement in heat resistance. Furthermore, there is a demand for polyamide block copolymers that have not only the excellent heat resistance of polyamide but also flexibility that enables molding processability and excellent tensile properties.

[0006] Therefore, an object of the present invention is to provide a polyamide block copolymer that is excellent in heat resistance and flexibility. [Means for solving the problem]

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

[0008] [1] A polymer block (A) containing 50 mol % or more of structural units derived from polyamide; and a polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters, The glass transition temperature of the polymer block (B) is 20°C or less, The melting point is 230°C or higher. Polyamide block copolymer. [2] The polyamide block copolymer according to [1] above, wherein the polyamide is a semi-aromatic polyamide. [3] The polyamide block copolymer according to [2] above, wherein the semi-aromatic polyamide contains diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units. [4] The polyamide block copolymer according to [2] or [3] above, wherein the semi-aromatic polyamide contains 30 mol% or more of diamine units derived from aliphatic diamines having 4 to 18 carbon atoms relative to the total diamine units. [5] The polyamide block copolymer according to any one of [2] to [4] above, wherein the semi-aromatic polyamide contains diamine units derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. [6] The polyamide block copolymer according to any one of [2] to [5] above, wherein the semi-aromatic polyamide contains dicarboxylic acid units 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. [7] The polyamide block copolymer according to any one of the above [1] to [6], wherein the polymer block (B) contains a structural unit derived from a polyetherdiamine. [8] The polyamide block copolymer according to any one of the above [1] to [7], wherein the polymer block (A) has an active terminal functional group content of 50 to 5,000 μmol / g. [9] The polyamide block copolymer according to any one of the above [1] to [8], wherein the polymer block (A) has a weight average molecular weight of 1,000 to 50,000.

[10] The polyamide block copolymer according to any one of the above [1] to [9], which has a weight average molecular weight of 40,000 to 200,000.

[11] The polyamide block copolymer according to any one of the above [1] to

[10] , which has a tensile elongation at break measured in accordance with JIS K 7161-1:2014 of 30% or more.

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

[11] .

[13] A molded article comprising the polyamide block copolymer according to any one of the above [1] to

[11] or the polyamide block copolymer composition according to the above

[12] .

[14] A method for producing the polyamide block copolymer according to the above item [1], comprising mixing and polymerizing a polymer constituting polymer block (A) containing 50 mol % or more of structural units derived from polyamide with a polymer constituting polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters. [Effects of the Invention]

[0009] According to the present invention, a polyamide block copolymer having excellent heat resistance and flexibility can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below based on an example of an embodiment, but the embodiment shown 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. In addition, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. When there are several numerical ranges for matters shown as numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. In this specification, when a numerical range is stated as "XX to YY", it 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, a "dicarboxylic acid unit" means "a structural unit derived from a dicarboxylic acid", and a "diamine unit" means "a structural unit derived from a diamine".

[0011] The polyamide block copolymer of this embodiment is The polyamide block copolymer is characterized by comprising a polymer block (A) containing 50 mol % or more of structural units derived from polyamide and a polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters, wherein the glass transition temperature of the polymer block (B) is 20°C or lower, and the melting point of the polyamide block copolymer is 230°C or higher.

[0012] The polyamide block copolymer of this embodiment is a copolymer containing a polyamide as the polymer block (A) and a polyether and / or polyester as the polymer block (B). The polyamide block copolymer of this embodiment contains a specific polyamide and a polyether and / or polyester as polymer blocks, and is therefore able to exhibit both the excellent heat resistance of polyamide and the excellent flexibility of polyether and / or polyester. On the other hand, for example, the polyamide block copolymer of Patent Document 1 does not provide sufficient heat resistance or mechanical strength. This is thought to be because the monomers and oligomers constituting the hard and soft segments are polymerized together, which does not result in the formation of polymer blocks sufficient to fully exhibit the respective physical properties of the hard and soft segments.

[0013] <Polymer block (A)> The polymer block (A) contains 50 mol % or more of structural units derived from polyamide. From the viewpoint of easily obtaining even better heat resistance, the polymer block (A) contains preferably 70 mol % or more, more preferably 90 mol % or more, and may contain 100 mol % of structural units derived from polyamide. In the polymer block (A), structural units other than the structural units derived from polyamide are not limited as long as the effects of the present invention can be obtained. The polyamide that can be used in this embodiment is not limited as long as it can obtain the effects of the present invention, and examples thereof include semi-aromatic polyamides, wholly aromatic polyamides, and aliphatic polyamides. Among them, semi-aromatic polyamides and aliphatic polyamides are polyamides that more significantly exhibit the effects of the present invention. From the viewpoint of more easily obtaining superior heat resistance, it is particularly preferable to use semi-aromatic polyamides as the polyamide. Examples of the aliphatic polyamide include polytetramethylene adipamide (polyamide 46) and polyhexamethylene adipamide (polyamide 66). Semi-aromatic polyamides that can be suitably used in this embodiment will be described in detail below.

[0014] [Semi-aromatic polyamide] The semi-aromatic polyamide refers to a polyamide containing diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, or a polyamide resin containing dicarboxylic acid units mainly composed of aliphatic dicarboxylic acid units and diamine units mainly composed of aromatic diamine units. Here, "mainly composed" means that the polyamide contains 50 to 100 mol %, preferably 60 to 100 mol %, of all units. In this embodiment, the semi-aromatic polyamide preferably contains diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, from the viewpoint of achieving better heat resistance.

[0015] (aliphatic diamine unit) 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 semi-aromatic polyamide preferably contains 30 mol% or more, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and may contain 100 mol% of diamine units derived from aliphatic diamines having 4 to 18 carbon atoms relative to the total diamine units. Furthermore, the aliphatic diamine used in the diamine unit is preferably an aliphatic diamine having 4 to 16 carbon atoms, more preferably an aliphatic diamine having 4 to 12 carbon atoms, even more preferably an aliphatic diamine having 6 to 12 carbon atoms, and even more preferably an aliphatic diamine having 6 to 10 carbon atoms.

[0016] 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 may be used alone or in combination of two or more. From the viewpoint of heat resistance, the aliphatic diamine is preferably at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines, and more preferably a combination of linear aliphatic diamines and branched aliphatic diamines.

[0017] From the viewpoint of more pronounced effect of the present invention and excellent raw material availability, the semi-aromatic polyamide preferably contains diamine units 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 diamine units derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. From the viewpoint of moldability, it is even more preferable to use both 1,9-nonanediamine and 2-methyl-1,8-octanediamine in combination. 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] 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. Only one type of structural unit derived from a diamine other than aliphatic diamines may be contained, or two or more types may be contained. The content of structural units derived from other than the above 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.

[0020] (aromatic dicarboxylic acid unit) Examples of the aromatic dicarboxylic acid unit include aromatic dicarboxylic acid 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, and the like, from the viewpoint that the polymerization reaction with diamine proceeds smoothly and is advantageous in improving physical properties such as heat resistance. In order to more significantly exhibit the effects of the present invention, the semi-aromatic polyamide preferably contains dicarboxylic acid units 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, and in order to further improve heat resistance, it is more preferable that the semi-aromatic polyamide contains dicarboxylic acid units 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.

[0021] From the viewpoint of heat resistance and mechanical strength, the content of dicarboxylic acid units derived from at least one selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid in the total amount of dicarboxylic acid units constituting the semi-aromatic polyamide is preferably 30 mol% or more, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and may even be 100 mol%.

[0022] Furthermore, the semi-aromatic polyamide may contain, as dicarboxylic acid units, structural units derived from other than aromatic dicarboxylic acids, such as aliphatic dicarboxylic acids, as long as the effects of the present invention are not impaired. Only one type of structural unit derived from other than aromatic dicarboxylic acids may be contained, or two or more types may be contained. 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, dodecanedicarboxylic acid, and dimethylmalonic acid; Branched aliphatic dicarboxylic acids such as 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and the like. The content of structural units derived from other than the aromatic dicarboxylic acids 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.

[0023] The content of the units derived from the aliphatic diamine having 4 to 18 carbon atoms 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 units derived from aromatic dicarboxylic acids relative to all constituent units constituting the semi-aromatic polyamide is preferably from 15 to 55 mol %, more preferably from 25 to 55 mol %. The total content of the units derived from the aliphatic diamine and aromatic dicarboxylic acid having 4 to 18 carbon atoms 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 be 90 mol% or more, or even 100 mol%.

[0024] (other building blocks) The semi-aromatic polyamide may contain other structural units in addition to the diamine unit and the dicarboxylic acid unit, such as a polycarboxylic acid unit, an aminocarboxylic acid unit, and a lactam unit, as long as the effects of the present invention are not impaired. Examples of the polycarboxylic acid unit include structural units derived from trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, etc. These polycarboxylic acid units can be contained to the extent that melt molding is possible. Examples of the aminocarboxylic acid unit 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, undecane lactam, lauryllactam, α-pyrrolidone, α-piperidone, and the like. The content of other structural units relative to all structural units constituting the semi-aromatic polyamide is preferably 30 mol % or less, and more preferably 10 mol % or less.

[0025] 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), 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), poly Examples include linonamethylene naphthalene dicarboxamide / poly(2-methyloctamethylene) naphthalene dicarboxamide copolymer (polyamide 9N / M8N), polydecamethylene terephthalamide (polyamide 10T), polyhexamethylene isophthalamide (polyamide 6I), a copolymer of polyamide 6I and polyamide 6T (polyamide 6I / 6T), a copolymer of polyamide 66, polyamide 6I and polyamide 6T (polyamide 66 / polyamide 6I / 6T), a copolymer of polyamide 6T and polyundecaneamide (polyamide 11) (polyamide 6T / 11), a copolymer of polyamide 6T and polyamide 10T (polyamide 6T / 10T), and a copolymer of polyamide 10T and polyundecaneamide (polyamide 11) (polyamide 10T / 11).

[0026] [End-capping agent] In this embodiment, the polyamide contained in the polymer block (A) may contain structural units derived from an end-capping agent. The content of the structural units derived from the terminal blocking agent is preferably 1.0 to 10 mol %, more preferably 2.0 to 7.5 mol %, and even more preferably 2.5 to 6.5 mol %, relative to the diamine units. The content of the structural units derived from the terminal blocking agent can be adjusted by the amount of terminal blocking agent charged relative to the diamine when charging the polymerization raw materials. Taking into consideration the volatilization of the monomer components during polymerization, it is desirable to finely adjust the amount of terminal blocking agent charged when charging the polymerization raw materials so that the desired amount of structural units derived from the terminal blocking agent is introduced into the resulting resin. Furthermore, when polymerizing the polymer constituting polymer block (A) and the polymer constituting polymer block (B), the terminal blocking agent can be charged so that the desired content is within the above-mentioned range. Furthermore, the terminal blocking agent can be charged to the polymer constituting polymer block (A) together with the terminal functionalizing agent described below so that the desired content is within the above-mentioned range.

[0027] As a method for determining the content of structural units derived from an end-capping agent in a polyamide, for example, as disclosed in JP-A-07-228690, the solution viscosity is measured, the total amount of end groups is calculated from the relational equation between the viscosity and the number average molecular weight, and the amount of amino groups and the amount of carboxyl groups determined by titration are subtracted from the total amount of end groups. As the terminal blocking 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 terminals, monocarboxylic acids are preferred as terminal blocking agents for terminal amino groups, and monoamines are preferred as terminal blocking agents for terminal carboxyl groups. From the viewpoints of ease of handling, monocarboxylic acids are more preferred as terminal blocking agents.

[0028] The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it is reactive with an amino group. Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric 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, methylnaphthalenecarboxylic acid, and phenylacetic acid; and mixtures thereof. Among these, at least one selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid is preferred in terms of reactivity, stability of the blocked terminal, cost, and the like.

[0029] The monoamine used as the terminal blocking agent is not particularly limited as long as it is reactive with a carboxyl group. Examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and mixtures thereof. Among these, at least one selected from butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferred in terms of reactivity, high boiling point, stability of the blocked terminal, and cost.

[0030] [Polyamide manufacturing method] When the polyamide is a semi-aromatic polyamide containing dicarboxylic acid units and diamine units, the semi-aromatic polyamide can be produced, for example, from dicarboxylic acid and diamine as raw materials by a method such as melt polymerization, solid-state polymerization, melt extrusion polymerization, etc. Specifically, the semi-aromatic polyamide can be produced as follows. First, a nylon salt is produced by mixing a diamine, a dicarboxylic acid, and, if necessary, an aminocarboxylic acid, a lactam, a catalyst, an end-capping agent, etc. Next, the produced nylon salt is heated to a temperature of 200 to 250°C for thermal polymerization, thereby obtaining a semi-aromatic polyamide as a prepolymer. Furthermore, the semi-aromatic polyamide can be adjusted to a desired molecular weight by subjecting the prepolymer to solid-state polymerization or by increasing the degree of polymerization using a melt extruder. When the high polymerization degree stage is carried out by solid-state polymerization, it is preferably carried out under reduced pressure or in an inert gas flow, and a polymerization temperature within the range of 200 to 280°C results in a high polymerization rate, excellent productivity, and effective suppression of coloration and gelation. Furthermore, when the high polymerization degree stage is carried out using a melt extruder, the polymerization temperature is preferably 370°C or lower, and polymerization under such conditions results in a semi-aromatic polyamide with almost no decomposition and minimal deterioration.

[0031] 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 the total mass (100% by 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. When the amount of catalyst used is equal to or greater than the lower limit, polymerization proceeds more smoothly.

[0032] [Terminal amino group content (before terminal conversion)] In this embodiment, the terminals of the polyamide can be adjusted to a desired functional group or amount of functional groups by using a terminal functionalizing agent described below. On the other hand, the terminal amino group content referred to here is the terminal amino group content in the polyamide before the terminals are converted with a terminal functionalizing agent. The polyamide before the above-mentioned terminal conversion has a terminal amino group content ([NH2]) of preferably 1 to 4,000 μmol / g, more preferably 1 to 3,000 μmol / g, even more preferably 1 to 2,500 μmol / g, and still more preferably 1 to 2,000 μmol / g. The terminal amino group content ([NH2]) referred to in this specification refers to the amount of terminal amino groups (unit: μmol) contained in 1 g of polyamide, and can be determined by neutralization titration using an indicator.

[0033] [Terminal carboxyl group content (before terminal conversion)] The polyamide before the above-mentioned terminal conversion has a terminal carboxyl group content ([COOH]) of preferably 1 to 5,000 μmol / g, more preferably 25 to 4,000 μmol / g, even more preferably 50 to 3,000 μmol / g, and still more preferably 75 to 2,500 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 polyamide, and can be determined by potentiometric titration.

[0034] [Melting point] The melting point of the polyamide is 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 polyamide is preferably 230°C or higher and 320°C or lower. In the present invention, the melting point can be determined as the peak temperature of a melting peak that appears when the temperature is raised 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.

[0035] [Molecular weight] 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 9,000, and still more preferably 400 to 8,000, and may be 400 to 7,000 or 400 to 6,000. 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 the 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 1,400 to 25,000 or 1,400 to 20,000. 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. 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.

[0036] [End-functionalizing agent] In this embodiment, a terminal functionalizing agent can be used to prepare polymer block (A) in which the terminals of the polyamide are adjusted to a desired functional group or amount of functional groups. For example, the polyamide terminals can be converted by reacting a terminal functionalizing agent with the above-mentioned polyamide prepolymer. Alternatively, the polyamide terminals can be converted by adding an excess of either dicarboxylic acid units or diamine units at the stage of charging the raw materials. By adjusting the terminals of polymer block (A) to the desired functional group or functional group amount, the polymer block (A) and polymer block (B) can be bonded more effectively. The units derived from the terminal functionalizing agent are included in polymer block (A).

[0037] When the polyamide obtained by the above-described method for producing a polyamide has the desired functional groups or the desired amount of functional groups, a terminal functionalizing agent does not need to be used. In other words, in this case, a polyamide block copolymer in which polymer block (A) and polymer block (B) are well bonded can be obtained by reacting the polyamide with at least one selected from the group consisting of polyethers and polyesters without using a terminal functionalizing agent. The amount of active terminal functional groups in the polyamide, which will be described later, can be adjusted, for example, by adjusting the amount of carboxyl groups and the amount of amino groups contained in the reaction raw materials in the production of the polyamide.

[0038] 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.

[0039] In this embodiment, it is preferable to use a dicarboxylic acid and a diamine as the terminal functionalizing agent. Dicarboxylic acids that can be used as end-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, dodecanedicarboxylic acid, and dimethylmalonic acid; Branched aliphatic dicarboxylic acids such as 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and the like. 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.

[0040] Diamines that can be used as end-functionalizing agents include aliphatic and aromatic diamines. Examples of aliphatic diamines include 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; and the like. Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, and 4,4'-methylenedi-2,6-diethylaniline. The terminal functionalizing agent may be used alone or in combination of two or more kinds.

[0041] (Active terminal functional group content) In the present invention, the "active terminal functional group content" refers to the content of the active terminal functional group of the polymer block (A) contained in the polyamide block copolymer, and the total content of the active terminal functional groups of the 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 of such groups include an amino group and a carboxyl group. When the terminals of a 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. For example, when a 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).

[0042] The active terminal functional group content of polymer block (A) is preferably 50 to 5,000 μmol / g, more preferably 75 to 4,500 μmol / g, even more preferably 100 to 4,000 μmol / g, and even more preferably 120 to 4,000 μmol / g. When the active terminal functional group content is 50 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, when 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 content of active terminal functional groups in this specification refers to the amount (unit: μmol) of active terminal functional groups contained in 1 g of polyamide (or polyamide after conversion when a terminal functionalizing agent is used), and can be determined by neutralization titration and potentiometric titration using an indicator. Specifically, it can be calculated by the method described in the Examples below.

[0043] <Polymer block (B)> The polymer block (B) contains 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters. From the viewpoint of easily obtaining even better flexibility, the polymer block (B) contains preferably 70 mol % or more, more preferably 90 mol % or more, and may contain 100 mol % of structural units derived from at least one selected from the group consisting of polyethers and polyesters. In the polymer block (B), there are no limitations on structural units other than the structural units derived from at least one selected from the group consisting of polyethers and polyesters, as long as the effects of the present invention can be obtained. The glass transition temperature of the polymer block (B) is not more than 20° C. 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 that the polyamide block copolymer is likely to exhibit excellent flexibility at room temperature. 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, the glass transition temperature can be a literature value or a manufacturer's measurement result.

[0044] [Polyether] Examples of polyethers that can be used include polyetherdiamines and polyetherdicarboxylic acids. Among them, polyetherdiamines are preferred because they are expected to impart superior flexibility to polyamide block copolymers having polymer block (A) as hard segments and to exhibit superior chemical resistance to the polyamide block copolymers. One or more types of polyethers can be used.

[0045] The polyether diamine may have amino groups at both ends of the polyether. Examples of polyetherdiamines 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 at both ends. These may be used alone or in combination. Such polyetherdiamines can be obtained, for example, by cyanoacetylation of polyetherdiol.

[0046] The polyether dicarboxylic acid may have carboxyl groups at both ends of the polyether. 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 polyether dicarboxylic acids having carboxyl groups at two ends of their copolymers. These may be used alone or in combination.

[0047] [polyester] Examples of polyester include aliphatic polyester, aromatic polyester, and copolymers thereof. The polyester may be one produced by polycondensation of a dicarboxylic acid and a diol. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. These may be used alone or in combination. Examples of diols include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; alicyclic diols other than 1,4-cyclohexanedimethanol, such as cyclohexanediol, hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and their alkylene oxide adducts having 2 to 4 carbon atoms (average addition molar number of 2 to 12); and aromatic diols such as hydroquinone, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, and 1,5-dihydroxynaphthalene. These may be used alone or in combination. Among polyesters, aliphatic polyesters are preferred from the viewpoint that they are expected to impart superior flexibility to polyamide block copolymers having polymer block (A) as hard segments and to further improve the heat resistance of the polyamide block copolymers.

[0048] From the viewpoint of easily imparting excellent flexibility to the polyamide block copolymer, the polymer block (B) preferably contains a structural unit derived from a polyether, and more preferably contains a structural unit derived from a polyetherdiamine.

[0049] [Molecular weight] The number average molecular weight of the polymer block (B) is preferably 200 to 5,000, more preferably 230 to 4,000, and even more preferably 300 to 2,000, and may be 350 to 1,500 or 350 to 1,000. Within the above numerical range, the polymerization reaction with the polymer block (A) proceeds smoothly, and the flexibility of the polyamide block copolymer can be further improved.

[0050] <Method of producing polyamide block copolymer> The method for producing a polyamide block copolymer of this embodiment is characterized by mixing and polymerizing a polymer constituting polymer block (A) containing 50 mol % or more of structural units derived from the above-mentioned polyamide and a polymer constituting polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of the above-mentioned polyethers and polyesters. The method for producing the polyamide block copolymer of this embodiment may also use the terminal functionalizing agent and / or the terminal capping agent. For example, the polyamide block copolymer can be produced by dry-blending the polymer constituting the polymer block (A) and the polymer constituting the polymer block (B) in the presence of the terminal functionalizing agent and / or the terminal capping agent, and then melt-kneading the resulting mixture. Alternatively, the semi-aromatic polyamide constituting the polymer block (A) may be reacted with the terminal functionalizing agent and / or the terminal capping agent, followed by pulverization to adjust the terminal functional groups of the polymer block (A). The polymer constituting the polymer block (B) may then be added and dry-blended, and the resulting mixture may be melt-kneaded. Furthermore, the semi-aromatic polyamide constituting the polymer block (A) may be reacted with the terminal functionalizing agent and / or the terminal capping agent through the upper hopper of a melt kneader, and then the polymer block (B) may be added through a side feed port downstream of the extruder to melt-knead the resulting mixture in a stepwise manner. Typically, methods such as melt polymerization, solid-state polymerization, and melt-extrusion polymerization can be used. Melt polymerization or melt-extrusion polymerization may be combined with solid-state polymerization. As the melt-extrusion polymerization, 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.

[0051] For example, when the monomer of the polymer constituting polymer block (A) is reacted with the polymer constituting polymer block (B) in the presence of a terminal functionalizing agent, it is difficult to produce the polyamide block copolymer of this embodiment. In this case, polymer block (A) is not completely formed and becomes a random copolymer, which makes it impossible to fully exhibit the physical properties exhibited by polymer block (A) and to impart excellent heat resistance.

[0052] <Mass ratio (A) / (B)> In the polyamide block copolymer of this embodiment, the mass ratio (A) / (B) of the polymer block (A) to the polymer block (B) is in the range of 1 / 99 to 99 / 1. If the mass ratio (A) / (B) is outside this range, the polyamide block copolymer cannot be imparted with excellent flexibility. From the viewpoint of achieving both heat resistance and flexibility, the mass ratio (A) / (B) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 95 / 5, and even more preferably 20 / 80 to 95 / 5, and may be 30 / 70 to 95 / 5, 40 / 60 to 95 / 5, 40 / 60 to 90 / 10, 45 / 55 to 90 / 10, or 50 / 50 to 90 / 10.

[0053] <Molecular weight of polyamide block copolymer> The number-average molecular weight of the polyamide block copolymer is preferably 3,000 to 40,000, more preferably 4,000 to 30,000, even more preferably 4,500 to 25,000, and even more preferably 5,000 to 20,000. The higher the molecular weight, the better the heat resistance, but the molding processability tends to be reduced. Within the above numerical range, the heat resistance of the polyamide block copolymer can be further improved and good molding processability can be expected. The weight-average molecular weight of the polyamide block copolymer is preferably 40,000 to 200,000, more preferably 43,000 to 200,000, even more preferably 45,000 to 200,000, and still more preferably 50,000 to 200,000, and may be 50,000 to 150,000. Within the above range, the polyamide block copolymer is expected to exhibit stronger material properties and have good moldability. 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. When the molecular weight distribution is within the above range, the heat resistance of the polyamide block copolymer can be further improved and good moldability can be expected.

[0054] <Physical properties> [Melting point] The melting point of the polyamide block copolymer is 230° C. or higher. If the melting point of the polyamide block copolymer is lower than 230° C., the heat resistance is poor. For example, a molded article obtained using the polyamide block copolymer may have insufficient thermal stability. The melting point of the polyamide block copolymer is preferably 235° C. or higher, more preferably 240° C. or higher. There is no particular upper limit to the melting point of the polyamide block copolymer, but from the viewpoint of moldability, etc., it is preferably 315° C. or lower.

[0055] [Tensile strength] The polyamide block copolymer of this embodiment has a tensile strength at break measured in accordance with JIS K 7161-1:2014 of preferably 5 MPa or more, more preferably 10 MPa or more, and even more preferably 15 MPa or more. In this specification, tensile properties are indicators of mechanical strength and flexibility. If the tensile strength at break is 5 MPa or more, the polyamide block copolymer can be said to have excellent mechanical strength. More specifically, the tensile breaking strength can be determined by the method described in the examples below.

[0056] [Tensile elongation at break] The polyamide block copolymer of this embodiment has a tensile elongation at break measured in accordance with JIS K 7161-1:2014 of preferably 30% or more, more preferably 50% or more, even more preferably 100% or more, and can also be 200% or more. In this specification, tensile properties are an index of flexibility. If the tensile elongation at break is 30% or more, the polyamide block copolymer can be said to have excellent flexibility. More specifically, the tensile elongation at break can be determined by the method described in the examples below.

[0057] [Polyamide block copolymer composition] In one embodiment of the present invention, a polyamide block copolymer composition containing the polyamide block copolymer can be provided. The polyamide block copolymer composition is produced by adding to the polyamide block copolymer other components, such as antioxidants, antiozonants, weather stabilizers, ultraviolet absorbers, hydrolysis-resistant stabilizers, fillers, crystal 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. Only one of these may be contained, or two or more of them may be contained. The content of the additives is not particularly limited as long as it does not impair the effects of the present invention, but can be 0.02 to 200 parts by mass per 100 parts by mass 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.

[0058] (Method of producing polyamide block copolymer composition) The method for producing the polyamide block copolymer composition is not particularly limited, and any method capable of uniformly mixing 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.

[0059] [Molded body] In one embodiment of the present invention, a molded article can be formed from the polyamide block copolymer or the polyamide block copolymer composition. The molded article of this embodiment can be used as various molded articles of any shape and for any purpose, such as electric and electronic parts, automobile parts, industrial parts, fibers, films, sheets, household goods, and the like.

[0060] <Application> The polyamide block copolymer and polyamide block copolymer composition of this embodiment exhibit flexibility and excellent heat resistance, and therefore can be used in a wide range of fields where these physical properties are required. For example, the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as various part materials, 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 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. More specifically, among electronic and electrical parts, it can be used as a material for hinges of mobile phones and game machines, camera grips, printer tractor belts, electrical wire coatings, tubes for home appliances, etc. 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 commodities and / or household goods, the material can be used as a material for hair dryer brushes, manicure cases, hot curlers, zipper pulls, bobbin cases, console shutters, corrugated tubes, corrugated hoses, etc. More specifically, the material can be used for sports parts such as running shoes, spiked shoes, and ski boots. More specifically, among medical components, the material can be used as a material for medical catheters, wearable devices, optical products, eye care components, etc. [Example]

[0061] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0062] <Measurement and evaluation methods> Various physical properties were measured or evaluated by the following methods.

[0063] [Molecular weight] The semi-aromatic polyamides produced in the Synthesis Examples and used as polymer block (A), 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), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) in terms of molecular weight converted into standard polymethyl methacrylate. A 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution prepared by dissolving 0.85 g of sodium trifluoroacetate in 1 kg of HFIP was used as the eluent. 1.5 mg of the sample, calculated as resin, was weighed and dissolved in 3 mL of the eluent. The solution was passed through a 0.4 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows: (Measurement conditions) Device: HLC-8320GPC (Tosoh Corporation) Column: Two TSK gel Super HM-H columns (manufactured by Tosoh Corporation) were connected in series. Eluent: 0.085% sodium trifluoroacetate / HFIP solution Flow rate: 0.5 mL / min (reference column: 0.25 mL / min) Sample injection volume: 30 μL Column temperature: 40℃ Standard polymethyl methacrylate: Showa Denko Shodex Standard M-75, Agilent Technologies Polymethlmethacrylate molecular weight 1010 and molecular weight 535 Detector: UV (254 nm) detector, UV (210 nm) detector

[0064] [Measurement of terminal amino group content ([NH2])] The semi-aromatic polyamide produced in the synthesis example was used 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. Titration was carried out using 0.01 or 0.1 N HCl aqueous solution with thymol blue as an indicator to measure the terminal amino group content ([NH], unit: μmol / g).

[0065] [Measurement of terminal carboxyl group content ([COOH])] The semi-aromatic polyamide prepared in the synthesis example was used 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 to measure the terminal carboxyl group content ([COOH], unit: μmol / g). (Measurement conditions) Measuring device: MCU-710M / S (Kyoto Electronics Manufacturing Co., Ltd.) Measurement unit: AT-710 Main control unit: MCU-710

[0066] [Active terminal functional group content] The active terminal functional group content of polymer block (A) was calculated from the amounts of each functional group [NH] and [COOH] of the semi-aromatic polyamide obtained from the above-mentioned measurements of the terminal amino group content and the terminal carboxyl group content, the parts by mass of the semi-aromatic polyamide ([parts by mass of PA]) shown in Table 3, and the parts by mass of the terminal functionalizing agent ([parts by mass of terminal functionalizing agent]) according to the following formula: It was confirmed that the terminal amino groups of the semi-aromatic polyamide were quantitatively converted to carboxyl groups by the terminal functionalizing agent (dicarboxylic acid monomer) described below. <formula>: Active terminal functional group content (μmol / g)= ([NH2] + [COOH]) × ([parts by mass of PA] ÷ ([parts by mass of PA] + [parts by mass of terminal functionalizing agent]))

[0067] [Melting point] The semi-aromatic 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 point was measured in accordance with ISO 11357-3 (2011, 2nd edition). Specifically, in a nitrogen atmosphere, a 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, 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).

[0068] [Evaluation of tensile strength and elongation at break] Tensile evaluation was carried out in the following manner. Small test pieces of type 1BA (2 mm thick) of the polyamide block copolymers obtained in the examples and comparative examples were left to stand in a dryer at 140°C for 6 hours, and then the tensile strength at break and the tensile elongation at break at 23°C were measured using an Instron universal testing machine (Instron Model 5566). Specifically, the chuck distance was 25 mm, and the test speed was 0.25 mm / min in the strain range of 0 to 0.3%, and then the test speed was 50 mm / min in the strain range of 0.3% or more. The tensile elongation at break was measured using the nominal strain value.

[0069] <Polymer block (A)> As the constituent elements of the polymer block (A), PA-1 to PA-9 produced in the following synthesis examples were used. [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 and 2-methyl-1,8-octanediamine, 18.2 g (0.15 mol) of benzoic acid, 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting prepolymer was dried at 120°C under reduced pressure for 24 hours and then crushed to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-1."

[0070] [Synthesis Example 2] Production of semi-aromatic polyamide (PA-2) 1015.6 g (6.11 mol) of terephthalic acid, 988.2 g (6.24 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 80 / 20), 21.2 g (0.17 mol) of benzoic acid, 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting prepolymer was dried at 120°C under reduced pressure for 24 hours and then crushed to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-2."

[0071] [Synthesis Example 3] Production of semi-aromatic polyamide (PA-3) 991.1 g (5.97 mol) of terephthalic acid, 972.3 g (6.14 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 85 / 15), 32.8 g (0.27 mol) of benzoic acid, 2.0 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 777 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting 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-3."

[0072] [Synthesis Example 4] Production of semi-aromatic polyamide (PA-4) 1116.4 g (6.72 mol) of terephthalic acid, 886.4 g (5.60 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 2.0 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 780 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting 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 was subjected to solid-state polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide, which is abbreviated as "PA-4."

[0073] [Synthesis Example 5] Production of semi-aromatic polyamide (PA-5) 1043.8 g (6.28 mol) of terephthalic acid, 965.5 g (6.10 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 2.0 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 782 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting 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 was subjected to solid-state polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide, which is abbreviated as "PA-5."

[0074] [Synthesis Example 6] Production of semi-aromatic polyamide (PA-6) 836.7 g (3.87 mol) of 2,6-naphthalenedicarboxylic acid, 637.6 g (4.03 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 85 / 15), 31.8 g (0.26 mol) of benzoic acid, 1.5 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 677 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting prepolymer was dried at 120°C under reduced pressure for 24 hours and then crushed to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-6."

[0075] [Synthesis Example 7] Production of semi-aromatic polyamide (PA-7) 732.7 g (4.41 mol) of terephthalic acid, 768.1 g (4.53 mol) of a mixture of 1,10-decanediamine and 2-methyl-1,8-octanediamine (molar ratio 80 / 20), 22.0 g (0.18 mol) of benzoic acid, 1.5 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 593 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting prepolymer was dried at 120°C under reduced pressure for 24 hours and then crushed to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-7."

[0076] [Synthesis Example 8] Production of semi-aromatic polyamide (PA-8) 732.7 g (4.41 mol) of terephthalic acid, 730.0 g (4.53 mol) of a mixture of 1,10-decanediamine / hexamethylenediamine (molar ratio 80 / 20), 22.0 g (0.18 mol) of benzoic acid, 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. During 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 water vapor was gradually released to allow the reaction. The reaction was continued for another hour to obtain a prepolymer. The resulting 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-8."

[0077] [Synthesis Example 9] Production of semi-aromatic polyamide (PA-9) The PA-8 obtained in Synthesis Example 8 was subjected to solid-state polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide. This polyamide is abbreviated as "PA-9."

[0078] [Monomer mixture] 39.9 g (0.24 mol) of terephthalic acid, 31.7 g (0.20 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 80 / 20), and 0.072 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials) were mixed and stirred. This mixture is referred to as the "monomer mixture."

[0079] [End-functionalizing agent] As a constituent element of the polymer block (A), the following dicarboxylic acid monomer was used as a terminal functionalizing agent. Adipic acid (abbreviated as "AA"): manufactured by Tokyo Chemical Industry Co., Ltd. Terephthalic acid (abbreviated as "TA"): manufactured by Tokyo Chemical Industry Co., Ltd.

[0080] The above-mentioned various physical property evaluations were carried out for PA-1 to 9. 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: "n / i" indicates the molar ratio of linear diamine units to branched diamine units. In the columns for PA-8 and PA-9, "n / i" indicates the molar ratio of 1,10-decanediamine to hexamethylenediamine. "[NH2]" indicates the terminal amino group content. "[COOH]" indicates the terminal carboxyl group content.

[0081] [Table 1]

[0082] <Polymer block (B)> The following was used as the polymer block (B). [Polyether] PE-1: Polyether diamine, manufactured by Sigma-Aldrich, Jeffamine® ED-600 PE-2: Polyether diamine, manufactured by Sigma-Aldrich, Jeffamine® ED-900 PE-3: Polyoxypropylenediamine, Sigma-Aldrich, D-400 PE-4: Polyoxyethylenediamine, manufactured by Koei Chemical Co., Ltd., PEGPA-400 PE-5: Polyoxyethylenediamine, manufactured by Koei Chemical Co., Ltd., PEGPA-1000 PE-6: Polyoxytetramethylenediamine, manufactured by Koei Chemical Co., Ltd., PTMGPA-1000

[0083] The physical properties of the polymer block (B) are shown in Table 2. The notations in Table 2 are as follows: "[NH2]" indicates the terminal amino group content. "Tg" indicates the glass transition temperature measured by the following [Method for measuring glass transition temperature]. Note that "<-70" indicates that the glass transition temperature is below -70°C, because an inflection point could not be confirmed above the instrument's measurement limit of -70°C. Additionally, the glass transition temperature (based on literature values) for polyether diol is listed as a reference value. "~-70" indicates a range between -80 and -60°C, and "~-85" indicates a range between -95 and -75°C. [Method for measuring glass transition temperature] The polymer block (B) was used as a sample, and the glass transition temperature thereof was measured using a differential scanning calorimeter "DSC25" manufactured by TA Instruments. The glass transition temperature (°C) was determined by cooling the sample from 25°C to -90°C at a rate of 2°C / min under a nitrogen atmosphere, holding it at -90°C for 10 minutes to allow the sample to cool completely, and then heating it again at a rate of 2°C / min to 25°C. The temperature at the inflection point that appeared when the temperature was increased was taken as the glass transition temperature.

[0084] [Table 2]

[0085] <Examples 1 to 16, Comparative Example 1> The components were mixed in advance in the ratios (parts by mass) shown in Table 3. For solid samples, mixing was performed by dry blending, and for liquid samples, mixing was performed by swelling the solid sample. 5–20 g of the prepared mixed sample was melt-mixed for 1–120 minutes using an Xplore Instruments compact mixer / injection molding machine ("Xplore MC15") at a cylinder temperature 0–60°C higher than the melting point of the polyamide. The extruded pellets were cooled and cut to produce polyamide block copolymer pellets. Tensile test specimens were prepared by melt-mixing the prepared mixed sample in the same manner as above, and then fabricating small Type 1BA test specimens (2 mm thick, 75 mm total length, 30 mm parallel length, 5 mm parallel width) using a T-runner mold in the injection molding machine at a mold temperature of 50–200°C and an injection pressure of 0.1–7.0 bar.

[0086] 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. The notations in Table 3 are as follows: "C9DA" refers to a 1,9-nonanediamine unit. "MC8DA" indicates a 2-methyl-1,8-octanediamine unit. "DDA" refers to a 1,10-decanediamine unit. "HMDA" refers to a hexamethylenediamine unit.

[0087] [Table 3]

[0088] The results in Table 3 show that the polyamide block copolymers obtained in Examples 1 to 16 had excellent heat resistance and flexibility. On the other hand, the polyamide block copolymer obtained in Comparative Example 1 was difficult to melt-process, had poor heat resistance, and was a hard and brittle material, so a tensile test could not be performed.

[0089] The results of Examples 8 to 12 and Comparative Example 1 show that when the molecular weight of the polymer block (A) is small, specifically when polymerization is carried out using a monomer mixture, the polymer block (A) exhibits poor melt processability with the polymer block (B), and the resulting polyamide block copolymer has a small molecular weight and is poor in heat resistance and flexibility.

[0090] From these results, it is clear that, in order to enable melt processing and further improve heat resistance and flexibility, it is important, as a particularly preferred embodiment of the present invention, that the polymer block (A) has a molecular weight of a certain level or more, that the polymer block (A) has a melting point of a certain level or less, and that the polymerization reaction temperature between the polymer block (A) and the polymer block (B) is carried out at a certain level or less. The polyamide block copolymer disclosed in Patent Document 1 uses a monomer mixture corresponding to that of Comparative Example 1, and the above results show that it is not preferable from the viewpoints of melt processability, heat resistance, and flexibility. [Industrial Applicability]

[0091] The polyamide block copolymer obtained by the reaction of polymer block (A) and polymer block (B) of this embodiment exhibits flexibility and excellent heat resistance. Therefore, the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as a material for various parts, such as electrical and electronic components, automobile parts, industrial material parts, industrial parts, daily necessities, household goods, 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 a resin-modifying additive.

Claims

1. a polymer block (A) containing 50 mol % or more of structural units derived from polyamide; and a polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters, the glass transition temperature of the polymer block (B) is 20°C or less, The polyamide block copolymer has a melting point of 230°C or higher, A polyamide block copolymer having a tensile elongation at break of 30% or more as measured in accordance with JIS K 7161-1:2014.

2. The polyamide block copolymer according to claim 1 , wherein the polyamide is a semi-aromatic polyamide.

3. The polyamide block copolymer according to claim 2 , wherein the semi-aromatic polyamide comprises diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units.

4. 4. The polyamide block copolymer according to claim 3, wherein the semi-aromatic polyamide contains 30 mol % or more of diamine units derived from aliphatic diamines having 4 to 18 carbon atoms relative to the total diamine units.

5. The polyamide block copolymer according to claim 2, wherein the semi-aromatic polyamide contains diamine units derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

6. The polyamide block copolymer according to claim 2, wherein the semi-aromatic polyamide contains dicarboxylic acid units 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.

7. The polyamide block copolymer according to claim 1 , wherein the polymer block (B) contains a structural unit derived from a polyetherdiamine.

8. 2. The polyamide block copolymer according to claim 1, wherein the polymer block (A) has an active terminal functional group content of 50 to 5,000 μmol / g.

9. 2. The polyamide block copolymer according to claim 1, wherein the polymer block (A) has a weight average molecular weight of 1,000 to 50,000.

10. 2. The polyamide block copolymer according to claim 1, having a weight average molecular weight of 40,000 to 200,000.

11. A polyamide block copolymer composition comprising the polyamide block copolymer according to any one of claims 1 to 10.

12. A molded article comprising the polyamide block copolymer according to any one of claims 1 to 10.

13. A molded body comprising the polyamide block copolymer composition of claim 11.

14. 2. The method for producing the polyamide block copolymer according to claim 1, comprising mixing and polymerizing a polymer constituting polymer block (A) containing 50 mol % or more of structural units derived from polyamide and a polymer constituting polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters.