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

Abstract

Provided is a polyamide block copolymer having a melting point of 230°C or higher and including: a polymer block (A) containing 50 mol% or more of a constituent unit derived from a polyamide; and a polymer block (B) having a glass transition temperature of 20°C or lower. On a temperature-loss tangent (tanδ) curve obtained for a test specimen, the temperature T0 (°C) at which the loss tangent in the temperature range of -100°C to 160°C reaches the maximum value tanδ (max) satisfies expression (1): -60°C ≤ T0 ≤ 120°C, and a first temperature T1 (°C), which is lower than the temperature T0 and at which the loss tangent is half the value of the maximum value tanδ (max), and a second temperature T2 (°C), which is higher than the temperature T0 and at which the loss tangent is half the value of the maximum value tanδ (max), satisfy expression (2): (T2-T1) ≤ 170.

Description

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

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

[0002] Thermoplastic elastomers can be melt-molded 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. 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.

[0003] For example, Patent Document 1 aims to provide an improved polyamide copolymer or polyamide elastomer (paragraph

[0016] ), and discloses a transparent polyamide elastomer containing alkyl-substituted bis(aminocyclohexyl)methane and / or bis(aminocyclohexyl)propane as a polyamide segment (claim 1).

[0004] Patent Document 2 relates to a heat-resistant polyether polyamide elastomer (paragraph

[0008] ). Patent Document 2 discloses a diamine structural unit containing an isopropenylene group (-CH(CH ３ ) CH ２ - or -CH ２ CH (CH ３ )-) and xylylenediamine, and a polyether polyamide elastomer using an α,ω-linear aliphatic dicarboxylic acid having 8 to 20 carbon atoms as a dicarboxylic acid constituent unit (Claim 1, paragraph

[0020] ).

[0005] Patent Publication No. 2010-534256 International Publication No. 2013 / 105607

[0006] Although the techniques disclosed in the above patent documents provide polyamide block copolymers with excellent physical properties, further improvements in physical properties may be required depending on the application, and there is room for improvement. Furthermore, the above patent documents do not disclose the influence of dynamic viscoelasticity and tensile properties on the various physical properties. Polyamide block copolymers with an excellent balance between strength and flexibility are still desired.

[0007] Therefore, an object of the present invention is to provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article, which have an excellent balance of strength and flexibility. Other objects of the present invention will be apparent to those skilled in the art upon reading this specification.

[0008] 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.

[0009] [1] A polyamide block copolymer having a melting point of 230°C or higher, comprising a polymer block (A) containing 50 mol% or more of structural units derived from polyamide, and a polymer block (B) having a glass transition temperature of 20°C or lower, wherein a temperature-loss tangent (tanδ) curve obtained by measuring a test piece having a length of 20 mm, a width of 5 mm, and a thickness of 100 μm using a viscoelasticity measuring device at a chuck distance of 10 mm, a frequency of 1 Hz, and a heating rate of 3°C / min in a temperature range of -100°C to 330°C satisfies the following formula (1): [1] -60°C≦T0≦120°C; and A polyamide block copolymer, wherein a first temperature T1 [°C] lower than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), and a second temperature T2 [°C] higher than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), satisfy the relationship of the following formula (2): Formula (2): (T2-T1)≦170. [2] The polyamide block copolymer according to [1], wherein the polyamide is a semi-aromatic polyamide. [3] The polyamide block copolymer according to [2], wherein the semi-aromatic polyamide contains diamine units mainly composed of structural units derived from an aliphatic diamine and dicarboxylic acid units mainly composed of structural units derived from an aromatic dicarboxylic acid. [4] The polyamide block copolymer according to [3], wherein the semi-aromatic polyamide contains diamine units derived from an aliphatic diamine having 4 to 18 carbon atoms in an amount of 30 mol % or more relative to all diamine units. [5] The polyamide block copolymer according to [3] or [4], wherein the aliphatic diamine contains structural units derived from at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines. [6] The polyamide block copolymer according to any one of [1] to [5], wherein the polyamide contains structural units derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.[7] The polyamide block copolymer according to any one of [3] to [5], wherein the aromatic dicarboxylic acid comprises structural 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. [8] The polyamide block copolymer according to any one of [1] to [7], wherein the polymer block (A) comprises structural units derived from the polyamide and structural units derived from a compound selected from the group consisting of a dicarboxylic acid and a diamine. [9] The polyamide block copolymer according to any one of [1] to [8], wherein the polymer block (B) comprises structural units derived from a polyether polyol, a polyester polyol, a polycarbonate polyol, a polysiloxane polyol, or an amine derivative or a carboxyl derivative thereof.

[10] The polyamide block copolymer according to any one of [1] to [9], wherein the number average molecular weight of the polyamide block copolymer is 50,000 or less.

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

[10] , wherein the polyamide block copolymer has a weight average molecular weight of 500,000 or less.

[12] The polyamide block copolymer according to any one of [1] to

[11] , wherein the polyamide block copolymer has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.0 to 14.5.

[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] .

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

[13] .

[0010] According to the present invention, it is possible to provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article that have an excellent balance between strength and flexibility.

[0011] 1 is a graph of a temperature-loss tangent curve obtained by measuring a test piece of the polyamide block copolymer of Example 1.

[0012] 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."

[0013] <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 polyamide and a polymer block (B) having a glass transition temperature of 20°C or lower, and has a melting point of 230°C or higher. The polyamide block copolymer of this embodiment has a temperature-loss tangent (tan δ) curve obtained by viscoelasticity measurement with a specific shape. The polyamide block copolymer of this embodiment has an excellent balance between strength and flexibility due to the specific shape of the temperature-loss tangent curve. In addition, in the polyamide block copolymer of this embodiment, the polymer block (A) is a hard segment and the polymer block (B) is a soft segment, allowing the properties of each polymer block to be fully exhibited.

[0014] <Melting Point (Tm)> The melting point (Tm) of the polyamide block copolymer of this embodiment is the peak temperature [°C] of the melting peak measured using a differential scanning calorimeter in accordance with ISO 11357-3 (2011, 2nd edition). Such differential scanning calorimetry can be performed in more detail by the method described in the Examples.

[0015] The polyamide block copolymer has sufficient heat resistance when its Tm is 230° C. or higher, preferably 231° C. or higher, more preferably 232° C. or higher, and even more preferably 233° C. or higher. From the viewpoint of moldability, the Tm is preferably 320° C. or lower.

[0016] <Temperature-Loss Tangent Curve> Specifically, in the polyamide block copolymer of this embodiment, in the temperature-loss tangent curve, the temperature T0 [°C] at which the loss tangent in the temperature range of -100°C to 160°C is the maximum value tan δ(max) satisfies the following formula (1): Formula (1): -60°C≦T0≦120°C, and a first temperature T1 [°C] that is lower than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), and a second temperature T2 [°C] that is higher than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), satisfy the following formula (2): Formula (2): (T2-T1)≦170.

[0017] The temperature-loss tangent curve is obtained by measuring a test piece having a length of 20 mm, a width of 5 mm, and a thickness of 100 μm using a viscoelasticity measuring device at a chuck distance of 10 mm, a frequency of 1 Hz, and a heating rate of 3°C / min in the temperature range of -100°C to 330°C. Such dynamic viscoelasticity measurement can be performed in more detail by the method described in the Examples. The test piece may be obtained by molding an unmolded polyamide block copolymer, or by cutting it out of a molded product of the polyamide block copolymer. To obtain a test piece by molding an unmolded polyamide block copolymer, more specifically, the method described in the Examples is preferably used. Even when the test piece is obtained by cutting it out of a molded product of the polyamide block copolymer, dynamic viscoelasticity measurement can be performed in the method described in the Examples.

[0018] <Temperature T0 Range: Formula (1)> As described above, the polyamide block copolymer of this embodiment has a temperature T0 of -60°C or higher and 120°C or lower (Formula (1)). Temperature T0 is the temperature at which the loss tangent value reaches a maximum value tanδ(max) in the temperature range of -100°C to 160°C on the temperature-loss tangent curve. When multiple peaks exist in the temperature range of -100°C to 160°C on the temperature-loss tangent curve, the maximum value tanδ(max) is the value of the loss tangent at the peak top of the maximum peak, and temperature T0 is the temperature at the peak top of the maximum peak.

[0019] The T0 of the polyamide block copolymer may be −55° C. or higher, −50° C. or higher, more preferably −45° C. or higher, or −40° C. or higher, and in some cases may be −35° C. or higher. The T0 of the polyamide block copolymer may be 115° C. or lower, 110° C. or lower, 105° C. or lower, or 100° C. or lower, and in some cases may be 95° C. or lower, 90° C. or lower, or 85° C. or lower. Preferred ranges for the temperature T0 are, for example, −55° C. to 120° C., −50° C. to 120° C., −45° C. to 120° C., −40° C. to 120° C., −60° C. to 115° C., −60° C. to 110° C., −55° C. to 115° C., −50° C. to 110° C., −45° C. to 100° C., or −40° C. to 100° C.

[0020] <Range of Temperature Width (T2-T1): Formula (2)> As described above, the polyamide block copolymer of this embodiment has a temperature width (T2-T1) of 170°C or less (Formula (2)). The first temperature T1 and the second temperature T2 are temperatures that indicate half of the maximum value tan δ (max) on the temperature-loss tangent curve. Note that, depending on the shape of the temperature-loss tangent curve, there may be multiple candidates for the first temperature and / or the second temperature. In such cases, the temperatures closest to T0 are used as the first temperature T1 and the second temperature T2.

[0021] The temperature range (T2-T1) for the polyamide block copolymer is preferably 160°C or less, more preferably 150°C or less, even more preferably 140°C or less or 130°C or less, and may be 120°C or less in some cases. The temperature range (T2-T1) may be, for example, 5°C or more, 10°C or more, or 15°C or more. From the viewpoint of the balance between strength and flexibility, the temperature range (T2-T1) is preferably 45°C or more, 50°C or more, or 60°C or more.

[0022] <Peaks of Temperature-Loss Tangent Curve> The temperature-loss tangent curve of the polyamide block copolymer of this embodiment will be described using FIG. 1 as an example. FIG. 1 is a graph of the temperature-loss tangent curve obtained when dynamic viscoelasticity measurement was performed on the polyamide block copolymer of Example 1 described below. As shown in FIG. 1, the temperature-loss tangent curve shows two maximum values ​​for the loss tangent in the temperature range of -100°C to 160°C. That is, the temperature-loss tangent curve shown in FIG. 1 has two peaks in the temperature range of -100°C to 160°C.

[0023] As a result of research by the present inventors, it was found that the temperature-loss tangent curve of a polyamide block copolymer containing a hard segment and a soft segment generally tends to have at least two peaks, as shown in Figure 1. One of the two peaks is a peak on the low temperature side, and the other is a peak on the high temperature side.

[0024] In the present invention, when the temperature-loss tangent curve of a polyamide block copolymer has two peaks, a low-temperature peak and a high-temperature peak, the peak with the larger loss tangent value at the peak top satisfies the above formulas (1) and (2). In other words, when dynamic viscoelasticity measurement is performed on a polyamide block copolymer containing hard segments and soft segments, if a temperature-loss tangent curve having peaks that satisfy both formula (1) and formula (2) is obtained, it can be said that the copolymer has an excellent balance of strength and flexibility.

[0025] The reason why polyamide block copolymers that provide a temperature-loss tangent curve with peaks that satisfy both the above formula (1) and the above formula (2) have an excellent balance of strength and flexibility is not fully understood. Here, in the polyamide block copolymer of this embodiment, the peak with the larger loss tangent value at the peak top, preferably the higher-temperature peak, derived from the hard segment polymer block (A) tends to satisfy both the above formula (1) and the above formula (2). This is thought to maintain the strength and other properties expected of the hard segment and allow the soft segment to fully exhibit its flexibility and other properties, resulting in an excellent balance of strength and flexibility. Additionally, although the balance between strength and flexibility can be evaluated from the perspectives of strength at break and elongation at critical point, it is thought that evaluating it from the perspectives of dynamic viscoelasticity and fracture energy will more reliably result in a polyamide block copolymer with an excellent balance of strength and flexibility.

[0026] <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.

[0027] The polyamides that can be used in this embodiment are not limited as long as they can achieve a melting point of 230°C or higher and can achieve the effects of the present invention. Examples include semi-aromatic polyamides, fully aromatic polyamides, and aliphatic polyamides. Among these, semi-aromatic polyamides and aliphatic polyamides are polyamides that more significantly exhibit the effects of the present invention. From the viewpoint of more readily achieving superior heat resistance, it is particularly preferable to use semi-aromatic polyamides as the polyamide. Examples of the aliphatic polyamides include polytetramethylene adipamide (polyamide 46) and polyhexamethylene adipamide (polyamide 66). Semi-aromatic polyamides that can be suitably used in this embodiment are described in detail below.

[0028] Semi-aromatic polyamide refers to a polyamide resin 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 this embodiment, from the viewpoint of more excellent 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.

[0029] 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 %).

[0030] [Aliphatic diamine unit] The aliphatic diamine used in the aliphatic 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 of smoothly proceeding the polymerization reaction with dicarboxylic acid and being advantageous in improving physical properties such as heat resistance and flexibility, the content of structural units derived from aliphatic diamines having 4 to 18 carbon atoms relative to all diamine 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%, or even 100 mol%.

[0031] 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 included. These may be used alone or in combination of two or more.

[0032] 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. That is, the semi-aromatic polyamide preferably contains diamine units mainly composed of structural units derived from at least one aliphatic diamine selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines, and dicarboxylic acid units mainly composed of structural units derived from aromatic dicarboxylic acids, and more preferably contains diamine units mainly composed of structural units derived from linear aliphatic diamines and branched aliphatic diamines, and dicarboxylic acid units mainly composed of structural units derived from aromatic dicarboxylic acids.

[0033] 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, and even more preferably 85:15 to 15:85, and the above molar ratio may also be 80:20 to 20:80, 70:30 to 30:70, or 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.

[0034] Furthermore, from the viewpoint of more significantly achieving the effects of the present invention and excellent raw material availability, the semi-aromatic polyamide preferably contains structural units derived from at least one aliphatic diamine 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, more preferably contains structural units derived from at least one aliphatic diamine selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine, and even more preferably contains structural units derived from at least one aliphatic diamine selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. Among these, it is even 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.

[0035] 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.

[0036] 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, and even more preferably 85:15 to 15:85, and the above molar ratio may also be 80:20 to 20:80, 70:30 to 30:70, or 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.

[0037] 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%.

[0038] 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.

[0039] 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.

[0040] [Aromatic Dicarboxylic Acid Unit] Examples of aromatic dicarboxylic acids used in the aromatic dicarboxylic acid unit include 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, and diphenylsulfone-4,4'-dicarboxylic acid. These aromatic dicarboxylic acids may be used alone or in combination of two or more. From the viewpoints of smoothly proceeding the polymerization reaction with the diamine and advantageously improving physical properties such as heat resistance, the aromatic dicarboxylic acid preferably contains a structural unit derived from at least one aromatic dicarboxylic acid 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 aromatic dicarboxylic acid selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid.

[0041] From the viewpoint of heat resistance and mechanical strength, the content of structural units derived from at least one aromatic dicarboxylic acid 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%.

[0042] 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.

[0043] (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%.

[0044] [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.

[0045] [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).

[0046] [End-capping Agent] In this embodiment, the polymer block (A), preferably the polyamide contained in the polymer block (A), more preferably the semi-aromatic polyamide contained in the polymer block (A), may or may not contain structural units derived from a terminal-capping agent. The content of the structural units derived from the terminal-capping agent, relative to the diamine units, is preferably 0 mol% or more and 10 mol% or less, more preferably more than 0 mol% and 10 mol% or less, even more preferably 1.0 to 10 mol%, even more preferably 2.0 to 7.5 mol%, and even more preferably 2.5 to 6.5 mol%. The content of the structural units derived from the terminal-capping agent can be adjusted by the amount of terminal-capping agent charged relative to the diamine when charging the polymerization raw materials. Note that, taking into account the volatilization of the monomer components during polymerization, it is desirable to fine-tune the amount of terminal-capping agent charged when charging the polymerization raw materials so that the desired amount of structural units derived from the terminal-capping agent is introduced into the resulting polyamide. Furthermore, when polymerizing the polymer constituting the polymer block (A) and the polymer constituting the polymer block (B), the terminal-capping agent can be charged so that the amount falls within the desired range. Furthermore, a terminal capping agent may be added to the polymer constituting the polymer block (A) together with a terminal functionalizing agent described below so that the amount falls within the above-mentioned desired range.

[0047] One method for determining the content of structural units derived from a terminal blocking agent in a polyamide is, for example, as disclosed in JP-A-07-228690, which involves measuring the solution viscosity, calculating the total amount of terminal groups from the relationship between this and the number average molecular weight, and then subtracting the amount of amino groups and the amount of carboxyl groups determined by titration. Monofunctional compounds reactive with terminal amino groups or terminal carboxyl groups can be used as terminal blocking agents. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the standpoints 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 standpoint of ease of handling, monocarboxylic acids are more preferred as terminal blocking agents.

[0048] 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, decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, behenic 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, and methylnaphthalenecarboxylic acid; monocarboxylic acids having an aromatic alkyl group such as phenylacetic acid; and mixtures thereof. Among these, 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 in terms of reactivity, stability of the blocked terminal, cost, and the like.

[0049] 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, dodecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; 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, high boiling point, stability of the blocked terminal, and cost.

[0050] [Method for Producing Polyamide] Polyamide can be produced, for example, by melt polymerization, solid-state polymerization, melt extrusion polymerization, or other methods using dicarboxylic acid and diamine as raw materials. Specifically, polyamide can be produced as follows. First, a diamine, a dicarboxylic acid, and optionally an aminocarboxylic acid, a lactam, a catalyst, an end-capping agent, and the like are mixed to produce a nylon salt. Next, the resulting nylon salt is heated to a temperature of 200 to 250°C and thermally polymerized to obtain a polyamide prepolymer. Furthermore, the 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, polyamide is obtained with almost no decomposition and little deterioration.

[0051] Examples of catalysts that can be used in producing 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 polyamide raw materials. 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.

[0052] [Terminal Amino Group Content (Before Terminal Conversion)] In this embodiment, the terminals of the 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 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, and still more preferably 1 to 1,000 μmol / g. ２ ]) indicates the amount of terminal amino groups (unit: μmol) contained in 1 g of polyamide, and can be determined by neutralization titration using an indicator.

[0053] [Terminal Carboxyl Group Content (Before Terminal Conversion)] The terminal carboxyl group content ([COOH]) of the 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, even more preferably 75 to 2,000 μmol / g, and even more preferably 75 to 1,500 μmol / g. The terminal carboxyl group content ([COOH]) referred to herein refers to the amount of terminal carboxyl groups (unit: μmol) contained in 1 g of polyamide, and can be determined by potentiometric titration.

[0054] [Melting Point] The melting point of the polyamide is preferably 120°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, even more preferably 205°C or higher, even more preferably 210°C or higher, even more preferably 230°C or higher, even more preferably 240°C or higher, and even more preferably 250°C or higher. If the melting point of the polyamide is 120°C or higher, the heat resistance and mechanical properties of the polyamide block copolymer tend to be good. Furthermore, if the melting point of the polyamide is 230°C or higher, the heat resistance of the polyamide block copolymer is easily further 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 120 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.

[0055] [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%.

[0056] 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 balance between strength and flexibility tends to be even better. 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, even more preferably 1,400 to 30,000, 1,600 to 25,000, or even 2,000 to 20,000. Within the above numerical ranges, the compatibility between polymer block (A) and polymer block (B) tends to be excellent, and the balance between strength and flexibility tends to be even better. The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of polymer block (A) is preferably 1.5 to 10.0, more preferably 1.7 to 8.0, even more preferably 1.8 to 6.0, still more preferably 2.0 to 5.0, and even more preferably 2.0 to 4.0. Within the above numerical ranges, the compatibility between polymer block (A) and polymer block (B) tends to be excellent, and the balance between strength and flexibility tends to be even better. In the present invention, the number-average molecular weight and the 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.

[0057] [Terminal Functionalizing Agent] In this embodiment, a terminal functionalizing agent can be used to adjust the terminal of the polymer block (A), preferably the terminal of the polyamide, and more preferably the terminal of the semi-aromatic polyamide, to the desired functional group or amount of functional groups. For example, the terminal of the polyamide can be converted by reacting the terminal functionalizing agent with the above-mentioned polyamide prepolymer. Alternatively, the terminal 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 terminal 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 unit derived from the terminal functionalizing agent is included in the polymer block (A).

[0058] If the polyamide has the desired functional group or amount of functional groups, a terminal functionalizing agent need not be used. That is, in this case, the polymer constituting the polymer block (A) and the polymer constituting the polymer block (B) are reacted without using a terminal functionalizing agent, thereby enabling the polymer block (A) and the polymer block (B) to be bonded well to each other. The amount of active terminal functional groups of the polyamide, which will be described later, can be adjusted, for example, by adjusting the amount of carboxyl groups and amino groups contained in the reaction raw materials during the production of the polyamide.

[0059] 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.

[0060] In this embodiment, the terminal functionalizing agent is preferably a compound selected from the group consisting of dicarboxylic acids and diamines. 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. Examples of dicarboxylic acids that can be used as the terminal functionalizing agent include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. From the viewpoint of increasing the strength of the polyamide block copolymer, it is preferable to use an aromatic dicarboxylic acid as the terminal functionalizing agent. From the viewpoint of increasing the flexibility of the polyamide block copolymer, it is preferable to use an aliphatic dicarboxylic acid as the terminal functionalizing agent. 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.

[0061] 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.

[0062] (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 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 reactive activity with the terminal functional group of the polymer block (B), and examples thereof include an amino group and a carboxyl group. When the terminal of the polyamide is converted using a terminal functionalizing agent, the "active terminal functional group content" refers to the content of the active terminal functional group after the conversion of the terminal functional group. 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).

[0063] 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 4,000 μmol / g, still more preferably 200 to 4,000 μmol / g, still more preferably 250 to 4,000 μmol / g, and still more preferably 300 to 4,000 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.

[0064] <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 20°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.

[0065] [Polymer Units] Examples of structural units derived from the polymer constituting the polymer block (B) include polyethers, polyesters, polycarbonates, polysiloxanes, etc., and preferably oxygen-atom-containing polymers (hereinafter referred to as "oxygen-atom-containing polymers") containing oxygen atoms in structural units derived from the polymer. Details of polyethers, polyesters, polycarbonates, and polysiloxanes will be described later. The oxygen-atom-containing polymer preferably contains oxygen atoms in the main chain. The polymer block (B) more effectively contributes to the development of flexibility by containing oxygen atoms, preferably ether bonds, in the main chain. From the viewpoint of easily achieving excellent flexibility in the polyamide block copolymer, the content of structural units 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%. The content of structural units derived from the oxygen-atom-containing polymer in the polymer block (B) may be 100 mol% or less. That is, the content of structural units derived from the oxygen atom-containing polymer in the polymer block (B) is preferably 50 to 100 mol %.

[0066] Among the above oxygen atom-containing polymers, polyethers are preferred from the viewpoint of easily imparting excellent flexibility. In the polymer block (B), there are no limitations on the constituent units other than the constituent units derived from the oxygen atom-containing polymer, as long as the effects of the present invention can be obtained.

[0067] Furthermore, polymer block (B) preferably contains 50 mol% or more of structural units derived from a polymer having an amino group or a carboxyl group as a terminal group. Polymer block (B) preferably contains 50 mol% or more of structural units derived from a polymer having an amino group or a carboxyl group as a terminal group from the viewpoint of reactivity with polymer block (A). From the viewpoint of reactivity, the content of structural units derived from a polymer having an amino group or a carboxyl group as a terminal group in polymer block (B) is more preferably 70 mol% or more, even more preferably 90 mol% or more, and may even be 100 mol%. Furthermore, the content of structural units derived from a polymer having an amino group or a carboxyl group as a terminal group in polymer block (B) may be 100 mol% or less. That is, the content of structural units derived from a polymer having an amino group or a carboxyl group as a terminal group in polymer block (B) is preferably 50 to 100 mol%. In the polymer block (B), the constituent units other than the constituent units derived from the polymer having an amino group or a carboxyl group as a terminal group are not limited as long as the effects of the present invention can be obtained.

[0068] <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.

[0069] Examples of polyether amine derivatives and carboxyl derivatives include polyetherdiamines and polyetherdicarboxylic acids. Among these, polyetherdiamines 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 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 the like, as well as polyetherdiamines having amino groups at two ends of their copolymers. These may be used alone or in combination. Such polyetherdiamines can be obtained, for example, by cyanoacetylation of polyetherdiol.

[0070] 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 of two or more.

[0071] <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), poly(methylvalerolactone), poly(butylene adipate), poly(ethylene adipate), poly(methylpentanediol adipate), and poly(butylene-1,4-hexanediol-1,6-adipate). One or more types of these can be used.

[0072] 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.

[0073] 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.

[0074] <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) and polytetrahydrofuran carbonate. These can be used alone or in combination.

[0075] Furthermore, examples of polycarbonate polyols that can be used include those produced by the esterification reaction of a carbonate ester with a polyhydric alcohol, and those produced by an interfacial polycondensation method in which a polyhydric alcohol is reacted with phosgene. One or more types of polycarbonate polyols can be used. Examples of carbonate esters include methyl carbonate, ethyl carbonate, and phenyl carbonate. One or more types of these can be used. 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. One or more types of these can be used.

[0076] 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.

[0077] <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.

[0078]

[0079] 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.

[0080] 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.

[0081] [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.

[0082] <Method for Producing Polyamide Block Copolymer> In the method for producing a polyamide block copolymer of this embodiment, it is preferable to mix and polymerize a polymer constituting the polymer block (A) containing 50 mol% or more of the above-described polyamide-derived structural units with a polymer constituting the polymer block (B) having a glass transition temperature of 20°C or lower. Furthermore, in the method for producing a polyamide block copolymer of this embodiment, the above-described terminal functionalizing agent and / or terminal capping agent may be used. For example, the monomer constituting the polymer block (A) may be mixed with the terminal capping agent and / or terminal functionalizing agent, and the resulting mixture may be melt-polymerized to obtain a polymer constituting the polymer block (A) having terminal functional groups adjusted. The polymer constituting the polymer block (B) may then be added and melt-polymerized to produce a polyamide block copolymer. As a first specific example, the polyamide block copolymer may be produced by dry-blending, optionally in the presence of the terminal capping agent, the polymer constituting the polymer block (A) having terminal functional groups adjusted by melt-polymerization in the presence of the terminal capping agent during the polymerization stage of the polymer block (A), with the polymer constituting the polymer block (B), optionally in the presence of the terminal capping agent, and melt-kneading the resulting mixture. As a second specific example, the polymer constituting the polymer block (A) may be reacted with the terminal functionalizing agent and / or the terminal capping agent, if necessary, followed by pulverization to adjust the terminal functional groups of the polymer block (A), and then the polymer constituting the polymer block (B) may be added and dry-blended, and the mixture may be melt-polymerized. As a third specific example, the polymer constituting the polymer block (A) may be charged into an upper hopper of a melt kneader and, if necessary, the terminal functionalizing agent and / or the terminal capping agent may be reacted, 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.As a fourth specific example, the polymerization may be carried out by reacting a monomer of the polymer constituting the polymer block (A), a polymer constituting the polymer block (B), a catalyst, and, if necessary, the terminal functionalizing agent and / or the terminal capping agent in a dispersion medium, preferably in water, at ordinary temperature, for example, room temperature, to form a salt, and then reacting the obtained salt under, for example, high-pressure and high-temperature conditions.

[0083] 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.

[0084] In order for a polyamide block copolymer to satisfy the above formula (1) and formula (2) with respect to the temperature-loss tangent curve, it is possible to consider, for example, changing the hardness ratio of the polymer block (A), changing the monomer constituting the polymer block (A), adjusting the presence or absence of an aliphatic dicarboxylic acid as a terminal functionalizing agent, adjusting the amount of a terminal blocking agent used, adjusting the number average molecular weight of the polymer block (B), or adjusting the compatibility between the polymer block (A) and the polymer block (B). However, the present invention is not limited to these methods. It is possible to adjust the polyamide block copolymer so as to satisfy the above formula (1) and formula (2) based on the results of comparisons between the examples and comparative examples described below and between the examples themselves.

[0085] <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 exhibit both excellent heat resistance and flexibility, which is preferable.

[0086] <Polymer Block Content> From the viewpoint of obtaining a polyamide block copolymer having excellent strength, 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 or flexibility, 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 or flexibility, 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 strength, 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 an excellent balance between strength and flexibility, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more.

[0087] <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, and still more preferably 5,000 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 42,000 to 280,000 or 50,000 to 280,000, and may be 63,000 to 280,000, 75,000 to 250,000, 100,000 to 230,000, 110,000 to 230,000, or 120,000 to 200,000. Within the above numerical ranges, 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 14.5, more preferably 3.0 to 14.0 or 3.0 to 13.8, and may be 3.5 to 13.5, 3.5 to 13.0, or 3.5 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.

[0088] From the viewpoint of obtaining a polyamide block copolymer having an excellent balance between strength and flexibility, it is also preferable that the aforementioned temperature range (T2-T1) for the polyamide block copolymer is 150°C or less, and the molecular weight distribution of the polyamide block copolymer is 14.0 or less. More preferably, the temperature range is 130°C or less, and the molecular weight distribution is 14.0 or less. Even more preferably, the temperature range is 120°C or less, and the molecular weight distribution is 12.0 or less. Even more preferably, the temperature range is 110°C or less, and the molecular weight distribution is 11.0 or less. Furthermore, from the viewpoint of obtaining a polyamide block copolymer having an even better balance between strength and flexibility, it is also preferable that the aforementioned temperature range (T2-T1) for the polyamide block copolymer is 150°C or less, and the molecular weight distribution of the polymer block (A) is 5.0 or less, and the molecular weight distribution of the polyamide block copolymer is 14.0 or less. More preferably, the temperature range is 130°C or less, the molecular weight distribution of the polymer block (A) is 4.0 or less, and the molecular weight distribution of the polyamide block copolymer is 14.0 or less. Even more preferably, the temperature range is 120°C or less, the molecular weight distribution of the polymer block (A) is 4.0 or less, and the molecular weight distribution is 12.0 or less. Even more preferably, the temperature range is 110°C or less, and the molecular weight distribution of the polymer block (A) is 4.0 or less, and the molecular weight distribution is 11.0 or less.

[0089] <Tensile Breaking Strength, Tensile Breaking Elongation, and Fracture Energy of Polyamide Block Copolymer> The tensile breaking 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 15 MPa or more, still more preferably 19 MPa or more or 20 MPa or more, and can also be 40 MPa or more.

[0090] The tensile elongation at break of the polyamide block copolymer of this embodiment, measured in accordance with JIS K 7161-1:2014, is preferably 30% or more, more preferably 50% or more, even more preferably 100% or more, even more preferably 155% or more, even more preferably 170% or more, even more preferably 190% or more, even more preferably 250% or more, and can even be 300% or more. The larger the tensile elongation at break value, the more excellent the tensile properties of the polyamide block copolymer. More specifically, the tensile strength and tensile elongation at break can be determined by the methods described in the Examples below.

[0091] For the polyamide block copolymer of this embodiment, in the stress-strain curve (SS curve) obtained as a result of measuring the tensile strength at break and the tensile elongation at break, the fracture energy corresponding to the integral value of the stress value from the start of the tensile test to the breaking point is preferably 28 mJ / mm ３ More preferably, 30 mJ / mm ３ More preferably, 32 mJ / mm ３ More preferably, 35 mJ / mm ３ The larger the breaking energy value, the better the balance between strength and flexibility of the polyamide block copolymer. There is no particular upper limit to the breaking energy, but it is preferably 300 mJ / mm ３ From the viewpoint that the polyamide block copolymer has an even better balance between strength and flexibility, the breaking energy may be 37 mJ / mm or less. ３ Above, 39mJ / mm ３ or more than 41 mJ / mm ３ More specifically, the breaking energy can be determined by the method described in the examples below.

[0092] From the viewpoint of strength and elongation, preferably, the tensile breaking strength is 10 MPa or more and the tensile breaking elongation is 30% or more. More preferably, the tensile breaking strength is 10 MPa or more and the tensile breaking elongation is 100% or more. Even more preferably, the tensile breaking strength is 15 MPa or more and the tensile breaking elongation is 100% or more. Even more preferably, the tensile breaking strength is 15 MPa or more and the tensile breaking elongation is 155% or more. From the viewpoint of strength and flexibility, preferably, the tensile breaking strength is 10 MPa or more and the tensile breaking elongation is 30% or more, and the breaking energy is preferably 28 mJ / mm ３ More preferably, the tensile breaking strength is 10 MPa or more, the tensile breaking elongation is 100% or more, and the breaking energy is preferably 28 mJ / mm ３ More preferably, the tensile breaking strength is 15 MPa or more, the tensile breaking elongation is 155% or more, and the breaking energy is preferably 30 mJ / mm ３ Even more preferably, the tensile breaking strength is 19 MPa or more, the tensile breaking elongation is 155% or more, and the breaking energy is preferably 35 mJ / mm ３ That's all.

[0093] <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.

[0094] [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.

[0095]

[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.

[0096] <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.

[0097] <Applications> The polyamide block copolymer and polyamide block copolymer composition of this embodiment can have an excellent balance of strength and flexibility and can be used 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 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 resin modification. They can also be used as foams manufactured 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 hinges of mobile phones and game consoles, 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.

[0098] <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.

[0099] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0100] <Measurement and Evaluation Methods> Various physical properties were measured or evaluated by the following methods.

[0101] [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. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) using standard polymethyl methacrylate-equivalent molecular weights. An HFIP solution prepared by dissolving 0.85 g of sodium trifluoroacetate in 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

[0102] [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). When it was difficult to determine the terminal amino group content even by titration using a 0.01 N HCl aqueous solution, the terminal amino group content was determined to be <10 μmol / g.

[0103] [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.

[0104] [Tm (melting point)] 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, under 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 temperature was again raised 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).

[0105] [Temperature T0 and Temperature Range (T2-T1)] (1) Preparation of Temperature-Loss Tangent (tan δ) Curve The polyamide block copolymers obtained in the Examples and Comparative Examples were heat-pressed at a temperature 20°C higher than their respective melting points to produce films with a thickness of 100 μm. A rectangular polyamide block copolymer test piece (a) measuring 20 mm in length, 5 mm in width, and 100 μm in thickness was cut from this film. Dynamic viscoelasticity measurements were performed on these test pieces (a) in accordance with JIS-K7244-4:1999. Using a Rheogel E-4000 viscoelasticity measuring device manufactured by UBM Corporation, dynamic viscoelasticity measurements were performed under conditions of a frequency of 1.0 Hz, a heating rate of 3°C / min, a temperature range of -100 to 330°C, a chuck distance of 10 mm, a strain amplitude of 0.3%, and tension mode, and the loss tangent (tan δ) values ​​at each temperature were obtained. This allowed the creation of a temperature-loss tangent curve. The temperature-loss tangent curve was created by plotting data acquired every 1°C. (2) Temperature T0 Among the loss tangent values ​​acquired in the temperature range of -100°C to 160°C, the maximum value tanδ(max) was identified, and the temperature T0 [°C] at that time was identified. If multiple peaks existed in the temperature range of -100°C to 160°C in the temperature-loss tangent curve, the value of the loss tangent at the peak top of the maximum peak was taken as the maximum value tanδ(max) at temperature T0. (3) Temperature range (T2-T1) Furthermore, among the loss tangent values ​​acquired in the temperature range of -100°C to 330°C, the temperature showing half the maximum value tanδ(max) (i.e., tanδ(max) / 2) was identified. At this time, there are usually at least two temperatures specified, with a first temperature lower than temperature T0 being designated as T1 [°C] and a second temperature higher than temperature T0 being designated as T2 [°C]. Note that, depending on the shape of the temperature-loss tangent curve, there may be multiple candidates for the first temperature and / or second temperature. In such cases, the temperatures closest to T0 are adopted as the first temperature T1 and the second temperature T2. Then, the temperature width is determined by calculating (Tm2 - Tm1).

[0106] [Tensile Break Strength, Tensile Break Elongation, and Fracture Energy] (1) 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, a small test piece Type 1BA (2 mm thick, total length 75 mm, parallel portion width 5 mm) for tensile evaluation was prepared under the conditions of a mold temperature of 140 ° C. and an injection pressure of 1.0 bar in the T-runner mold of the injection molding machine. The obtained small test piece Type 1BA of the polyamide block copolymer was left to stand in a 140 ° C. dryer for 6 hours, and then subjected to a tensile test at 23 ° C. in accordance with JIS K 7161-1:2014 using an Instron Universal Testing Machine "Model 5566" manufactured by Instron. In this way, the tensile strength and elongation at break were measured. Specifically, the distance between chucks was 50 mm (i.e., the mounting volume of the test piece was about 500 mm ３ The test speed was 0.25 mm / min in the strain range of 0 to 0.3%, and then 50 mm / min in the strain range of 0.3% or more. The test force [N] and stroke value [mm] were obtained every 0.1 seconds. The cross-sectional area was approximately 10 mm ２By inputting a 50 mm distance between the chucks (= 2 mm × 5 mm), it was possible to create a stress-strain curve (SS curve) showing the relationship between stress value [GPa] and strain value [%]. The break point was determined as the strain value obtained immediately before strain values ​​could no longer be obtained. The nominal strain value according to Method A of JIS K 7161-1:2014 was used as the tensile elongation at break. (2) Fracture Energy: The strain energy [mJ] from the start of the tensile test (0% strain) to the break point was calculated using the test force [N] and stroke value [mm] obtained every 0.1 seconds in the tensile test. To calculate the strain energy, the stroke difference [mm] was calculated as the difference between the stroke value obtained at that time and the stroke value obtained immediately before. The integrated value of the test force for each stroke difference was then calculated up to the break point. In addition, to determine the strain energy, both the first strain energy in the strain range of 0 to 0.3% and the second strain energy in the strain range of 0.3% or more were determined depending on the test speed. The determined strain energy [mJ] and the mounting volume of the test piece [mm ３ ], the fracture energy [mJ / mm ３ The fracture energy calculated in this way was calculated as the integral value [mJ / mm ] from the start of the tensile test (strain 0%) to the fracture point for the stress value [GPa] in the stress-strain curve (SS curve) that can be created as a result of the tensile test. ３ ] is equivalent to calculating

[0107] <Materials> The materials used in the examples and comparative examples are as follows.

[0108] <Polymer Block (A)> As the constituent elements of the polymer block (A), PA-1 to PA-8 produced in the following synthesis examples were used.

[0109] 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 ratio 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, 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 semi-aromatic polyamide 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.

[0110] Synthesis Example 2: Production of Semi-Aromatic Polyamide (PA-2) 983.0 g (5.92 mol) of terephthalic acid, 972.3 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, 1.0 g of phosphorous acid (Kishida Chemical Co., Ltd., 0.05% by mass relative to the total mass of the raw materials), and 778 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 was raised 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, yielding a semi-aromatic polyamide 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.

[0111] Synthesis Example 3: Production of Semi-Aromatic Polyamide (PA-3) 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. 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 semi-aromatic polyamide 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.

[0112] Synthesis Example 4: Preparation of Semi-Aromatic Polyamide (PA-4) 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. 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 semi-aromatic polyamide 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.

[0113] Synthesis Example 5: Preparation of Semi-Aromatic Polyamide (PA-5) 1,121.0 g (6.75 mol) of terephthalic acid, 886.4 g (5.60 mol) of a 50 / 50 molar mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, 2.0 g (0.1% by mass relative to the total mass of the raw materials) of sodium hypophosphite monohydrate, and 781 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 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 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. This polyamide is abbreviated as "PA-5." The semi-aromatic ratio is shown in Table 1.

[0114] Synthesis Example 6: Preparation of Semi-Aromatic Polyamide (PA-6) 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 mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio), 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 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.

[0115] Synthesis Example 7: Preparation of Semi-Aromatic Polyamide (PA-7) 1,116.4 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 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 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-7." The semi-aromatic ratio is shown in Table 1.

[0116] Synthesis Example 8: Preparation of Aliphatic Polyamide (PA-8) 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-8." The semi-aromatic ratio is shown in Table 1.

[0117] [Terminal functionalizing agent] The following dicarboxylic acid monomers were used as terminal functionalizing agents as components of 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.

[0118] The various physical property evaluations described above were carried out on PA-1 to PA-8. The results are shown in Tables 1 and 3 together with the physical properties of the terminal functionalizing agents. The notations in Table 1 are as follows. In Table 1, "n / i" indicates the molar ratio of 1,9-nonanediamine / 2-methyl-1,8-octanediamine. "[NH ２ ]" indicates the terminal amino group content. "[COOH]" indicates the terminal carboxyl group content.

[0119]

[0120] <Polymer Block (B)> The following oxygen atom-containing polymers were used as polymer block (B). [Polyether] PE-1: Polyether diamine (diamine of polyethylene glycol and polypropylene glycol copolymer), manufactured by Sigma-Aldrich Corporation, Jeffamine (registered trademark) ED-900 PE-2: Polyether diamine (polyoxytetramethylene diamine), manufactured by Koei Chemical Co., Ltd., PTMGPA-1000 PE-3: Polyether diamine (polyoxyethylene diamine), manufactured by Koei Chemical Co., Ltd., PEGPA-1000 PE-4: Polyoxypropylene diamine, poly(propylene glycol) bis(2-aminopropyl ether) manufactured by Sigma-Aldrich Corporation (number average molecular weight: 400, product number: 406678; measured number average molecular weight: 430)

[0121] 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.

[0122]

[0123] Example 1 The raw materials used in the reaction were used in the mass ratios listed in Table 3. Specifically, 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 and adipic 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. Next, "PE-1" was added, and the mixture was stirred for an additional hour at a resin temperature of 280°C, after which the distillate was removed. The reaction system was then depressurized to 10 Pa and stirred for an additional hour at a resin temperature of 280°C, after which the polyamide block copolymer was removed. The mass ratio (A) / (B) listed in Table 3 is illustratively explained as follows: in Example 1, 68 parts by mass (e.g., 68.5 g) of polyamide PA-1 functionalized with a terminal functionalizing agent was used in combination with 32 parts by mass (e.g., 31.5 g) of polyether PE-1.

[0124] Examples 2 to 3, 5 to 9 and Comparative Examples 2 and 3 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.

[0125] Example 4 The reaction was carried out using raw materials in the mass ratios shown in Table 3. Specifically, 588.6 g (3.54 mol) of terephthalic acid, 488.7 g (0.54 mol) of "PE-1," 226 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 homogeneous. Subsequently, 474.8 g (3.00 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (50 / 50 molar ratio) and 162 mL of distilled water were added to the mixture, and stirring was continued. A homogeneous 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 280°C while stirring under a nitrogen stream of 200 mL / min. The reaction system was then reduced in pressure to 10 Pa and stirred for 3 hours at a resin temperature of 280°C, after which the polyamide block copolymer was removed.

[0126] Comparative Example 1 The reaction was carried out using raw materials in the mass ratios shown in Table 3. Specifically, 448.6 g (2.70 mol) of terephthalic acid, 900.0 g (0.9 mol) of "PE-2," 238 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 homogeneous. Subsequently, 284.9 g (1.80 mol) of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio 70 / 30) and 171 mL of distilled water were added to the mixture, and stirring was continued. Thereafter, a homogeneous salt was obtained from the reaction solution. The obtained 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.

[0127] 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.

[0128]

[0129] From the results in Table 3, the polyamide block copolymers obtained in Examples 1 to 9 had a fracture energy value of 30 mJ / mm ３ or more, it was found that the balance between strength and flexibility was excellent. This is thought to be because the T0 value was -60°C or more and the temperature width (T2-T1) value was 170°C or less, which allowed the polymer block (A) to maintain the properties such as strength expected of the polymer block (A) and allowed the polymer block (B) to fully exhibit properties such as flexibility. On the other hand, the polyamide block copolymers obtained in Comparative Examples 1 and 2 both had fracture energy values ​​of 30 mJ / mm３ The results showed that the balance between strength and flexibility was inferior to that of the polyamide block copolymers obtained in the Examples. From a comparison of Examples 1 to 9 and Comparative Examples 1 and 2, it was considered that the factors that resulted in an impairment of the balance between strength and flexibility in the polyamide block copolymers were that the T0 value was less than -60°C and that the temperature range (T2 - T1) value was greater than 170°C. It was also considered that the T0 value was greater than 120°C.

[0130] Furthermore, the results in Table 3 show that the polyamide block copolymers obtained in Examples 1 to 9 have 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 9 can be used under higher temperature conditions than the polyamide block copolymer obtained in Comparative Example 3.

[0131] The polyamide block copolymer of this embodiment has an excellent balance of strength 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, automobile 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 having a melting point of 230°C or higher, comprising a polymer block (A) containing 50 mol% or more of structural units derived from polyamide, and a polymer block (B) having a glass transition temperature of 20°C or lower, wherein a test piece having a length of 20 mm, a width of 5 mm, and a thickness of 100 μm is measured using a viscoelasticity measuring device in a temperature range of -100°C to 330°C with a chuck distance of 10 mm, a frequency of 1 Hz, and a heating rate of 3°C / min. In the temperature-loss tangent (tan δ) curve obtained, the temperature T0 [°C] at which the loss tangent in the temperature range of -100°C to 160°C reaches a maximum value tan δ (max) satisfies the following formula (1): Formula (1): -60°C≦T0≦120°C; and a first temperature T1 [°C] which is lower than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), and a second temperature T2 [°C] which is higher than the temperature T0 and at which the loss tangent is half the maximum value tan δ(max), satisfy the relationship of the following formula (2):

2. The polyamide block copolymer of 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 structural units derived from an aliphatic diamine and dicarboxylic acid units mainly composed of structural units derived from an aromatic dicarboxylic acid.

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

5. The polyamide block copolymer according to claim 3, wherein the aliphatic diamine comprises a structural unit derived from at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines.

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

7. The polyamide block copolymer according to claim 3, wherein the aromatic dicarboxylic acid 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.

8. The polyamide block copolymer according to claim 1, wherein the polymer block (A) contains a structural unit derived from the polyamide and a structural unit derived from a compound selected from the group consisting of a dicarboxylic acid and a diamine.

9. The polyamide block copolymer according to claim 1, wherein the polymer block (B) contains a structural unit derived from a polyether polyol, a polyester polyol, a polycarbonate polyol, a polysiloxane polyol, an amine derivative thereof, or a carboxyl derivative thereof.

10. The polyamide block copolymer according to claim 1, wherein the polyamide block copolymer has a number average molecular weight of 50,000 or less.

11. The polyamide block copolymer according to claim 1, wherein the weight average molecular weight of the polyamide block copolymer is 500,000 or less.

12. The polyamide block copolymer according to claim 1, wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the polyamide block copolymer is 2.0 to 14.

5.

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.