Polyamide elastomer and its manufacturing method

Abstract

The polyamide-based elastomer of the present invention is a polyamide-based elastomer comprising a hard segment containing a polyamide structure (A) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the following general formula (I), and a soft segment containing a polyether structure (B), wherein the structural unit (D) is more than 0 part by mass and not more than 0.50 parts by mass per 100 parts by mass of the hard segment: JPEG0007666766000026.jpg15161 (In the general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms.

Description

[Technical field]

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

[0002] Polyamide-based elastomers having a polyether structure are excellent in terms of high elasticity, transparency, elongation recovery, and melt moldability, and are therefore used in automobile parts, peripheral parts for electronic devices, battery materials, packings, sealing materials, etc.

[0003] The polyamide-based elastomer having a polyether structure has a polyamide structure as a hard segment and a polyether structure as a soft segment. Patent Documents 1 to 3 describe laminates having a layer of a polyamide-based elastomer and a layer of another elastomer or a polyurethane resin. Patent Document 1 describes that by mixing a polyamide resin and a modified polypropylene resin with a polyamide-based elastomer, strength, rigidity, and impact resistance can be achieved in addition to adhesion to a thermoplastic resin elastomer layer. Patent Document 2 describes that a layer based on polyamide containing a polyamide-based elastomer and a layer based on thermoplastic polyurethane (TPU) have good adhesion and impact resistance. Patent Document 3 describes that a polyamide elastomer containing a structural unit derived from a branched diamine compound has good adhesion to thermoplastic polyurethane and also has mechanical properties. Furthermore, Patent Document 4 describes that a polyamide elastomer having a specific combination of hard segment structural units has a low melting point and excellent material strength. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-106249 A [Patent Document 2] JP 2009-029142 A [Patent Document 3] International Publication No. 2007 / 145324 [Patent Document 4] Patent Publication No. 2022-77106 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is room for further study in order to provide a structure with the appropriate flexibility required for a polyamide-based elastomer when used alone as a molded product. Furthermore, polyamide-based elastomers are required to have moldability, and depending on the application of the molded product, they are also required to have heat resistance and low-temperature properties. In addition, when used as a layer in a laminate, they are required to have adhesion to thermoplastic resins. Therefore, an object of the present invention is to provide a polyamide-based elastomer which has appropriate flexibility, and is excellent in moldability, heat resistance, low-temperature properties and adhesion to thermoplastic resins. [Means for solving the problem]

[0006] The present invention relates to, for example, the following items [1] to

[25] . [1] A polyamide-based elastomer comprising a hard segment containing a polyamide structure (A) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the following general formula (I), and a soft segment containing a polyether structure (B): The polyamide-based elastomer has a content of the structural unit (D) of more than 0 part by mass and not more than 0.50 parts by mass per 100 parts by mass of the hard segment. [ka] (In the general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms. [2] The polyamide-based elastomer according to [1], wherein the polyamide-based elastomer contains more than 0 mass% and less than 0.22 mass% of the structural unit (D) relative to 100 mass% of all structural units of the polyamide-based elastomer. [3] The polyamide-based elastomer according to [1] or [2], wherein the polyamide structure (A) contains a structural unit derived from at least one compound selected from the group consisting of an aminocarboxylic acid compound and a lactam compound. [4] The polyamide-based elastomer according to any one of [1] to [3], wherein a mass ratio of the hard segment to the soft segment is hard segment / soft segment=95 / 5 to 20 / 80. [5] The polyamide elastomer according to any one of [1] to [4], wherein the polyether structure (B) contains an XYX triblock polyether represented by the following general formula (5): [ka] (In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.) [6] The polyamide-based elastomer according to any one of [1] to [5], wherein the hard segment contains a structural unit (C) derived from a dicarboxylic acid compound (c) not containing an imino group. [7] The polyamide structure (A) has a constitutional unit derived from an aminocarboxylic acid compound represented by the following general formula (1) and / or a lactam compound represented by the following general formula (2), and the polyether structure (B) has a constitutional unit derived from an XYX type triblock polyether diamine compound represented by the following general formula (3), The polyamide-based elastomer according to any one of [1] to [5], further having a structural unit (C) derived from a dicarboxylic acid compound represented by the following general formula (4) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the above general formula (I). [ka] [In the formula, R 3 represents a linking group containing a hydrocarbon chain. [ka] [In the formula, R 3 represents a linking group containing a hydrocarbon chain. [ka] [In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.] [ka] [In the formula, R 4 represents a linking group that contains a single bond or a hydrocarbon chain and does not contain an imino group. [8] A polyamide-based elastomer according to any one of [1] to [7], which has a melting point of 136.0°C or higher, as determined from the endothermic peak of melting when heated to 210°C at a rate of 10°C / min using a differential scanning calorimeter. [9] A polyamide-based elastomer according to any one of [1] to [8] having a tensile modulus of 91 to 1100 MPa as measured in accordance with ISO-527.

[10] (Step 1) ring-opening polymerization of a lactam compound in the presence of any dicarboxylic acid (c) not containing an imino group at a polymerization temperature of 150 to 350° C. and a polymerization pressure of 0.1 to 5.0 MPa to produce a polyamide prepolymer having the polyamide structure (A), the structural unit (D) and any structural unit (C); (Step 2) reacting the polyether compound having the polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide elastomer according to any one of [1] to [9],

[11] (Step 1) ring-opening polymerizing a lactam compound in the presence of the iminodialkanoic acid compound (d) and any dicarboxylic acid not containing an imino group (c) to produce a polyamide prepolymer having the polyamide structure (A), the structural unit (D) and any structural unit (C); (Step 2) A polyether compound having the polyether structure (B) and1 and reacting the polyamide prepolymer obtained in step (2) with the polyamide prepolymer obtained in step (1). The method for producing a polyamide elastomer according to any one of [1] to [9],

[12] (Step 1) polycondensing an aminocarboxylic acid compound in the presence of the iminodialkanoic acid compound (d) and any dicarboxylic acid not containing an imino group (c) to produce a polyamide prepolymer having the polyamide structure (A), the structural unit (D) and any structural unit (C); (Step 2) reacting the polyether compound having the polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide elastomer according to any one of [1] to [9],

[13] A method for producing a polyamide-based elastomer according to any one of [1] to [9], comprising polymerizing a polyamide-forming monomer, a polyether compound having the polyether structure (B), the iminodialkanoic acid compound (d), and a dicarboxylic acid (c) not containing any imino group.

[14] A layer made of any one of the polyamide-based elastomers described in [1] to [9].

[15] A laminate comprising a layer (X1) made of a polyamide-based elastomer according to any one of [1] to [9], and a layer (Y1) having a composition different from that of the layer (X1).

[16] The laminate according to

[15] , wherein the layer (X1) and the layer (Y1) are adjacent to each other.

[17] The laminate according to

[15] , wherein the layer (Y1) contains at least one resin selected from the group consisting of polyurethane resins, polyamide-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyolefin-based elastomers, and polystyrene-based elastomers.

[18] A molded article containing any of the polyamide-based elastomers described in [1] to [9].

[19] A resin composition comprising the polyamide elastomer according to any one of [1] to [9].

[20] At least one thermoplastic resin selected from the group consisting of polyamide resins other than polyamide-based elastomers, polyamide-imide resins, polyester resins, polyolefin resins, polystyrene resins, halogenated polyolefin resins, (meth)acrylic resins, polyphenylene ether resins, polycarbonate resins, polyacetal resins, thermoplastic polyurethane resins, and ABS resins.

[19] Tree Fat composition.

[21]

[19] or

[20] Tree A layer comprising an oil composition.

[22]

[19] or

[20] resin A laminate comprising a layer (X2) made of a composition and a layer (Y2) having a composition different from that of the layer (X2).

[23] The laminate according to

[22] , wherein the layer (X2) and the layer (Y2) are adjacent to each other.

[24] The laminate according to

[22] , wherein the layer (Y2) contains at least one resin selected from the group consisting of polyurethane resins, polyamide-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyolefin-based elastomers, and polystyrene-based elastomers.

[25]

[19] or

[20] Tree A molded article comprising the oil composition. Effect of the Invention

[0007] The polyamide elastomer of the present invention has appropriate flexibility and is excellent in moldability, heat resistance, low-temperature properties and adhesion to thermoplastic resins. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention provides a polyamide-based elastomer comprising a hard segment containing a polyamide structure (A) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the following general formula (I), and a soft segment containing a polyether structure (B): The polyamide elastomer has the structural unit (D) in an amount of more than 0 part by mass and not more than 0.50 part by mass relative to 100 parts by mass of the hard segment. [ka] (In the general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms. In this specification, "more than 0 parts by mass" and "more than 0% by mass" are meant to exclude cases where absolutely nothing is included.

[0009] The polyamide-based elastomer contains a hard segment and a soft segment, the hard segment contains a polyamide structure (A) and a structural unit (D), and the soft segment contains a polyether structure (B).

[0010] In the polyamide-based elastomer, the polyether structure (B) is a soft segment, and the rest are usually hard segments. The polyamide structure (A) and the structural unit (D) in the polyamide-based elastomer of the present invention are hard segments.

[0011] Examples of polyamide-based elastomers include polyether ester amide elastomers in which hard segments and soft segments are bonded by ester bonds, and polyether polyamide elastomers in which hard segments and soft segments are bonded by amide bonds. From the viewpoint of exerting the effects of the present invention and from the viewpoint of excellent hydrolysis resistance, polyether polyamide elastomers in which hard segments and soft segments are bonded by amide bonds are preferred.

[0012] <Polyamide structure (A)> The hard segment includes a polyamide structure (A). The polyamide structure (A) is preferably a polycondensate having a constitutional unit derived from a polyamide-forming monomer, which is at least one selected from the group consisting of a nylon salt consisting of a diamine and a dicarboxylic acid, an aminocarboxylic acid compound, and a lactam compound. Among these, the polyamide-forming monomer is preferably at least one selected from the group consisting of an aminocarboxylic acid compound and a lactam compound, and from the viewpoint of generating the iminodialkanoic acid compound (d) represented by the above general formula (I) during the reaction, a lactam compound is more preferable, and when the iminodialkanoic acid compound (d) is added, an aminocarboxylic acid compound is more preferable. In this specification, the constitutional unit derived from the lactam compound constituting the polyamide structure (A) does not include the constitutional unit (D) derived from the iminodialkanoic acid compound (d) generated by ring-opening of the lactam compound.

[0013] The aminocarboxylic acid compound is preferably represented by the following general formula (1). [ka] [In the formula, R 3 represents a linking group containing a hydrocarbon chain.

[0014] In the above general formula (1), R 3 is preferably a divalent hydrocarbon group containing an aliphatic group, an alicyclic group and / or an aromatic group having 2 to 20 carbon atoms, more preferably the above-mentioned hydrocarbon group having 3 to 18 carbon atoms, even more preferably the above-mentioned hydrocarbon group having 4 to 15 carbon atoms, still more preferably the above-mentioned hydrocarbon group having 10 to 15 carbon atoms, and particularly preferably an alkylene group having 10 to 15 carbon atoms.

[0015] R 3 The hydrocarbon chain may have a substituent in place of some or all of the hydrogen atoms, such as a halogen atom such as a fluorine atom, a nitro group, a cyano group, an alkyloxy group (straight-chain, branched-chain, cyclic), etc.

[0016] Specific examples of the aminocarboxylic acid compound include aliphatic ω-aminocarboxylic acids having 5 to 20 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, etc. These may be used alone or in combination of two or more.

[0017] The lactam compound is preferably represented by the following general formula (2). [ka] [In the formula, R 3 represents a linking group containing a hydrocarbon chain.

[0018] In the above general formula (2), R 3 is R in general formula (1). 3 is the same as:

[0019] Examples of the lactam compound include aliphatic lactams having 4 to 20 carbon atoms, such as γ-butyrolactam, ε-caprolactam, ω-enantholactam, ω-undecalactam, laurolactam (ω-lauryllactam), etc. These may be used alone or in combination of two or more.

[0020] Among the aminocarboxylic acid compounds and lactam compounds, laurolactam (ω-lauryllactam), 11-aminoundecanoic acid, and 12-aminododecanoic acid are preferred from the viewpoints of dimensional stability, chemical resistance, and mechanical properties due to low water absorption, and laurolactam is more preferred from the viewpoint of by-producing the iminodialkanoic acid compound represented by the above general formula (I).

[0021] Examples of diamines in nylon salts include aliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexane-1,6-diamine, 2,4,4-trimethylhexane-1,6-diamine, and 3-methylpentane-1,5-diamine. Alicyclic and aromatic diamines may also be used. These may be used alone or in combination of two or more.

[0022] As the dicarboxylic acid in the nylon salt, at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used, and examples thereof include dicarboxylic acid compounds such as aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. These can be used alone or in combination of two or more.

[0023] The lactam compound undergoes ring-opening polymerization, and the aminocarboxylic acid compound and nylon salt undergo polycondensation to form a polyamide structure (A).

[0024] The polyamide structure (A) preferably has carboxyl groups at both ends. In this case, the hard segment contains, in addition to the polyamide structure (A) and the structural unit (D), at least one dicarboxylic acid (c) selected from the group consisting of an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid, or a structural unit (C) derived from a derivative thereof (hereinafter also referred to as "structural unit (C)"). The dicarboxylic acid (c) does not contain an imino group.

[0025] In the presence of dicarboxylic acid (c), the polyamide-forming monomers can be subjected to ring-opening polymerization or polycondensation in a conventional manner to obtain a polyamide structure having carboxyl groups at both ends. The dicarboxylic acid (c) is preferably represented by the following general formula (4).

[0026] [ka] [In the formula, R 4 represents a linking group that contains a single bond or a hydrocarbon chain and does not contain an imino group.

[0027] In the above general formula (4), R 4 is preferably a divalent hydrocarbon group containing an aliphatic group, an alicyclic group and / or an aromatic group having 1 to 20 carbon atoms, more preferably the above-mentioned hydrocarbon group having 1 to 15 carbon atoms, even more preferably the above-mentioned hydrocarbon group having 2 to 12 carbon atoms, still more preferably the above-mentioned hydrocarbon group having 4 to 10 carbon atoms, and particularly preferably an alkylene group having 4 to 10 carbon atoms.

[0028] Specific examples of the dicarboxylic acid (c) include dicarboxylic acids having 2 to 25 carbon atoms, preferably 3 to 22 carbon atoms (R 4Examples of the dimer acid include linear aliphatic dicarboxylic acids having 1 to 20 carbon atoms, dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acids) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation of triglycerides, and hydrogenated products thereof (hydrogenated dimer acids), alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. As the dimer acid and hydrogenated dimer acid, those available under the trade names "Pripol 1004", "Pripol 1006", "Pripol 1009", and "Pripol 1013" manufactured by Croda Co., Ltd. can be used. These can be used alone or in combination of two or more. Among these, adipic acid, sebacic acid, and dodecanedioic acid are preferred.

[0029] The number average molecular weight of the polyamide structure (A) is preferably 300 to 15000, and from the viewpoint of flexibility and moldability, more preferably 300 to 6000. In this specification, the number average molecular weight is a value determined by gel permeation chromatography.

[0030] <Polyether Structure (B)> The soft segment contains a polyether structure (B), and the polyether structure (B) contains a polyether unit (b). The polyether unit (b) is preferably a polyoxyalkylene, and the repeating unit in the polyether unit (b) is more preferably an oxyalkylene having 2 to 4 carbon atoms. The alkylene group of the oxyalkylene is preferably a linear or branched alkylene group having 2 to 4 carbon atoms, such as an ethylene group, an n-propylene group, an i-propylene group, a 1-methylethylene group, a 2-methylethylene group, an n-butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a dimethylethylene group, and an ethylethylene group. The constituent unit of the polyether unit (b) may be one type alone or two or more types, but two or more types are preferred.

[0031] Specific examples of the polyether unit (b) of the soft segment include polyoxyethylene derived from polyethylene glycol, polyoxypropylene derived from polypropylene glycol, polytetramethylene ether derived from polytetramethylene ether glycol, XYX triblock polyether, etc. These may be used alone or in combination of two or more. An example of the XYX triblock polyether is a structure represented by the following general formula (5).

[0032] [ka] (In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.)

[0033] In the above general formula (5), x and z are each independently preferably an integer of 1 to 18, more preferably an integer of 1 to 16, still more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12. In addition, y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, still more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.

[0034] In the unit represented by the general formula (5), it is preferable that x and z are in the above ranges from the viewpoint of transparency of the elastomer, and it is preferable that y is in the above range from the viewpoint of rubber elasticity. Also, it is preferable that x, y and z are in the above ranges from the viewpoint of toughness of the elastomer.

[0035] The number average molecular weight of the polyether unit (b) is preferably 200-6,000, and more preferably 650-2,000.

[0036] The polyether structure (B) preferably has a terminal hydroxyl group or an amino group, more preferably a polyether diol having hydroxyl groups at both ends and a polyether diamine having amino groups at both ends, and even more preferably a polyether diamine. When both ends are amino groups, the polyether structure (B) has an amino group at the end or both ends of the polyether unit (b). The XYX triblock polyether diamine compound having a polyether structure having amino groups at both ends is represented by, for example, the following general formula (3).

[0037] [ka] [In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.]

[0038] In the above general formula (3), x and z are each independently preferably an integer of 1 to 18, more preferably an integer of 1 to 16, still more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12. Furthermore, y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, still more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.

[0039] <Structural unit (D) derived from iminodialkanoic acid compound (d)> The hard segment contains a structural unit (D) (also referred to as "structural unit (D)") derived from an iminodialkanoic acid compound (d) represented by the following general formula (I).

[0040] [ka]

[0041] In the above general formula (I), R 1 and R 2are each independently an alkylene group having 2 to 20 carbon atoms, preferably each independently an alkylene group having 8 to 15 carbon atoms, more preferably each independently an alkylene group having 9 to 11 carbon atoms, and particularly preferably each independently an alkylene group having 11 carbon atoms. The alkylene group may be either linear or branched, but is preferably linear.

[0042] From the viewpoints of elasticity, heat resistance, low-temperature properties, moldability and adhesion, the content of the structural unit (D) in 100% by mass of all structural units of the polyamide-based elastomer is preferably more than 0% by mass and less than 0.22% by mass, more preferably 0.01 to 0.20% by mass, and even more preferably 0.02 to 0.18% by mass.

[0043] From the viewpoints of elasticity, heat resistance, low-temperature properties, moldability and adhesion, the structural unit (D) derived from the iminodialkanoic acid compound (d) represented by general formula (I) is more than 0 part by mass and not more than 0.50 parts by mass, preferably 0.005 to 0.46 parts by mass, and more preferably 0.01 to 0.25 parts by mass, relative to 100 parts by mass of the hard segment containing the polyamide structure (A) and the structural unit (D) (structural unit (D) derived from the compound represented by general formula (I) / 100 parts by mass of hard segment).

[0044] The iminodialkanoic acid compound (d) represented by the general formula (I) is likely to react with the terminals of the polyamide structure (A), and since it has two COOH groups and one NH group, it is likely to crosslink the polyamide structure (A) as a compound having three reaction sites. Therefore, by setting the mass ratio of the structural unit (D) to the hard segment within the above range, the degree of crosslinking can be made appropriate, and the polyamide elastomer is likely to have properties such as a good tensile modulus and improved adhesion to different resins without impairing flexibility.

[0045] The method of introducing the structural unit (D) into the polyamide-based elastomer includes a method of adding an iminodialkanoic acid compound (d) to the raw material and polymerizing it, and / or a method of using a lactam compound as the raw material of the polyamide structure (A). The details of the production method will be described later.

[0046] The mass ratio of the structural unit (D) to the hard segment can be adjusted by adjusting the amount of lactam, the polymerization temperature and polymerization pressure (polymerization conditions) during ring-opening polymerization of the lactam, the amount of the iminodialkanoic acid compound (d) represented by general formula (I), and the like.

[0047] <Polyamide elastomer> The combination of the hard segment and the soft segment may be the combination of the hard segment and the soft segment described above. For example, the combination of polyamide structure (A) / structural unit (D) / structure (B) and the combination of polyamide structure (A) / structural unit (C) / structural unit (D) / structure (B) are preferred, and the combination of polyamide structure (A) / structural unit (D) / XYX triblock polyether structure and the combination of polyamide structure (A) / structural unit (C) / structural unit (D) / XYX triblock polyether structure are particularly preferred.

[0048] A preferred embodiment of the polyamide-based elastomer is a polymer containing a constituent unit derived from an aminocarboxylic acid compound represented by the above general formula (1) and / or a lactam compound represented by the above general formula (2), a constituent unit derived from an XYX triblock polyether diamine compound represented by the above general formula (3), a constituent unit derived from a dicarboxylic acid compound represented by the above general formula (4), and a constituent unit derived from an iminodialkanoic acid compound represented by the above general formula (I). That is, it is preferable that the polyamide elastomer has the polyamide structure (A) having a constituent unit derived from an aminocarboxylic acid compound represented by the above general formula (1) and / or a lactam compound represented by the above general formula (2), the polyether structure (B) having a constituent unit derived from an XYX type triblock polyether diamine compound represented by the above general formula (3), and further having a constituent unit (C) derived from a dicarboxylic acid compound represented by the above general formula (4) and a constituent unit (D) derived from an iminodialkanoic acid compound represented by the above general formula (I).

[0049] The ratio (mass ratio) of the hard segment to the soft segment is preferably hard segment / soft segment=95 / 5 to 20 / 80. Within this range, bleeding out from the molded product is easily avoided and sufficient flexibility is easily ensured. The hard segment / soft segment (mass ratio) is more preferably 95 / 5 to 25 / 75, and even more preferably 95 / 5 to 40 / 60.

[0050] In the present invention, the ratio (mass ratio) of the hard segment to the soft segment is a value calculated based on the amount of the monomer components constituting each segment. Usually, the ratio (mass ratio) of the hard segment to the soft segment of the obtained polyamide-based elastomer is equal to the value calculated based on the amount of the monomer components constituting each segment.

[0051] If the hard segment / soft segment (mass ratio) is less than the above range, the crystallinity of the polyamide component may be low, which may be undesirable since mechanical properties such as strength and elastic modulus may be reduced.If the hard segment / soft segment (mass ratio) is more than the above range, it may be undesirable since the functions and performance of an elastomer such as rubber elasticity and flexibility may be difficult to exhibit.

[0052] The degree of polymerization of the polyamide-based elastomer is not particularly limited, but the relative viscosity measured at 25°C by dissolving 0.25 g of the polyamide-based elastomer in 50 ml of m-cresol (special grade reagent) in accordance with JIS K 6920-2 is preferably 1.10 to 5.00, more preferably 1.50 to 4.50, and even more preferably 1.50 to 3.00.

[0053] The polyamide-based elastomer preferably has a melting point of 136.0°C or higher, more preferably 136.0 to 200.0°C, as determined from the endothermic peak of melting when the temperature is raised to 210°C at 10°C / min using a differential scanning calorimeter. When the melting point is in the above range, the heat resistance is excellent. It is considered that the melting point of the present invention is high up to the above range because the hard segment has a polyamide structure, which is a high-melting engineering plastic.

[0054] The tensile modulus of the polyamide elastomer measured in accordance with ISO-527 is preferably 91 to 1100 MPa, more preferably 100 to 1080 MPa. Within the above range, the polyamide elastomer has a suitable flexibility. As described above, it is believed that such a suitable flexibility is achieved by the polyamide elastomer containing the structural unit (D) derived from the iminodialkanoic acid compound represented by general formula (I) in a specific ratio.

[0055] From the viewpoint of flexibility, the hardness (Shore D) of the polyamide elastomer is preferably in the range of 15 to 70, more preferably in the range of 18 to 70, further preferably in the range of 20 to 70, and particularly preferably in the range of 25 to 70. The hardness (Shore D) is the median value of hardness measurements at five points measured using a type D durometer in accordance with ISO868.

[0056] <Method of manufacturing polyamide elastomer> The production of polyamide-based elastomers can be carried out by a batch system or a continuous system, and a batch system reaction vessel, a single-vessel or multi-vessel continuous reactor, a tubular continuous reactor, etc. can be used alone or in appropriate combination.

[0057] Methods for producing polyamide-based elastomers can be broadly classified into the following four methods, (Production Method 1) to (Production Method 4), depending on the type of monomer that forms the polyamide structure (A) and the method for introducing the structural unit (D) derived from the iminodialkanoic acid compound (d), which is represented by the above general formula (I), into the elastomer.

[0058] (Manufacturing method 1) (Step 1) carrying out ring-opening polymerization of a lactam compound in the presence of an optional dicarboxylic acid (c) not containing an imino group at a polymerization temperature of 150 to 350°C and a polymerization pressure of 0.1 to 5.0 MPa to produce a polyamide prepolymer having a polyamide structure (A), a structural unit (D) and an optional structural unit (C); (Step 2) reacting a polyether compound having a polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide-based elastomer comprising the steps of:

[0059] In step 1 of production method 1, a lactam compound is subjected to ring-opening polymerization. At that time, a certain amount of iminodialkanoic acid compound (d) represented by general formula (I), which is a ring-opened dimer of lactam compound, is produced. As a result, a polyamide prepolymer containing polyamide structure (A), which is a ring-opened polymer of lactam, and structural unit (D) derived from iminodialkanoic acid compound represented by general formula (I) is obtained. Ring-opening polymerization can also be carried out in the presence of dicarboxylic acid (c) that does not contain an imino group, and in that case, a polyamide prepolymer containing structural unit (C) can be obtained.

[0060] In step 1, the proportion of the structural unit (D) contained in the polyamide prepolymer varies depending on the polymerization temperature and polymerization pressure, and the higher the polymerization temperature and the polymerization pressure, the greater the proportion of the structural unit (D) contained in the polyamide prepolymer tends to be. Therefore, from the viewpoint of controlling the proportion of the structural unit (D) contained in the polyamide elastomer, the ring-opening polymerization is carried out at a polymerization temperature of 150 to 350°C, preferably 250 to 300°C, and at a polymerization pressure of 0.1 to 5.0 MPa, preferably 1.0 to 4.0 MPa.

[0061] The polymerization time in step 1 is preferably 2 to 15 hours, more preferably 5 to 12 hours. If the polymerization time is shorter than the above range, the molecular weight is likely to increase insufficiently, whereas if the polymerization time is longer, coloration due to thermal decomposition or the like is likely to occur. In either case, a polyamide-based elastomer having desired physical properties may not be obtained.

[0062] In step 2 of the production method 1, the polyamide prepolymer obtained in step 1 is reacted with a polyether compound having a polyether structure (B) to obtain a polyamide elastomer. The polyether compound is preferably a polyether polyamine. At that time, the polymerization is preferably carried out at a temperature of 150 to 300°C, more preferably 200 to 250°C.

[0063] (Manufacturing method 2) (Step 1) ring-opening polymerization of a lactam compound in the presence of an iminodialkanoic acid compound (d) and an optional dicarboxylic acid (c) not containing an imino group to produce a polyamide prepolymer having a polyamide structure (A), a structural unit (D) and an optional structural unit (C); (Step 2) A polyether compound having a polyether structure (B) and 1 and reacting the polyamide prepolymer obtained in step (2) with the polyamide prepolymer obtained in step (1). The method for producing a polyamide-based elastomer comprising the steps of:

[0064] In step 1 of the production method 2, a lactam compound is subjected to ring-opening polymerization. The ring-opening polymerization is carried out in the presence of an iminodialkanoic acid compound (d) and an optional dicarboxylic acid (c) that does not contain an imino group. A polyamide prepolymer having a polyamide structure (A), a structural unit (D) and an optional structural unit (C) is obtained.

[0065] In step 1, the polymerization temperature is not particularly limited as long as the polymerization proceeds and no unnecessary side reactions occur. Depending on the temperature and pressure conditions, the iminodialkanoic acid compound (d) represented by general formula (I) is produced, and in production method 2, the proportion of the structural unit (D) contained in the polyamide elastomer is also controlled by adding the iminodialkanoic acid compound (d). The polymerization time in step 1 is the same as that in step 1 of production method 1.

[0066] In step 2 of the production method 2, a polyether compound having a polyether structure (B) is reacted with the polyamide prepolymer obtained in step 1. The polyether compound is preferably a polyether polyamine. At that time, the polymerization is carried out at a temperature of preferably 150 to 300°C, more preferably 200 to 250°C.

[0067] (Manufacturing method 3) (Step 1) polycondensing an aminocarboxylic acid compound in the presence of an iminodialkanoic acid compound (d) and an optional dicarboxylic acid (c) not containing an imino group to produce a polyamide prepolymer having a polyamide structure (A), a structural unit (D) and an optional structural unit (C); (Step 2) reacting a polyether compound having a polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide-based elastomer comprising the steps of:

[0068] In step 1 of production method 3, an aminocarboxylic acid compound is polycondensed in the presence of an iminodialkanoic acid compound (d) and an arbitrary dicarboxylic acid (c) not containing an imino group to obtain a polyamide prepolymer having a polyamide structure (A), a structural unit (D) and an arbitrary structural unit (C). The polymerization temperature is preferably 150 to 350°C, more preferably 180 to 280°C. The ratio of the structural unit (D) contained in the polyamide prepolymer can be controlled by adjusting the amount of the iminodialkanoic acid compound (d) relative to the aminocarboxylic acid compound. The polymerization time in step 1 is preferably 2 to 15 hours, more preferably 3 to 12 hours.

[0069] In step 2 of the production method 3, the polyamide prepolymer obtained in step 1 is reacted with a polyether compound having a polyether structure (B) to obtain a polyamide elastomer. The polyether compound is preferably a polyether polyamine. At that time, the polymerization is preferably carried out at a temperature of 150 to 300°C, more preferably 200 to 250°C.

[0070] (Manufacturing method 4) A method for producing a polyamide-based elastomer, comprising polymerizing a polyamide-forming monomer, a polyether compound having a polyether structure (B), an iminodialkanoic acid compound (d) represented by general formula (I), and a dicarboxylic acid (c) not containing any imino group.

[0071] In the production method 4, a polyamide-forming monomer, a polyether compound having a polyether structure (B), an iminodialkanoic acid compound (d) represented by the general formula (I), and an optional dicarboxylic acid (c) not containing an imino group are reacted at once to obtain a polyamide-based elastomer having a polyamide structure (A), a structural unit (D), an optional structural unit (C), and a polyether structure (B). The polyether compound is preferably a polyether polyamine.

[0072] When an aminocarboxylic acid is used as the polyamide-forming monomer, the polyamide can be produced by a process comprising the steps of atmospheric pressure melt polymerization or atmospheric pressure melt polymerization followed by reduced pressure melt polymerization. On the other hand, when a lactam compound, or a compound synthesized from a diamine compound and a dicarboxylic acid compound and / or a salt thereof is used as a polyamide-forming monomer, the polyamide can be produced in the presence of an appropriate amount of water by a method comprising melt polymerization under a pressure of 0.1 to 5.0 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization.

[0073] (Manufacturing method 5) A method for producing a polyamide-based elastomer, comprising reacting a polyamide-based elastomer having a hard segment containing a polyamide structure (A) and a soft segment containing a polyether structure (B) with an iminodialkanoic acid compound (d) represented by general formula (I).

[0074] In the production method 5, when the polyamide elastomer is reacted with the iminodialkanoic acid compound (d), the polyamide can be produced by a method comprising a process of normal pressure melt polymerization or a process of normal pressure melt polymerization followed by reduced pressure melt polymerization.

[0075] (others) During the production of polyamide-based elastomers, monoamines and diamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, monocarboxylic acids such as acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, and dodecanedioic acid, and dicarboxylic acids can be added as necessary in order to adjust the molecular weight or stabilize the melt viscosity during molding. The amount of these used is preferably appropriate so that the relative viscosity of the finally obtained elastomer falls within the range of 1.10 to 5.00. The method for measuring the relative viscosity is as described above.

[0076] The amounts of the monoamines, diamines, monocarboxylic acids, dicarboxylic acids, etc. added are preferably within a range that does not impair the properties of the resulting polyamide elastomer.

[0077] When producing a polyamide elastomer, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. can be added as a catalyst as necessary, and inorganic phosphorus compounds such as phosphorous acid, hypophosphorous acid, and their alkali metal salts and alkaline earth metal salts can be added to achieve both the effects of a catalyst and a heat stabilizer. The catalyst may be used alone or in combination of two or more. The amount added is usually 50 to 3000 ppm by mass based on the charged raw material.

[0078] A heat resistant agent may be used when producing a polyamide elastomer. Organic and inorganic heat resistant agents can be used depending on the purpose. Examples of organic heat resistant agents include phenolic compounds, phosphorus compounds, sulfur compounds, and nitrogen compounds. Examples of inorganic heat resistant agents include copper compounds and potassium halides. The heat resistant agents may be used alone or in combination of two or more.

[0079] To the polyamide-based elastomer, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slipping agents, crystal nucleating agents, tackifiers, sealability improvers, anti-fogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, reinforcing materials, and the like can be added as long as the properties of the polyamide-based elastomer are not impaired.

[0080] <Resin composition containing polyamide-based elastomer> The polyamide-based elastomer can be used as a resin composition together with other thermoplastic resins. The thermoplastic resin contained in the resin composition containing the polyamide-based elastomer includes at least one selected from the group consisting of polyamide resins other than polyamide-based elastomers, polyamideimide resins, polyester resins, polyolefin resins, polystyrene resins, halogenated polyolefin resins, (meth)acrylic resins, polyphenylene ether resins, polycarbonate resins, polyacetal resins, thermoplastic polyurethane resins, and ABS resins. Among these, at least one selected from the group consisting of polyamide resins other than polyamide-based elastomers, polyvinyl chloride resins, thermoplastic polyurethane resins, and ABS resins is preferred from the viewpoint of compatibility with the polyamide-based elastomers.

[0081] To the resin composition containing the polyamide-based elastomer, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slipping agents, crystal nucleating agents, tackifiers, sealability improvers, anti-fogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, reinforcing materials, heat resistance agents, and the like can be added as long as the properties of the resin composition are not impaired.

[0082] A known method can be used to produce a resin composition containing a polyamide-based elastomer, and the composition can be produced, for example, by dry blending a polyamide-based elastomer with another thermoplastic resin and, if necessary, various additives, using a tumbler and / or a mixer, or by dry blending in advance at the concentration to be used during molding and melt-kneading, etc. Melt-kneading can be carried out using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.

[0083] <Molding and molded products> The polyamide-based elastomer and the resin composition containing the polyamide-based elastomer can be molded into a molded product by a known molding method such as injection molding, extrusion molding, blow molding, vacuum molding, or pressure molding. Each molded article can be used for various applications requiring flexibility, such as automobile parts, peripheral parts for electronic devices, battery materials, packing, and sealing materials.

[0084] <Laminate> Polyamide-based elastomers and resin compositions containing polyamide-based elastomers have good adhesion to other thermoplastic resins, and can be used for laminates. Examples of the laminates include laminates containing at least one layer of a polyamide-based elastomer and laminates containing at least one layer of a resin composition containing a polyamide-based elastomer.

[0085] Examples of preferred laminates include a laminate including a layer (X1) made of a polyamide-based elastomer and a layer (Y1) having a different composition from the layer (X1), and a laminate including a layer (X2) made of a composition containing a polyamide-based elastomer and a layer (Y2) having a different composition from the layer (X2). The layer (X1) and the layer (Y1) are preferably adjacent to each other. The layer (X2) and the layer (Y2) are preferably adjacent to each other. The thickness of each layer is not particularly limited, and may be adjusted depending on the type of polymer constituting each layer, the total number of layers in the laminate, the application, and the like. The number of layers in the laminate is two or more, but the total number of layers in the laminate is not particularly limited.

[0086] The layer (Y1) may have a composition different from that of the layer (X1). The resin contained in the layer (Y1) may be at least one selected from the group consisting of a polyurethane resin, a polyamide-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, and a polystyrene-based elastomer. From the viewpoint of adhesion to the layer (X1), the resin contained in the layer (Y1) is preferably a polyurethane resin or a polyurethane-based elastomer.

[0087] The layer (Y2) may have a different composition from the layer (X2). Examples of the resin contained in the layer (Y2) include the same resins as those in the layer (Y1), and the preferred resins include the same resins as those in the layer (Y1).

[0088] Each of the layer (Y1) and the layer (Y2) can contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slipping agent, a crystal nucleating agent, a tackifier, a sealability improver, an antifogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material, a heat resistance agent, and the like, within the range that does not impair the properties of the layer (Y1) and the layer (Y2).

[0089] Examples of the method for producing a laminate include a method of melt extrusion using an extruder corresponding to the number of layers or materials, and laminating simultaneously inside or outside a die (co-extrusion molding method), or a method of first producing a single layer or a laminate produced by the above method in advance, and then laminating the resin on the outside in sequence, if necessary, using an adhesive to integrate the resin (coating method). The laminate is preferably produced by a co-extrusion molding method in which various materials are co-extruded in a molten state, and the two are heat-sealed (melt-bonded) to produce the laminate in one step. That is, the method for producing a laminate preferably includes co-extrusion molding.

[0090] Furthermore, when the obtained laminate has a complex shape or is to be subjected to a heat bending process after molding to form a molded article, in order to remove residual distortion in the molded article, after forming the laminate, it is possible to obtain the desired molded article by heat treating the laminate for 0.01 to 10 hours at a temperature lower than the lowest melting point of the resins constituting the laminate.

[0091] The laminate can be used for applications such as shoe soles. EXAMPLES

[0092] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The various evaluation methods and materials used are shown below. In the evaluation, ◯ means pass and × means fail.

[0093] [Physical property measurement, molding, evaluation method] (1) Quantitative determination of structural units derived from iminodidodecanoic acid contained in polyamide elastomers (when the hard segments are derived from laurolactam and adipic acid) 3 mL of hydrobromic acid was added to 0.1 g of polyamide-based elastomer, and the mixture was hydrolyzed by heating at 140°C for 15 hours. The mixture was then dissolved in dimethyl sulfoxide (DMSO) and adjusted to a volume of 100 mL. The obtained sample solution was subjected to quantitative analysis of iminodidodecanoic acid using a liquid chromatograph / mass spectrometer (LC / MS) manufactured by Agilent Technologies, with a mobile phase of 0.1% aqueous formic acid / acetonitrile. The amount was determined to be the amount of structural units derived from iminodidodecanoic acid contained in the polyamide-based elastomer before hydrolysis.

[0094] (2) Tensile modulus The polyamide-based elastomer was preheated at 200°C for 3 minutes using a hot press machine manufactured by Shinto Metal Industry Co., Ltd., and then hot pressed at 5 MPa for 1 minute. It was then cold pressed at 30°C and 5 MPa for 3 minutes to produce an unstretched polyamide-based elastomer sheet with a thickness of approximately 130 μm. The obtained unstretched polyamide-based elastomer sheet was cut into test pieces of 150 mm length × 10 mm width using a sample cutter manufactured by Dumbbell Co., Ltd. A tensile test was performed on the test pieces in accordance with ISO-527 using a Tensilon tensile tester (Shimadzu AG-I, manufactured by Shimadzu Corporation) in an environment of 23°C and 50% RH, with a chuck distance of 50 mm and a test speed of 300 mm / min, to measure the tensile modulus.

[0095] The tensile modulus was evaluated according to the following criteria. 〇: 91~1100MPa Moderate flexibility. ×: Less than 91 MPa Too soft, no tension. ×: Over 1100 MPa Hard and lacking in flexibility.

[0096] (3) Melting point and crystallization temperature measurement Using a Hitachi High-Tech Science DSC7020, 1 mg of polyamide-based elastomer was heated to 210°C in an aluminum pan under a nitrogen atmosphere and then cooled at 30°C / min. The exothermic peak of crystallization was recorded as the crystallization temperature (Tc), and the endothermic peak of melting was recorded when the temperature was lowered to 30°C and then further heated to 210°C at 10°C / min. as the melting point (Tm).

[0097] The crystallization temperature was evaluated according to the following criteria. ◯: 142.0°C or less The crystallization speed is moderate. ×: Over 142.0° C. The crystallization speed is too fast, and molding defects are likely to occur.

[0098] The melting point was evaluated according to the following criteria. 〇: 136.0℃ or higher Good heat resistance. ×: Less than 136.0℃. Poor heat resistance.

[0099] (4) Dynamic viscoelasticity measurement of solids The polyamide-based elastomer was preheated at 200°C for 3 minutes using a hot press machine manufactured by Shinto Metal Industry Co., Ltd., and then hot pressed at 5 MPa for 1 minute. It was then cold pressed at 30°C and 5 MPa for 3 minutes to produce an unstretched polyamide-based elastomer sheet with a thickness of approximately 130 μm. The unstretched polyamide-based elastomer sheet obtained above was cut into test pieces measuring 38 mm in length and 6 mm in width using a sample cutter manufactured by Dumbbell Co., Ltd. 、T Using an RSA-G2 dynamic mechanical analyzer (DMA) manufactured by A Instruments, the loss modulus E" was measured by increasing the temperature from -135°C to break at a tensile mode, strain of 0.2%, and frequency of 1 Hz. The relaxation temperature was taken as the peak temperature of E".

[0100] The peak temperature of E″ was evaluated according to the following criteria. ○: -53.0℃ or lower. The loss elasticity of the molded product at low temperatures is good. ×: Over -53.0°C The loss elasticity of the molded product at low temperatures is poor.

[0101] (5) Initial peel strength and average peel strength (T-type peel test) To evaluate the adhesion to urethane resin, a T-peel test was performed on a test piece in which two thermoplastic polyurethane sheets were heat-welded via a polyamide-based elastomer, as described below. One side of the thermoplastic polyurethane sheet was pre-welded to a polyimide film so that the thermoplastic polyurethane sheet held during the test would not break. In this test, the adhesion of the polyamide-based elastomer to each thermoplastic polyurethane resin was evaluated for the cases in which BASF's Elastollan ET860D50 (hereinafter referred to as TPU(X)) and BASF's Elastollan 1164D50TR (hereinafter referred to as TPU(Y)) were used as the thermoplastic polyurethane resin.

[0102] (Preparation of test specimens) The polyamide elastomer was preheated at 200°C for 3 minutes using a heat press made by Shinto Metal Industries Co., Ltd., and then heat-pressed at 5 MPa for 1 minute, and then cold-pressed at 30°C and 5 MPa for 3 minutes to produce an unstretched polyamide elastomer sheet with a thickness of about 130 μm. The thermoplastic polyurethane resin was preheated together with one polyimide film using a heat press made by Shinto Metal Industries Co., Ltd., and then heat-pressed at 5 MPa for 1 minute, and then cold-pressed at 30°C and 5 MPa for 3 minutes to produce a two-layered welded sheet of an unstretched thermoplastic polyurethane sheet and a polyimide film with a thickness of about 130 μm. Two of the two-layered welded sheets sandwiched one of the unstretched polyamide elastomer sheets, with the thermoplastic polyurethane sheet side of both of the two two-layered welded sheets facing the polyamide elastomer sheet, and 30 mm from the edge of the sheet was used as a gripping margin for the test, and the sheets were separated so as not to be bonded. Type The sheet was sandwiched between the two sheets, and the other surfaces were heat-pressed at 170°C (corresponding to a temperature above the melting point of the polyamide-based elastomer and below the melting point of the thermoplastic polyurethane) and 5 MPa for 1 minute to obtain a five-layer sheet laminated in the following order: polyimide film / thermoplastic polyurethane sheet / polyamide-based elastomer sheet / thermoplastic polyurethane sheet / polyimide film. The five-layer sheet was cut to a width of 10 mm and a length of 200 mm to prepare a test piece for the T-shaped peel test.

[0103] (T-peel test) The test pieces for the T-peel test prepared in the above steps were subjected to a T-peel test at a test speed of 100 mm / min in an environment of 23°C and 50% RH using a Tensilon tensile tester (Shimadzu AG-I, manufactured by Shimadzu Corporation). The peel strength (N / mm) was calculated by dividing the test force (N) by the test piece width (mm). The maximum peel strength immediately before the first decrease in peel strength after the start of the test was determined as the initial peel strength, and the average value of the peel strengths between peel distances of 50 mm and 100 mm was determined as the average peel strength.

[0104] The adhesion to TPU(X) was evaluated according to the following criteria. Initial peel strength 〇: 10.0N mm ―1 As a result of the above, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, or the substrate of the thermoplastic polyurethane sheet or the polyamide-based elastomer sheet is destroyed, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is good. ×:10.0N mm ―1 At a temperature of less than this, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is poor. Average Peel Strength 〇: 9.5N mm ―1 As a result of the above, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, or the substrate of the thermoplastic polyurethane sheet or the polyamide-based elastomer sheet is destroyed, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is good. ×:9.5N mm ―1 At a temperature of less than this, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is poor.

[0105] The adhesion to TPU (Y) was evaluated according to the following criteria. Initial peel strength 〇: 8.0N mm ―1 As a result of the above, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, or the substrate of the thermoplastic polyurethane sheet or the polyamide-based elastomer sheet is destroyed, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is good. ×:8.0N mm ―1 At a temperature of less than this, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is poor. Average Peel Strength 〇: 7.5N mm ―1 As a result of the above, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, or the substrate of the thermoplastic polyurethane sheet or the polyamide-based elastomer sheet is destroyed, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is good. ×:7.5N mm ―1 At a temperature of less than this, interfacial peeling occurs between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet, and the adhesion between the thermoplastic polyurethane sheet and the polyamide-based elastomer sheet is poor.

[0106] (6) Regarding the proportion of each constituent unit in Table 1, the amount of the constituent unit derived from iminododecanoic acid was calculated according to (1) when the hard segment was derived from laurolactam and adipic acid, and when the hard segment was derived from 12-aminododecanoic acid and adipic acid, it was calculated as a percentage from the charged amount, taking into account the loss of condensation water. The proportion of the constituent units other than those derived from iminododecanoic acid in the hard segment was calculated as a percentage by subtracting the amount of iminododecanoic acid produced or the charged amount taking into account the loss of condensation water from the charged amount of prepolymer. The soft segment was calculated as a percentage from the charged amount of polyetherdiamine. The terminal group used to bond the hard segment and the soft segment is included in the segment having the terminal group. In the table, (A) lactam-derived constituent units do not include constitutional units derived from iminododecanoic acid.

[0107] In the examples and comparative examples, the polyether diamine used was ELASTAMINE RT-1000 (trade name, manufactured by HUNTSMAN), which is an XYX type triblock polyether diamine represented by the above general formula (3) (x=3, y=9, z=2).

[0108] [Example 1] 16.6680g of laurolactam, 3.3342g of adipic acid, and 2.9572g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 270°C and immersed for 10 hours. The ultimate pressure was 2.0MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0109] Next, 7.0339 g of the obtained polyamide 12 prepolymer, 8.3205 g of polyether diamine, and 25.8 mg of sodium hypophosphite were charged into a 34 mmΦ polymerization test tube equipped with a stirrer, a nitrogen inlet tube, and a distillation tube, and the atmosphere was replaced with nitrogen. The mixture was then placed in a salt bath at 230°C, immersed for 6 hours at a stirring speed of 30 rpm and a nitrogen inlet rate of 50 mL / min, and polymerized at normal pressure to obtain a polyamide elastomer. After polymerization, the polyamide elastomer was removed from the test tube, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to perform the above evaluations. The results are shown in Table 1. As shown in Table 1, the polyamide elastomer contained a structural unit derived from iminodidodecanoic acid.

[0110] [Example 2] 16.6706g of laurolactam, 3.3367g of adipic acid, and 4.4715g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 270°C and immersed for 10 hours. The ultimate pressure was 3.0MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0111] Next, a polyamide-based elastomer was obtained in the same manner as in Example 1, except that 7.0578 g of the obtained polyamide 12 prepolymer, 8.3614 g of polyether diamine, and 24.5 mg of sodium hypophosphite were charged, which was then cut into pellets and dried under reduced pressure. The polyamide-based elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1. As shown in Table 1, the polyamide-based elastomer contained a structural unit derived from iminodidodecanoic acid.

[0112] [Example 3] 17.6000g of 12-aminododecanoic acid, 3.3601g of adipic acid, and 0.0085g of iminodidodecanoic acid were charged into a 34mmΦ polymerization test tube equipped with a nitrogen inlet tube and a distillation tube, and the atmosphere was replaced with nitrogen. The tube was then placed in a salt bath at 230°C and immersed for 6 hours without stirring at a nitrogen inlet rate of 50mL / min, and polymerized at normal pressure to obtain a polyamide 12 prepolymer.

[0113] Next, 23.1220g of polyetherdiamine and 70.4mg of sodium hypophosphite were added to the polymerization test tube containing the obtained polyamide 12 prepolymer, and a stirrer was inserted and replaced with nitrogen. The mixture was then placed in a salt bath at 230°C, immersed for 6 hours at a stirring speed of 30 rpm and a nitrogen introduction rate of 50 mL / min, and polymerized at normal pressure to obtain a polyamide elastomer, which was cut into pellets and dried under reduced pressure. The polyamide elastomer was used to carry out the above evaluations. The results are shown in Table 1.

[0114] [Example 4] 16.6673g of laurolactam, 3.3336g of adipic acid, and 4.4735g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 290°C and immersed for 8 hours. The ultimate pressure was 3.5MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0115] Next, a polyamide-based elastomer was obtained in the same manner as in Example 1, except that 7.0165 g of the obtained polyamide 12 prepolymer, 8.2986 g of polyether diamine, and 24.7 mg of sodium hypophosphite were added, which was then cut into pellets and dried under reduced pressure. The polyamide-based elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2. As shown in Table 1, the polyamide-based elastomer contained a structural unit derived from iminodidodecanoic acid.

[0116] [Example 5] 19.7675g of laurolactam, 0.2314g of adipic acid, and 2.3487g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 270°C and immersed for 10 hours. The ultimate pressure was 2.0MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0117] Next, a polyamide-based elastomer was obtained in the same manner as in Example 1, except that 19.1863 g of the obtained polyamide 12 prepolymer, 1.5548 g of polyether diamine, and 18.1 mg of sodium hypophosphite were charged, which was then cut into pellets and dried under reduced pressure. The polyamide-based elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1. As shown in Table 1, the polyamide-based elastomer contained a structural unit derived from iminodidodecanoic acid.

[0118] [Example 6] 19.7678g of laurolactam, 0.2324g of adipic acid, and 4.5744g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 270°C and immersed for 10 hours. The ultimate pressure was 3.0MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0119] Next, a polyamide-based elastomer was obtained in the same manner as in Example 1, except that 14.3927 g of the obtained polyamide 12 prepolymer, 1.1863 g of polyether diamine, and 13.0 mg of sodium hypophosphite were charged, cut into pellets, and dried under reduced pressure. The polyamide-based elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1. As shown in Table 1, the polyamide-based elastomer contained a structural unit derived from iminodidodecanoic acid.

[0120] [Example 7] 19.7683g of laurolactam, 0.2330g of adipic acid, and 4.4912g of pure water were charged into a 21mmΦ test tube and inserted into an 80mL autoclave. After replacing the atmosphere in the autoclave with nitrogen, the tube was placed in a salt bath at 290°C and immersed for 8 hours. The ultimate pressure was 3.5MPa. After the reaction, the inserted test tube was removed to obtain a polyamide 12 prepolymer with carboxyl groups at both ends.

[0121] Next, a polyamide-based elastomer was obtained in the same manner as in Example 1, except that 14.1417 g of the obtained polyamide 12 prepolymer, 1.1769 g of polyether diamine, and 15.4 mg of sodium hypophosphite were charged, cut into pellets, and dried under reduced pressure. The polyamide-based elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1. As shown in Table 1, the polyamide-based elastomer contained a structural unit derived from iminodidodecanoic acid.

[0122] [Example 8] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 21.1600 g of 12-aminododecanoic acid, 0.2225 g of adipic acid, and 0.0297 g of iminodidodecanoic acid were charged.

[0123] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 1.6123 g of polyether diamine and 19.2 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1.

[0124] [Example 9] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 17.6000 g of 12-aminododecanoic acid, 3.3450 g of adipic acid, and 0.0937 g of iminodidodecanoic acid were charged.

[0125] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 23.1220 g of polyether diamine and 70.4 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2.

[0126] [Example 10] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 17.5000 g of 12-aminododecanoic acid, 0.9254 g of adipic acid, and 0.0118 g of iminodidodecanoic acid were charged.

[0127] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 6.5700 g of polyether diamine and 60.0 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2.

[0128] [Example 11] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 17.5000 g of 12-aminododecanoic acid, 0.9200 g of adipic acid, and 0.0423 g of iminodidodecanoic acid were charged.

[0129] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 6.5700 g of polyether diamine and 60.0 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Table 1.

[0130] [Example 12] As shown in Table 3, 30 g of a polyamide-based elastomer having a Shore D hardness of 55 manufactured by UBE Corporation, which has a polyamide structure consisting of laurolactam and adipic acid-derived structural units, a hard segment containing a structural unit derived from a dicarboxylic acid compound, and a soft segment consisting of a structural unit derived from a polyetherdiamine containing an XYX-type triblock polyether, and 0.051 g of iminodidodecanoic acid were charged into a 34 mmΦ polymerization test tube equipped with a nitrogen inlet tube and a distillation tube, and nitrogen was substituted. Then, the mixture was placed in a metal bath at 230°C and polymerized at normal pressure for 1 hour under a nitrogen atmosphere to obtain a polyamide-based elastomer having the above structural units as well as structural units derived from iminodidodecanoic acid, which was cut into pellets and dried under reduced pressure. The results of the above evaluation are shown in Table 3.

[0131] [Example 13] As shown in Table 3, 30 g of PEBAX (registered trademark) 6333 manufactured by ARKEMA, which has a polyamide structure consisting of laurolactam and adipic acid-derived structural units, a hard segment containing a structural unit derived from a dicarboxylic acid compound, and a soft segment consisting of a structural unit derived from a polyether diol, and 0.051 g of iminodidodecanoic acid were charged into a 34 mmΦ polymerization test tube equipped with a nitrogen inlet tube and a distillation tube, and nitrogen was substituted. Then, the mixture was placed in a metal bath at 230°C and polymerized at normal pressure under a nitrogen atmosphere for 1 hour to obtain a polyamide-based elastomer having the above structural units as well as structural units derived from iminodidodecanoic acid, which was cut into pellets and dried under reduced pressure. The results of the above evaluation are shown in Table 3.

[0132] [Comparative Example 1] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that iminodidodecanoic acid was not added, and only 17.6000 g of 12-aminododecanoic acid and 3.3616 g of adipic acid were added.

[0133] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 23.1220 g of polyether diamine and 70.4 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2.

[0134] [Comparative Example 2] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 17.6000 g of 12-aminododecanoic acid, 3.3428 g of adipic acid, and 0.1065 g of iminodidodecanoic acid were charged.

[0135] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 23.1220 g of polyether diamine and 70.4 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2.

[0136] [Comparative Example 3] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that iminodidodecanoic acid was not added, and only 17.5000 g of 12-aminododecanoic acid and 0.9275 g of adipic acid were added.

[0137] Next, in the polymerization test tube still containing the obtained polyamide 12 prepolymer, 6.5700 g of polyether diamine and 60.0 mg of sodium hypophosphite were added, and the polyamide elastomer was obtained in the same manner as in Example 3, cut into pellets, and dried under reduced pressure. The polyamide elastomer was used to carry out the above-mentioned evaluations. The results are shown in Tables 1 and 2.

[0138] [Comparative Example 4] A polyamide 12 prepolymer was obtained in the same manner as in Example 3, except that 17.5000 g of 12-aminododecanoic acid, 0.9109 g of adipic acid, and 0.0940 g of iminodidodecanoic acid were charged.

[0139] [Table 1]

[0140] [Table 2]

[0141] [Table 3]

[0142] In Tables 1, 2 and 3, the proportion of each structural unit is the value when all structural units of the polyamide-based elastomer containing that structural unit are taken as 100 mass %. As can be seen from Table 1, Examples 1 to 11, which contain a constituent unit derived from iminodidodecanoic acid as a constituent unit, have appropriate flexibility represented by the tensile modulus, and also have good heat resistance, low-temperature properties, and moldability. Comparative Example 1, in which the hard segment / soft segment (mass ratio) was 1 or less and which did not contain any structural units derived from iminodidodecanoic acid, had a low tensile modulus and was too flexible. Comparative Example 3, in which the hard segment / soft segment (mass ratio) was 1 or more and the structural units did not include a structural unit derived from iminodidodecanoic acid, had poor low-temperature properties. In Comparative Example 2, in which the hard segment / soft segment (mass ratio) is 1 or less and the constituent units derived from iminodidodecanoic acid exceed 0.50 parts by mass per 100 parts by mass of the hard segment, the tensile modulus is low and the flexibility is too high, and the melting point is low and the heat resistance is poor. Comparative Example 4, in which the hard segment / soft segment (mass ratio) is 1 or more and the content of the constitutional unit derived from iminodidodecanoic acid exceeds 0.50 parts by mass per 100 parts by mass of the hard segment, has poor low-temperature properties. From Table 2, it can be seen that the Examples show sufficiently good values ​​for both the initial peel strength and the average peel strength, and have good adhesion to the urethane resin, whereas the Comparative Examples show poor values ​​for the average peel strength, and have poor adhesion to the urethane resin. [Industrial Applicability]

[0143] Polyamide-based elastomers are used as molded articles by injection molding, extrusion molding, blow molding, vacuum molding, pressure molding, etc., and the molded articles can be used for various applications requiring flexibility, such as automobile parts, peripheral parts for electronic devices, battery materials, packing, sealing materials, etc. Furthermore, as laminates, they can be used for shoe soles, etc.

Claims

1. A polyamide-based elastomer comprising a hard segment including a polyamide structure (A) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the following general formula (I), and a soft segment including a polyether structure (B): the structural unit (D) is more than 0 part by mass and 0.50 parts by mass or less with respect to 100 parts by mass of the hard segment, The polyamide structure (A) is composed of a structural unit derived from an aminocarboxylic acid compound. Polyamide elastomer. 【Chemistry 14】 (In the general formula (I), R １ and R ２ are each independently an alkylene group having 2 to 20 carbon atoms.

2. The polyamide-based elastomer according to claim 1 , wherein the polyamide-based elastomer contains more than 0% by mass and less than 0.22% by mass of the structural unit (D), based on 100% by mass of all structural units of the polyamide-based elastomer.

3. 2. The polyamide-based elastomer according to claim 1, wherein a mass ratio of the hard segment to the soft segment is hard segment / soft segment=95 / 5 to 20 / 80.

4. The polyamide-based elastomer according to claim 1 , wherein the polyether structure (B) contains an XYX triblock polyether represented by the following general formula (5): 【Chemistry 15】 (In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.)

5. The polyamide elastomer according to claim 1 , wherein the hard segment comprises a structural unit (C) derived from a dicarboxylic acid compound (c) not containing an imino group.

6. The polyamide structure (A) has a structural unit derived from an aminocarboxylic acid compound represented by the following general formula (1), and the polyether structure (B) has a structural unit derived from an XYX type triblock polyether diamine compound represented by the following general formula (3), The polyamide-based elastomer according to claim 1, further comprising a structural unit (C) derived from a dicarboxylic acid compound represented by the following general formula (4) and a structural unit (D) derived from an iminodialkanoic acid compound (d) represented by the general formula (I): 【Chemistry 16】 [In the formula, R ３ represents a linking group containing a hydrocarbon chain. 【Chemistry 17】 [In the formula, R ３ represents a linking group containing a hydrocarbon chain. 【Chemistry 18】 [In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20.] 【Chemistry 19】 [In the formula, R ４ represents a linking group that contains a single bond or a hydrocarbon chain and does not contain an imino group.

7. 2. The polyamide elastomer according to claim 1, which has a melting point of 136.0° C. or higher as determined from an endothermic peak of melting when heated to 210° C. at a rate of 10° C. / min using a differential scanning calorimeter.

8. 2. The polyamide elastomer according to claim 1, having a tensile modulus of elasticity of 91 to 1100 MPa as measured in accordance with ISO-527.

9. (Step 1) A step of ring-opening polymerization of a lactam compound in the presence of an iminodialkanoic acid compound (d) represented by the following general formula (I) and any dicarboxylic acid (c) not containing an imino group to produce a polyamide prepolymer having a polyamide structure (A), a structural unit (D) derived from the iminodialkanoic acid compound (d) and any structural unit (C) derived from the dicarboxylic acid (c) not containing an imino group; (Step 2) reacting a polyether compound having a polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide-based elastomer comprising the steps of: 【Chemistry 14】 (In general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms.)

10. (Step 1) A step of polycondensing an aminocarboxylic acid compound in the presence of an iminodialkanoic acid compound (d) represented by the following general formula (I) and any dicarboxylic acid (c) not containing an imino group to produce a polyamide prepolymer having a polyamide structure (A), a structural unit (D) derived from the iminodialkanoic acid compound (d) and any structural unit (C) derived from the dicarboxylic acid (c) not containing an imino group; (Step 2) reacting a polyether compound having a polyether structure (B) with the polyamide prepolymer obtained in Step 1; The method for producing a polyamide-based elastomer comprising the steps of: 【Chemistry 14】 (In general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms.)

11. A method for producing a polyamide-based elastomer, comprising polymerizing a polyamide-forming monomer, a polyether compound having a polyether structure (B), an iminodialkanoic acid compound (d) represented by the following general formula (I), and a dicarboxylic acid (c) not containing any imino group: 【Chemistry 14】 (In general formula (I), R 1 and R 2 are each independently an alkylene group having 2 to 20 carbon atoms.)

12. A layer comprising the polyamide elastomer according to any one of claims 1 to 8.

13. A laminate comprising a layer (X1) made of the polyamide-based elastomer according to any one of claims 1 to 8, and a layer (Y1) having a composition different from that of the layer (X1).

14. The laminate according to claim 13, wherein the layer (X1) and the layer (Y1) are adjacent to each other.

15. The laminate according to claim 13, wherein the layer (Y1) contains at least one resin selected from the group consisting of a polyurethane resin, a polyamide-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, and a polystyrene-based elastomer.

16. A molded article comprising the polyamide elastomer according to any one of claims 1 to 8.

17. A resin composition comprising the polyamide elastomer according to any one of claims 1 to 8.

18. The resin composition according to claim 17, which contains at least one thermoplastic resin selected from the group consisting of polyamide resins other than polyamide-based elastomers, polyamideimide resins, polyester resins, polyolefin resins, polystyrene resins, halogenated polyolefin resins, (meth)acrylic resins, polyphenylene ether resins, polycarbonate resins, polyacetal resins, thermoplastic polyurethane resins, and ABS resins.

19. A layer comprising the resin composition according to claim 17.

20. A laminate comprising a layer (X2) made of the resin composition according to claim 17 and a layer (Y2) having a composition different from that of the layer (X2).

21. The laminate according to claim 20, wherein the layer (X2) and the layer (Y2) are adjacent to each other.

22. The laminate according to claim 20, wherein the layer (Y2) contains at least one resin selected from the group consisting of a polyurethane resin, a polyamide-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, and a polystyrene-based elastomer.

23. A molded article comprising the resin composition according to claim 17.

Images