WO2024225376A1 - ポリアミドブロック共重合体、ポリアミドブロック共重合体組成物、及び成形体 - Google Patents

ポリアミドブロック共重合体、ポリアミドブロック共重合体組成物、及び成形体 Download PDF

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WO2024225376A1
WO2024225376A1 PCT/JP2024/016237 JP2024016237W WO2024225376A1 WO 2024225376 A1 WO2024225376 A1 WO 2024225376A1 JP 2024016237 W JP2024016237 W JP 2024016237W WO 2024225376 A1 WO2024225376 A1 WO 2024225376A1
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polyamide
block copolymer
temperature
polyamide block
acid
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French (fr)
Japanese (ja)
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大樹 南口
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to CN202480027533.0A priority Critical patent/CN121039206A/zh
Priority to EP24797121.1A priority patent/EP4703408A1/en
Priority to JP2025516884A priority patent/JPWO2024225376A1/ja
Publication of WO2024225376A1 publication Critical patent/WO2024225376A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polyamide block copolymer, a polyamide block copolymer composition, and a molded article.
  • Thermoplastic elastomers can be melt-molded and are used in a wide range of fields, such as automotive interior and exterior parts, electronic equipment parts, and sporting goods.
  • Thermoplastic elastomers contain soft segments that exhibit flexibility and hard segments that exhibit crosslinking points, and are classified into, for example, olefin-based, amide-based, urethane-based, ester-based, acrylic-based, and styrene-based.
  • Thermoplastic elastomers can exhibit good physical properties such as mechanical strength, abrasion resistance, heat resistance, and oil resistance according to the above classification, and further improvements are being considered.
  • 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).
  • Patent Document 2 relates to a heat-resistant polyether polyamide elastomer (paragraph [0008]).
  • This patent document 2 discloses a polyether polyamide elastomer that uses a polyether diamine compound containing an isopropenylene group (-CH(CH 3 )CH 2 - or -CH 2 CH(CH 3 )-) and xylylene diamine as diamine constituent units, and uses an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 8 to 20 carbon atoms as a dicarboxylic acid constituent unit (claim 1, paragraph [0020]).
  • an object of the present invention is to provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article that have an excellent balance between strength and flexibility. Furthermore, other objects of the present invention will be apparent to those skilled in the art upon reading this specification.
  • the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.
  • a polyamide block copolymer having a melting point of 230° C. or higher comprising a polymer block (A) containing 50 mol % or more of a structural unit derived from polyamide and a polymer block (B) having a glass transition temperature of 20° C. or lower,
  • a test piece having a length of 20 mm, a width of 5 mm, and a thickness of 100 ⁇ m 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.
  • the temperature T0 [° C.] at which the loss tangent in the temperature range of ⁇ 100° C. to 160° C. reaches a maximum value tan ⁇ (max) is calculated by 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 ⁇ (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 ⁇ (max) are expressed by the following formula (2): Formula (2): (T2-T1) ⁇ 170 Satisfy the relationship Polyamide block copolymer.
  • polyamide block copolymer according to any one of [1] to [8], wherein the polymer block (B) contains a structural unit derived from a polyether polyol, a polyester polyol, a polycarbonate polyol, a polysiloxane polyol, or an amine derivative or a carboxyl derivative thereof.
  • polyamide block copolymer according to any one of [1] to [9], wherein the polyamide block copolymer has a number average molecular weight of 50,000 or less.
  • 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.
  • polyamide block copolymer according to any one of [1] to [11], wherein the molecular weight distribution (weight average molecular weight/number average molecular weight) of the polyamide block copolymer is 2.0 to 14.5.
  • a polyamide block copolymer composition comprising the polyamide block copolymer according to any one of [1] to [12].
  • the present invention can provide a polyamide block copolymer, a polyamide block copolymer composition, and a molded article that have an excellent balance between strength and flexibility.
  • Example 1 is a graph of a temperature-loss tangent curve obtained by measuring a test piece of the polyamide block copolymer of Example 1.
  • unit means "a structural unit derived from", for example, a “dicarboxylic acid unit” means “a structural unit derived from a dicarboxylic acid”, and a “diamine unit” means “a structural unit derived from a diamine”.
  • 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 less, and has a melting point of 230° C. or more.
  • the polyamide block copolymer of this embodiment has a temperature-loss tangent (tan ⁇ ) curve obtained by viscoelasticity measurement having a specific shape.
  • the polyamide block copolymer of this embodiment has a temperature-loss tangent curve with a specific shape, and therefore has an excellent balance between strength and flexibility.
  • the polymer block (A) is a hard segment and the polymer block (B) is a soft segment, and the properties of each polymer block can be fully exhibited.
  • 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 ISO11357-3 (2011, 2nd edition). Such differential scanning calorimetry can be performed in more detail by the method described in the Examples.
  • a polyamide block copolymer has sufficient heat resistance when its Tm is 230°C or higher. It is 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.
  • the temperature T0 [°C] at which the loss tangent in the temperature range of -100°C to 160°C reaches a maximum value tan ⁇ (max) in the temperature-loss tangent curve is , 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 ⁇ (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 ⁇
  • the second temperature T2 [°C] indicating the half value of (max) is expressed by the following formula (2): Formula (2): (T2-T1) ⁇ 170 Satisfy the relationship.
  • 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 ⁇ m using a viscoelasticity measuring device at a chuck distance of 10 mm, a frequency of 1 Hz, and a temperature rise rate of 3° C./min in the temperature range of ⁇ 100° C. to 330° C.
  • a viscoelasticity measuring device at a chuck distance of 10 mm, a frequency of 1 Hz, and a temperature rise rate of 3° C./min in the temperature range of ⁇ 100° C. to 330° C.
  • Such dynamic viscoelasticity measurement can be carried out 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 out from a molded body of the polyamide block copolymer.
  • the method described in the Examples is preferably used. Even when the test piece is obtained by cutting out from a molded body of the polyamide block copolymer, the dynamic viscoelasticity measurement can be performed by the method described in the Examples.
  • the polyamide block copolymer of this embodiment has a temperature T0 of -60°C or more and 120°C or less (Equation (1)).
  • Temperature T0 is the temperature at which the loss tangent value is a maximum value tan ⁇ (max) in the temperature range of -100°C to 160°C on the temperature-loss tangent curve.
  • the maximum value tan ⁇ (max) is the value of the loss tangent at the peak top of the maximum peak
  • temperature T0 is the temperature at the peak top of the maximum peak.
  • the T0 of the polyamide block copolymer may be -55°C or higher, -50°C or higher, more preferably -45°C or higher, -40°C or higher, or in some cases -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, 100°C or lower, or in some cases 95°C or lower, 90°C or lower, or 85°C or lower.
  • Preferred ranges of 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, and -40°C to 100°C.
  • the polyamide block copolymer of this embodiment has a temperature range (T2-T1) of 170°C or less (Equation (2)).
  • the first temperature T1 and the second temperature T2 are temperatures that indicate half the maximum value tan ⁇ (max) on the temperature-loss tangent curve.
  • there may be multiple candidates for the first temperature and/or the second temperature there may be multiple candidates for the first temperature and/or the second temperature. In this case, the temperatures closest to T0 are adopted as the first temperature T1 and the second temperature T2.
  • 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, it is preferable that the temperature range (T2-T1) is 45°C or more, 50°C or more, or 60°C or more.
  • 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 later.
  • the loss tangent of the temperature-loss tangent curve has two maximum values in the temperature range of -100°C to 160°C.
  • the temperature-loss tangent curve shown in Fig. 1 has two peaks in the temperature range of -100°C to 160°C.
  • the temperature-loss tangent curve of a polyamide block copolymer containing hard segments and soft segments usually tends to have at least two peaks, as shown in Figure 1.
  • One of the two peaks is a low-temperature peak and the other is a high-temperature peak.
  • the present invention specifies that when the temperature-loss tangent curve of a polyamide block copolymer has two peaks, one on the low-temperature side and one on the high-temperature side, the peak with the larger loss tangent value at the peak top satisfies the above formulas (1) and (2).
  • the peak with the larger loss tangent value at the peak top satisfies the above formulas (1) and (2).
  • the copolymer has an excellent balance of strength and flexibility.
  • the reason why a polyamide block copolymer that has a temperature-loss tangent curve with peaks that satisfy both the above formula (1) and the above formula (2) has an excellent balance between strength and flexibility is not completely clear.
  • the peak with a larger loss tangent value at the peak top, preferably the high-temperature peak, derived from the hard segment polymer block (A) tends to satisfy both the above formula (1) and the above formula (2), and therefore the properties such as strength expected of the hard segment are maintained, and the soft segment can fully exhibit properties such as flexibility, resulting in an excellent balance between strength and flexibility.
  • the polymer block (A) contains 50 mol% or more of structural units derived from polyamide. From the viewpoint of easily obtaining even more excellent heat resistance, the polymer block (A) contains preferably 70 mol% or more, more preferably 90 mol% or more, and may contain 100 mol% of structural units derived from polyamide. In the polymer block (A), structural units other than the structural units derived from polyamide are not limited as long as the effects of the present invention can be obtained.
  • the polyamide that can be used in the present embodiment is not limited as long as it can realize a melting point of 230° C. or higher of the polyamide block copolymer and can obtain the effects of the present invention, and examples thereof include semi-aromatic polyamides, fully aromatic polyamides, and aliphatic polyamides.
  • semi-aromatic polyamides and aliphatic polyamides are polyamides in which the effects of the present invention are more pronounced. From the viewpoint of easily obtaining even more excellent heat resistance, it is particularly preferable to use semi-aromatic polyamides as the polyamide.
  • the aliphatic polyamide include polytetramethylene adipamide (polyamide 46) and polyhexamethylene adipamide (polyamide 66).
  • Semi-aromatic polyamides that can be suitably used in this embodiment will be described in detail below.
  • the semi-aromatic polyamide refers to a polyamide containing 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, or a polyamide resin containing dicarboxylic acid units mainly composed of structural units derived from an aliphatic dicarboxylic acid and diamine units mainly composed of structural units derived from an aromatic diamine.
  • "mainly composed” means that the diamine units or dicarboxylic acid units constitute 50 to 100 mol %, preferably 60 to 100 mol %, of all units in the diamine units or dicarboxylic acid units.
  • 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.
  • the polymer block (A) preferably contains 50 mol % or more of structural units derived from a semi-aromatic polyamide, more preferably the polymer block (A) contains less than 50 mol % or less of structural units derived from a non-semi-aromatic polyamide, even more preferably the polymer block (A) contains 10 mol % or less of structural units derived from a non-semi-aromatic polyamide, and even more preferably the polymer block (A) does not contain any structural units derived from a non-semi-aromatic polyamide (i.e., 0 mol %).
  • 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.
  • the content of constituent 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 may be 100 mol%.
  • 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-di
  • 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 a linear aliphatic diamine and a branched aliphatic diamine.
  • 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.
  • 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.
  • the above molar ratio may also be 80:20 to 20:80, 70:30 to 30:70, or 65:35 to 35:65.
  • the semi-aromatic polyamide preferably contains a structural unit 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 a structural unit 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 a structural unit derived from at least one aliphatic diamine selected from the group consisting of 1,9-nonan
  • the semi-aromatic polyamide contains structural units derived from both 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 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 the semi-aromatic polyamide contains structural units derived from both 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
  • 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%.
  • 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.
  • 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.
  • the molar ratio may be 80:20 to 20:80, 70:30 to 30:70, or 65:35 to 35:65.
  • 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%.
  • 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 even more preferably 85:15 to 15:85.
  • the semi-aromatic polyamide may contain, as a diamine unit, a structural unit derived from a diamine other than an aliphatic diamine, such as an aromatic diamine, as long as the effect of the present invention is not impaired.
  • the structural unit derived from a diamine other than an aliphatic diamine may be contained in one type or in two or more types.
  • the content of structural units derived from other than the 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.
  • 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.
  • 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, and from the viewpoint of further improving heat resistance, it is more preferable that the aromatic dicarboxylic acid contains a structural unit derived from at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • the content of constituent units derived from at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid relative to the total dicarboxylic acid units is preferably 30 mol% or more, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and may be 100 mol%.
  • the semi-aromatic polyamide may contain, as a dicarboxylic acid unit, a constitutional unit derived from a dicarboxylic acid other than an aromatic dicarboxylic acid, such as an aliphatic dicarboxylic acid, as long as the effect of the present invention is not impaired. Only one type of constitutional unit derived from a dicarboxylic acid other than an aromatic dicarboxylic acid may be contained, or two or more types of constitutional units derived from a dicarboxylic acid other than an aromatic dicarboxylic acid may be contained.
  • aliphatic dicarboxylic acid examples 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; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and the like.
  • linear aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, se
  • the content of constituent units derived from other than the aromatic dicarboxylic acid in the dicarboxylic acid unit 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.
  • the content of the constituent units derived from the aliphatic diamine relative to all the constituent units constituting the semi-aromatic polyamide is preferably from 15 to 55 mol %, and more preferably from 25 to 55 mol %.
  • the content of the constituent units derived from aromatic dicarboxylic acid relative to all the constituent units constituting the semi-aromatic polyamide is preferably 15 to 55 mol %, and more preferably 25 to 55 mol %.
  • the total content of the constituent units derived from the aliphatic diamine and aromatic dicarboxylic acid relative to all the constituent units constituting the semi-aromatic polyamide is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and even more preferably 70 to 100 mol%, and may be 90 to 100 mol%, or may be 100 mol%.
  • the semi-aromatic polyamide may contain other structural units than the diamine unit and the dicarboxylic acid unit, as long as the effect of the present invention is not impaired.
  • the other structural units include a polycarboxylic acid unit, an aminocarboxylic acid unit, and a lactam unit.
  • the polyvalent carboxylic acid unit include structural units derived from trivalent or higher polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, etc. These polyvalent carboxylic acid units can be contained to the extent that melt molding is possible.
  • aminocarboxylic acid unit examples include structural units derived from lactams such as caprolactam and lauryllactam; and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
  • lactam unit examples include structural units derived from ⁇ -caprolactam, enantholactam, undecane lactam, lauryllactam, ⁇ -pyrrolidone, ⁇ -piperidone, and the like.
  • the content of other structural units relative to all structural units constituting the semi-aromatic polyamide is preferably 30 mol % or less, and more preferably 10 mol % or less.
  • 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-methylpentamethylene)terephthalamide copolymer (polyamide 6T/M5T), polynonamethylene terephthalamide (polyamide 9T), poly(2-methyloctamethylene)terephthalamide copolymer (polyamide 9T/M5 ...
  • phthalamide 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) naphthalene dicarboxamide 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
  • 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 a structural unit derived from an end-capping agent.
  • the content of the structural units derived from the terminal blocking 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 still more preferably 2.5 to 6.5 mol %.
  • the content of the structural unit derived from the terminal blocking agent can be adjusted by the amount of the terminal blocking agent charged relative to the diamine when the polymerization raw materials are charged. In consideration of the volatilization of the monomer component during polymerization, it is desirable to finely adjust the amount of the terminal blocking agent charged when the polymerization raw materials are charged so that a desired amount of the structural unit derived from the terminal blocking agent is introduced into the obtained polyamide.
  • the terminal blocking agent can also be charged so as to be in the above-mentioned desired range.
  • the terminal blocking agent can also be charged to the polymer constituting the polymer block (A) together with the terminal functionalizing agent described later so as to be in the above-mentioned desired range.
  • a method for determining the content of structural units derived from an end-capping agent in a polyamide for example, as disclosed in JP-A-07-228690, a method can be mentioned in which the solution viscosity is measured, the total amount of end groups is calculated from the relational equation between the viscosity and the number average molecular weight, and the amount of amino groups and the amount of carboxyl groups determined by titration are subtracted from the total amount of end groups.
  • a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used.
  • Specific examples include monocarboxylic acid, acid anhydride, monoisocyanate, monoacid halide, monoester, monoalcohol, monoamine, etc.
  • a monocarboxylic acid is preferable as a terminal blocking agent for a terminal amino group
  • a monoamine is preferable as a terminal blocking agent for a terminal carboxyl group.
  • a monocarboxylic acid is more preferable as a terminal blocking agent.
  • monocarboxylic acid used as the terminal blocking agent, so long as it is reactive with amino groups.
  • monocarboxylic acids 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 cyclopentane carboxylic acid and cyclohexane carboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalene carboxylic acid, ⁇ -naphthalene carboxylic acid, and methylnaphthalene carboxylic acid; monocarboxylic acids having aromatic alkyl groups such as phenyl acetic acid; and mixtures of any of
  • 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 blocked terminals, and price.
  • monoamines used as the end-capping agent there are no particular limitations on the monoamines used as the end-capping agent, so long as they are reactive with carboxyl groups.
  • monoamines 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 of 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 end, and price.
  • Polyamide can be produced, for example, from dicarboxylic acid and diamine as raw materials by a method such as melt polymerization, solid-state polymerization, melt extrusion polymerization, etc.
  • polyamide can be produced as follows. First, a nylon salt is produced by mixing a diamine, a dicarboxylic acid, and, if necessary, an aminocarboxylic acid, a lactam, a catalyst, an end-capping agent, etc. Next, the produced nylon salt is heated to a temperature of 200 to 250° C. and thermally polymerized to obtain a polyamide prepolymer.
  • the molecular weight of the polyamide can be adjusted to a desired level by subjecting the prepolymer to solid-phase polymerization or by increasing the degree of polymerization using a melt extruder.
  • the high polymerization stage is carried out by solid-state polymerization, it is preferably carried out under reduced pressure or in an inert gas flow, and the polymerization rate is high, productivity is excellent, and coloration and gelation can be effectively suppressed if the polymerization temperature is within the range of 200 to 280° C.
  • the polymerization temperature is preferably 370° C. or less, and when polymerization is carried out under such conditions, a polyamide with almost no decomposition and little deterioration can be obtained.
  • 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; ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, octadecyl esters, decyl esters, stearyl esters, and phenyl esters of phosphoric acid, phosphorous acid, or hypophosphorous acid.
  • the amount of catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the raw material of the polyamide (100% by mass).
  • the amount of catalyst used is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. If the amount of catalyst used is the above lower limit or more, polymerization proceeds more smoothly.
  • the terminals of the polyamide can be adjusted to a desired functional group or amount of functional groups by using a terminal functionalizing agent described later.
  • the terminal amino group content referred to here is the terminal amino group content in the polyamide before the terminals are converted with a terminal functionalizing agent.
  • the polyamide before the above-mentioned terminal conversion has a terminal amino group content ([NH 2 ]), which is the content of its terminal amino groups, of preferably 1 to 4,000 ⁇ mol/g, more preferably 1 to 3,000 ⁇ mol/g, even more preferably 1 to 2,500 ⁇ mol/g, still more preferably 1 to 2,000 ⁇ mol/g, even more preferably 1 to 1,500 ⁇ mol/g, and still more preferably 1 to 1,000 ⁇ mol/g.
  • the terminal amino group content ([NH 2 ]) referred to in this specification refers to the amount (unit: ⁇ mol) of terminal amino groups contained in 1 g of polyamide, and can be determined by neutralization titration using an indicator.
  • the polyamide before the above-mentioned terminal conversion has a terminal carboxyl group content ([COOH]), which is the content of terminal carboxyl groups, of preferably 1 to 5,000 ⁇ mol/g, more preferably 25 to 4,000 ⁇ mol/g, even more preferably 50 to 3,000 ⁇ mol/g, still more preferably 75 to 2,500 ⁇ mol/g, even more preferably 75 to 2,000 ⁇ mol/g, and still more preferably 75 to 1,500 ⁇ mol/g.
  • the terminal carboxyl group content ([COOH]) in this specification refers to the amount of terminal carboxyl groups (unit: ⁇ mol) contained in 1 g of polyamide, and can be determined by potentiometric titration.
  • 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 more easily improved.
  • the melting point of the polyamide is preferably 320°C or lower. That is, the melting point of the polyamide is preferably 120 to 320°C.
  • the melting point can be determined as the peak temperature of a melting peak that appears when the temperature is raised at a rate of 10° C./min using a differential scanning calorimetry (DSC) analyzer. More specifically, the melting point can be determined by the method described in the examples below.
  • the semi-aromatic ratio (%) of the polyamide can be determined by a method well known to those skilled in the art.
  • the semi-aromatic ratio of the polyamide means the ratio (percentage) of the repeating units of the semi-aromatic polyamide among the repeating units constituting the polyamide.
  • the semi-aromatic ratio of the polyamide can be determined, for example, by using NMR, and in this case, it is a molar ratio.
  • the semi-aromatic ratio of the 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 the polyamide may be 100%.
  • the semi-aromatic ratio of the polyamide is 90% or more, preferably 94% or more.
  • the semi-aromatic ratio of the polyamide is 100%.
  • 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 may be 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 the strength and flexibility tends to be even more excellent.
  • the weight average molecular weight of the polymer block (A) is preferably 1,000 to 50,000, more preferably 1,100 to 45,000, even more preferably 1,200 to 40,000, still more preferably 1,300 to 40,000, still more preferably 1,400 to 30,000, 1,600 to 25,000, or 2,000 to 20,000.
  • the compatibility between the polymer block (A) and the polymer block (B) is likely 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 the 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.
  • the compatibility between the polymer block (A) and the polymer block (B) is likely to be excellent, and the balance between the strength and flexibility tends to be even better.
  • the number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography, and more specifically, are values measured by the method described in the examples.
  • a terminal functionalizing agent can be used to adjust the terminal of the polymer block (A), preferably the terminal of the polyamide, more preferably the terminal of the semi-aromatic polyamide, to a desired functional group or amount of functional groups.
  • the terminals of the polyamide can be converted by reacting a terminal functionalizing agent with the above-mentioned polyamide prepolymer. It is also possible to convert the terminals of the polyamide by making either the dicarboxylic acid unit or the diamine unit in excess at the stage of charging the raw materials.
  • the polymer block (A) and the polymer block (B) can be bonded more satisfactorily.
  • the units derived from the terminal functionalizing agent are included in the polymer block (A).
  • the polyamide has a desired functional group or amount of functional groups
  • a terminal functionalizing agent 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, whereby the polymer block (A) and the polymer block (B) can be satisfactorily bonded to each other.
  • the amount of active terminal functional groups in the polyamide which will be described later, can be adjusted, for example, by adjusting the amount of carboxyl groups and the amount of amino groups contained in the reaction raw materials in the production of the polyamide.
  • terminal functionalizing agent 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 to the terminals of polyamide.
  • the terminal functionalizing agent is preferably a compound selected from the group consisting of dicarboxylic acids and diamines.
  • 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 dicarboxylic acids and diamines.
  • 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 aromatic dicarboxylic acids as the terminal functionalizing agent.
  • aliphatic dicarboxylic acids examples 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; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and the like.
  • linear aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, se
  • 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
  • Diamines that can be used as end-functionalizing agents include aliphatic and aromatic diamines.
  • the aliphatic diamines include linear aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, and 1,18-octadecanediamine; 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 2-e
  • aromatic diamines examples 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 agent may be used alone or in combination of two or more kinds.
  • the “active terminal functional group content” refers to the content of the active terminal functional group of the polymer block (A) contained in the polyamide block copolymer, and the total content of the active terminal functional groups of the polyamide is
  • the "active terminal functional group” is a functional group that exhibits a reaction activity with the terminal functional group of the polymer block (B), and is an amino group and a carboxyl group. groups, etc.
  • the “active terminal functional group content” refers to the content of the active terminal functional group after the terminal functional group is converted.
  • a polyamide having an amino group at its terminal is converted to a carboxyl group using a terminal functionalizing agent, the total content of the converted terminal carboxyl group and the unconverted terminal amino group is the active terminal functional group content of the polymer block (A). .
  • the active terminal functional group content of the polymer block (A) may be any content of functional groups capable of sufficiently reacting with the terminal functional groups of the polymer block (B), and is preferably 5 ⁇ mol/g or more or 50 to 5,000 ⁇ mol/g, more preferably 75 to 4,500 ⁇ mol/g, even more preferably 100 to 4,000 ⁇ mol/g, still more preferably 120 to 4,000 ⁇ mol/g, still more preferably 150 to 4,000 ⁇ mol/g, still more preferably 200 to 4,000 ⁇ mol/g, still more preferably 250 to 4,000 ⁇ mol/g, and still more preferably 300 to 4,000 ⁇ mol/g.
  • the active terminal functional group content is 5 ⁇ mol/g or more, the compatibility between the polymer block (A) and the polymer block (B) is excellent, and the flexibility of the polyamide block copolymer can be further improved. Furthermore, if the content of the active terminal functional group is 5,000 ⁇ mol/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: ⁇ mol) of active terminal functional groups contained in 1 g of polyamide (or polyamide after conversion in the case of using a terminal functionalizing agent), and can be determined by neutralization titration method and potentiometric titration method using an indicator.
  • 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 glass transition temperature can be determined as the temperature of the inflection point that appears when the temperature is raised 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, when it is difficult to measure the glass transition temperature by the above method, the glass transition temperature can be a literature value or a measurement result by a manufacturer. However, the glass transition temperature is preferentially determined by the method described in the Examples below.
  • DSC differential scanning calorimetry
  • Examples of the polymer-derived structural units constituting the polymer block (B) include polyether, polyester, polycarbonate, polysiloxane, etc., and preferably include an oxygen-atom-containing polymer (hereinafter referred to as an "oxygen-atom-containing polymer") that contains an oxygen atom in the polymer-derived structural unit. Details of polyether, polyester, polycarbonate, and polysiloxane will be described later.
  • the oxygen-atom-containing polymer preferably contains an oxygen atom in the main chain.
  • the polymer block (B) more effectively contributes to the development of flexibility by containing an oxygen atom, preferably an ether bond, in the main chain.
  • the content ratio of the constitutional unit derived from the oxygen atom-containing polymer in the polymer block (B) is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and may be 100 mol% or less. Also, the content ratio of the constitutional unit derived from the oxygen atom-containing polymer in the polymer block (B) may be 100 mol% or less. That is, the content of the structural units derived from the oxygen atom-containing polymer in the polymer block (B) is preferably 50 to 100 mol %.
  • polyethers are preferred from the viewpoint of easily imparting excellent flexibility.
  • the polymer block (B) there are no limitations on the constituent units other than the constituent units derived from the oxygen atom-containing polymer, so long as the effects of the present invention can be obtained.
  • the 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.
  • the 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 the polymer block (A).
  • the content of the structural units derived from a polymer having an amino group or a carboxyl group as a terminal group in the polymer block (B) is more preferably 70 mol% or more, further preferably 90 mol% or more, and may be 100 mol% or less.
  • the content of the structural units derived from a polymer having an amino group or a carboxyl group as a terminal group in the 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 the polymer block (B) is preferably 50 to 100 mol %.
  • the constituent units other than the above-mentioned constituent units derived from a 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.
  • polyether means polyether polyol, and includes derivatives such as amine derivatives and carboxyl derivatives of polyether polyol.
  • One or more types of polyether can be used.
  • the polymer block (B) contains a structural unit derived from polyether polyol, its carboxyl derivative, or its amine derivative.
  • the polymer block (B) contains 50 mol% or more of structural units derived from polyether polyol, its amine derivative, or its carboxyl derivative.
  • polyethers examples 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 of two or more.
  • polyetherdiamines examples include polyetherdiamines and polyetherdicarboxylic acids, etc.
  • polyetherdiamines are preferred from the viewpoint of imparting better flexibility to the polyamide block copolymer having the polymer block (A) as a hard segment and being expected to exhibit good chemical resistance to the polyamide block copolymer.
  • polyether diamines examples 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, and polyether diamines having amino groups at two ends of their copolymers. These can be used alone or in combination. Such polyether diamines can be obtained, for example, by cyanoacetylation of polyether diol.
  • polyether dicarboxylic acids examples 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 polyether dicarboxylic acids having carboxyl groups at two ends of their copolymers. These can be used alone or in combination of two or more kinds.
  • polyester means polyester polyol, and includes derivatives such as amine derivatives and carboxyl derivatives of polyester polyol.
  • One or more types of polyester can be used.
  • the oxygen atom-containing polymer is polyester polyol, its amine derivative, or its carboxyl derivative
  • the polymer block (B) contains a structural unit derived from polyester polyol, its amine derivative, or its carboxyl derivative.
  • polyesters include poly(caprolactone), poly(methyl valerolactone), poly(butylene adipate), poly(ethylene adipate), poly(methyl pentanediol adipate), poly(butylene-1,4-hexanediol-1,6-adipate), etc. These can be used alone or in combination of two or more.
  • the polyester that can be used is, for example, one produced by polycondensation of a dicarboxylic acid and a polyhydric alcohol.
  • 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 kinds selected from unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid.
  • 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.
  • Examples of the amine derivative in polyester include those in which an amino group is introduced at the end of polyester polyol, etc. These may be used alone or in combination of two or more kinds.
  • the above-mentioned carboxyl derivative in polyester may be, for example, a polyester polyol having a carboxyl group introduced at the end.
  • the above-mentioned carboxyl derivative may have at least one carboxyl group at the end, and may have, for example, a carboxyl group at all ends, or may have both a carboxyl group and a hydroxyl group at the end. These may be used alone or in combination.
  • polycarbonate means polycarbonate polyol, and includes derivatives such as amine derivatives and carboxyl derivatives of polycarbonate polyol.
  • One or more types of polycarbonate can be used.
  • the oxygen atom-containing polymer is polycarbonate polyol, its amine derivative, or its carboxyl derivative
  • the polymer block (B) contains a structural unit derived from polycarbonate polyol, its amine derivative, or its carboxyl derivative.
  • examples of polycarbonates include poly(hexanediol-1,6-carbonate), polytetrahydrofuran carbonate, etc. These may be used alone or in combination of two or more.
  • the polycarbonate polyol may be, for example, one produced by an esterification reaction between a carbonate ester and a polyhydric alcohol, or one produced by an interfacial polycondensation method in which a polyhydric alcohol is reacted with phosgene.
  • One or more kinds of polycarbonate polyols may be used.
  • Examples of carbonate esters include methyl carbonate, ethyl carbonate, phenyl carbonate, etc. These may be used alone or in combination of two or more.
  • polyhydric alcohols examples 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.
  • the amine derivatives in polycarbonate include, for example, polycarbonate polyols having amino groups at the terminals thereof, etc. These may be used alone or in combination of two or more.
  • the above-mentioned carboxyl derivative in polycarbonate may be, for example, a polycarbonate polyol having a carboxyl group introduced at the end.
  • the above-mentioned carboxyl derivative may have at least one carboxyl group at the end, and may have, for example, a carboxyl group at all ends, or may have both a carboxyl group and a hydroxyl group at the end. These may be used alone or in combination.
  • polysiloxane means polysiloxane polyol, and includes derivatives such as amine derivatives and carboxyl derivatives of polysiloxane polyol.
  • derivatives such as amine derivatives and carboxyl derivatives of polysiloxane polyol.
  • One or more types of polysiloxane can be used.
  • the oxygen atom-containing polymer is polysiloxane polyol, its amine derivative, or its carboxyl derivative
  • the polymer block (B) contains a structural unit derived from polysiloxane polyol, its amine derivative, or its carboxyl derivative.
  • polysiloxanes examples include compounds having a hydroxyl group at the end of a polyorganosiloxane having a repeating unit represented by the following formula (X): Specific examples include polydimethylsiloxane diol, polydiphenylsiloxane diol, polytrifluoropropylmethylsiloxane diol, polyphenylmethylsiloxane diol, polydiethylsiloxane diol, polydivinylsiloxane diol, polyvinylmethylsiloxane diol, poly(5-hexenyl)methylsiloxane diol, and the like.
  • formula (X) Specific examples include polydimethylsiloxane diol, polydiphenylsiloxane diol, polytrifluoropropylmethylsiloxane diol, polyphenylmethylsiloxane diol, polydiethylsiloxane diol
  • R and R' in formula (X) are organic groups and may be the same or different.
  • the organic groups are not limited as long as they do not impair the effects of the present invention, but examples include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups; alkenyl groups having 1 to 5 carbon atoms, such as vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylvinyl, and 1-methylallyl groups; alicyclic alkyl groups, such as cyclohexyl groups; aryl groups, such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl groups; and the like.
  • Examples of the amine derivative in the polysiloxane include those in which an amino group has been introduced at the end of a polysiloxane polyol, etc. These may be used alone or in combination of two or more kinds.
  • the carboxyl derivative in the polysiloxane may be, for example, one in which a carboxyl group has been introduced at the end of polysiloxane polyol, etc. These may be used alone or in combination of two or more kinds.
  • the number average molecular weight of the polymer block (B) is preferably 100 or more, 150 or more, or 200 or more, more preferably 300 or more, or 400 or more, and may be 500 or more, 700 or more, or 800 or more from the viewpoint of obtaining a polyamide block copolymer having excellent flexibility, particularly tensile properties.
  • the number average molecular weight of the polymer block (B) is not limited as long as the polymerization reaction with the polymer block (A) proceeds well, 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 the polymer block (B) is preferably 100 to 7,000, more preferably 200 to 5,000. Within the above numerical range, the polymerization reaction with the polymer block (A) proceeds well, and the flexibility of the polyamide block copolymer is excellent, so that the tensile properties tend to be even more excellent.
  • the method for producing the polyamide block copolymer of this embodiment preferably comprises mixing and polymerizing a polymer constituting the polymer block (A) containing 50 mol % or more of structural units derived from the above-mentioned polyamide and a polymer constituting the above-mentioned polymer block (B) having a glass transition temperature of 20° C. or lower.
  • the method for producing the polyamide block copolymer of this embodiment may also use the above-mentioned terminal functionalizing agent and/or the above-mentioned terminal capping agent.
  • a polyamide block copolymer may be produced by mixing the monomer constituting the polymer block (A) with, if necessary, the terminal capping agent and/or the terminal functionalizing agent, melt-polymerizing the mixture to obtain a polymer constituting the polymer block (A) in which the terminal functional groups have been adjusted, and then adding the polymer constituting the polymer block (B) and melt-polymerizing the mixture.
  • a polyamide block copolymer may be produced by dry-blending a polymer constituting the polymer block (A), in which the terminal functional groups have been adjusted by melt polymerization in the presence of the terminal capping agent as necessary in the polymerization stage of the polymer block (A), with a polymer constituting the polymer block (B), in the presence of the terminal capping agent as necessary, and melt-kneading the mixture.
  • the polymer constituting the polymer block (A) may be reacted with the terminal functionalizing agent and/or the terminal capping agent as 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.
  • the polymer constituting the polymer block (A) and, if necessary, the terminal functionalizing agent and/or the terminal capping agent may be charged from an upper hopper of a melt kneader and reacted, and then the polymer block (B) may be added from a side feed port downstream of the extruder, thereby performing melt extrusion polymerization in a stepwise manner.
  • 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 may be reacted in a dispersion medium, preferably in water, at normal temperature, for example, room temperature, to form a salt, and then the obtained salt may be reacted, for example, under high pressure and high temperature conditions, thereby polymerizing the 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.
  • Polymerization methods that can be used include, in general, melt polymerization, solid-phase polymerization, and melt extrusion polymerization. Solid-phase polymerization may be combined with melt polymerization or melt extrusion polymerization.
  • a method of melt kneading using a single screw extruder, twin screw extruder, kneader, Banbury mixer, or the like is preferably used as the melt extrusion polymerization method.
  • 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 of about 0 to 60°C higher than the melting point of the polyamide is preferred from the viewpoint of making it easier to achieve the effects of the present invention.
  • the polyamide block copolymer In order for the polyamide block copolymer to satisfy the above formula (1) and formula (2) in terms of the temperature-loss tangent curve, it is possible to change the hardness ratio in the polymer block (A), change the monomer constituting the polymer block (A), adjust the presence or absence of an aliphatic dicarboxylic acid as a terminal functionalizing agent, adjust the amount of the terminal blocking agent used, adjust the number average molecular weight of the polymer block (B), or adjust the compatibility of the polymer block (A) and the polymer block (B).
  • 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 a comparison between the examples and comparative examples described below, and a comparison between the examples themselves.
  • the mass ratio (A)/(B) of the polymer block (A) to the polymer block (B) is preferably 1/99 to 99/1, and more preferably 5/95 to 95/5 is preferred, 10/90 to 95/5 is more preferred, 20/80 to 95/5 is even more preferred, 40/60 to 90/10 is even more preferred, and 50/50 to 85/15 is even more preferred. If the mass ratio (A)/(B) is within the above range, the polyamide block copolymer is more likely to have both excellent heat resistance and flexibility, which is preferable.
  • the content of the 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 strength.
  • the content of the 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, and 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 the 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 elongation or flexibility.
  • the content of the 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, from the viewpoint of obtaining a polyamide block copolymer having excellent strength.
  • the total amount of polymer block (A) and polymer block (B) in the total amount of the polyamide block copolymer (100% by mass) 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, the total amount is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • 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 even more preferably 5,000 to 20,000.
  • the heat resistance of the polyamide block copolymer can be further improved and good molding processability can be expected.
  • the weight average molecular weight of the polyamide block copolymer is preferably 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 range, the polyamide block copolymer is expected to exhibit stronger material properties and have good molding processability.
  • the molecular weight distribution (weight average molecular weight/number average molecular weight) of the polyamide block copolymer is preferably 2.0 to 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 numerical range, the heat resistance of the polyamide block copolymer can be further improved and good moldability can be expected.
  • the aforementioned temperature width (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 width is 130°C or less, and the molecular weight distribution is 14.0 or less. Even more preferably, the temperature width is 120°C or less, and the molecular weight distribution is 12.0 or less. Even more preferably, the temperature width is 110°C or less, and the molecular weight distribution is 11.0 or less.
  • the above-mentioned temperature width (T2-T1) for the polyamide block copolymer is 150° C. or less, 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 width 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 width is 120° C.
  • 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 width is 110° C. or less, the molecular weight distribution of the polymer block (A) is 4.0 or less, and the molecular weight distribution is 11.0 or less.
  • the polyamide block copolymer of this embodiment has a tensile break strength measured in accordance with JIS K 7161-1:2014 of 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.
  • the tensile elongation at break 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, still more preferably 170% or more, even more preferably 190% or more, even more preferably 250% or more, and can also be 300% or more. It can be said that the larger the tensile elongation at break value, the more excellent the tensile properties of the polyamide block copolymer. More specifically, the tensile breaking strength and tensile breaking elongation can be determined by the method described in the examples below.
  • the fracture energy corresponding to the integral value of the stress value from the start of the tensile test to the break point is preferably 28 mJ/mm3 or more , more preferably 30 mJ/ mm3 or more, even more preferably 32 mJ/mm3 or more , and still more preferably 35 mJ/mm3 or more . It can be said that the polyamide block copolymer has a better balance between strength and flexibility as the value of the fracture energy is larger.
  • the upper limit of the fracture energy is not particularly limited, but may be, for example, 300 mJ/ mm3 or less. From the viewpoint of having a better balance between strength and flexibility, the fracture energy of the polyamide block copolymer may be 37 mJ/mm3 or more , 39 mJ/mm3 or more , or 41 mJ/mm3 or more . More specifically, the breaking energy can be determined by the method described in the examples below.
  • the tensile breaking strength is preferably 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.
  • the tensile breaking strength is 10 MPa or more, the tensile breaking elongation is 30% or more, and the breaking energy is preferably 28 mJ/ mm3 or more. 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/ mm3 or more. Even 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/mm3 or more . 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/ mm3 or more.
  • One embodiment of the present invention is 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, such as additives such as antioxidants, antiozonants, weather stabilizers, UV absorbers, hydrolysis-resistant stabilizers, fillers, crystal nucleating agents, reinforcing agents, carbon black, pigments, inorganic dyes, organic dyes, colorants, color inhibitors, gelling inhibitors, matting agents, antistatic agents, plasticizers, lubricants, mold release agents, shrinkage resistance agents, compatibilizers, flame retardants, flame retardant assistants, and foaming agents.
  • additives such as antioxidants, antiozonants, weather stabilizers, UV absorbers, hydrolysis-resistant stabilizers, fillers, crystal nucleating agents, reinforcing agents, carbon black, pigments, inorganic dyes, organic dyes, colorants, color inhibitors, gelling
  • the content of the additives is not particularly limited as long as it does not impair the effects of the present invention, but can be 0.02 to 200 parts by mass based on 100 parts by mass of the polyamide block copolymer.
  • Examples of the method for adding the additives include a method of adding them during polymerization of the polyamide block copolymer, and a method of dry blending the additives with the polyamide block copolymer and melt kneading the mixture.
  • Method of producing polyamide block copolymer composition There is no particular limitation on the method for producing the polyamide block copolymer composition, and any method capable of uniformly mixing the polyamide block copolymer and the above-mentioned additives can be preferably used.
  • the mixing is usually preferably performed by melt-kneading using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like.
  • the melt-kneading conditions are not particularly limited, and examples thereof include a method of melt-kneading for about 1 to 120 minutes at a temperature range of about 0 to 60° C. higher than the melting point of the polyamide block copolymer.
  • 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 various molded articles of any shape and application, including electric and electronic parts, automobile parts, industrial parts, fibers, films, sheets, household goods, and the like.
  • the method for producing the molded product 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, compressed air molding, bead molding, batch foam molding, etc.
  • Examples of the form of the molded product include pellets, sheets, plates, pipes, tubes, rods, granules, and foams.
  • the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be used in a wide range of fields where the properties are required because they can have an excellent balance between strength and flexibility.
  • the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as various parts materials such as electric and electronic parts, automobile parts, industrial material parts, industrial parts, daily necessities, household goods, sports parts, leisure parts and medical parts.
  • they can be applied as complex shaped parts by injection molding, hollow molded parts by blow molding, hose and tube shaped parts, films and sheets by extrusion molding, lightweight members and heat insulating materials by injection and/or extrusion foam molding, and additives for resin modification.
  • foams can also be applied as foams by injection molding, blow molding, press molding, extrusion molding, calendar molding, vacuum molding, compressed air molding, bead molding or batch foam molding.
  • electronic and electrical parts it can be used as a material for hinges of mobile phones and game machines, camera grips, printer tractor belts, electric wire coverings, tubes for home appliances, etc.
  • automobile 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, automobile belts, fuel tether caps, door locks, steering switches, seat locks, accelerator pedals, air ducts, airless tires, tire frames, tire inner liners, etc.
  • the material can be used as a material for submersible pumps, seal members, bushes, tubes, spiral tubes, diaphragms, mop joints, noiseless gears, mandrels, films, nonwoven fabrics, monofilaments, ball joint sheets, resistor rods, fire hoses, conveyor belts, pulleys, wire cables, etc.
  • the material can be used as a material for hair dryer brushes, manicure cases, hot curlers, zipper pulls, bobbin cases, console shutters, corrugated tubes, corrugated hoses, cushioning materials for pillows, cushioning materials for mattresses, cushioning materials for chairs, etc.
  • the material can be used for sports parts such as running shoes, spiked shoes, and ski boots.
  • the material can be used as a material for medical catheters, wearable devices, optical products, eye care parts, etc.
  • the method for producing a foam includes, for example, the steps of (1) extrusion, (2) crosslinking, (3) foaming, (4) expansion process, and (5) molding.
  • (1) extrusion step mixing and kneading are performed as necessary.
  • (2) Crosslinking is performed by at least one of chemical crosslinking and physical crosslinking.
  • a foaming agent for example, an organic foaming agent, or a supersaturated gas, preferably an inert gas, may be used, or both a foaming agent and a supersaturated gas may be used.
  • free expansion may be performed, for example, in an oven, or limited expansion may be performed, for example, in a mold.
  • 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 method for producing a foam is not limited to the above examples.
  • any of the following processes may be used instead of or in addition to the above processes: 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).
  • Applications of the foam include soccer balls, sports glove pads (goalkeeper, boxing, etc.
  • automotive product trays gaskets; flexographic printing rolls; single-sided adhesive coated tapes, double-sided adhesive coated tapes; orthopedic insoles or inlays, footwear insoles or inner soles, footwear midsoles, footwear linings, waterproof, breathable insoles or inner soles, footwear shafts or heel inserts, forefoot inserts; transdermal pads, transdermal absorption pads, wound healing plasters; sportswear, and clothing linings.
  • Measuring device MCU-710M/S (Kyoto Electronics Manufacturing Co., Ltd.) Measurement unit: AT-710 Main control unit: MCU-710
  • the terminal carboxyl group content ([COOH], unit: ⁇ mol/g) of adipic acid and terephthalic acid used as the terminal functionalizing agent was calculated from the molecular weight based on the fact that one molecule has two carboxyl groups.
  • 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 point was measured in accordance with ISO11357-3 (2011, 2nd edition). Specifically, in a nitrogen atmosphere, the sample was heated from 30°C to 340°C at a rate of 10°C/min, held at 340°C for 5 minutes to completely melt the sample, and then cooled to 50°C at a rate of 10°C/min and held at 50°C for 5 minutes.
  • the peak temperature of the melting peak that appeared when the temperature was raised again to 340°C at a rate of 10°C/min was taken as the melting point (°C).
  • the peak temperature of the melting peak on the highest temperature side was taken as the melting point (°C).
  • thermo viscoelasticity measuring device “Rheogel E-4000” manufactured by UBM Co., Ltd.
  • dynamic viscoelasticity measurement was carried out 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 a tensile mode in a nitrogen atmosphere, and the loss tangent (tan ⁇ ) value at each temperature was obtained.
  • a temperature-loss tangent curve was prepared.
  • a temperature-loss tangent curve was constructed by plotting the data taken every 1°C.
  • Temperature T0 Among the loss tangent values obtained in the temperature range of -100°C to 160°C, the maximum value tan ⁇ (max) was identified, and the temperature T0 [°C] at that time was identified. When multiple peaks existed in the temperature range of -100°C to 160°C in the temperature-loss tangent curve, the loss tangent value at the peak top of the maximum peak was taken as the maximum value tan ⁇ (max) at temperature T0. (3) Temperature range (T2-T1) In addition, among the loss tangent values obtained in the temperature range of -100°C to 330°C, the temperature showing half the maximum value tan ⁇ (max) (i.e., tan ⁇ (max)/2) was specified.
  • T1 [°C] a first temperature lower than temperature T0
  • T2 [°C] a second temperature higher than temperature T0
  • Tm2-Tm1 a first temperature lower than temperature T0
  • Tm2-Tm1 a second temperature higher than temperature T0
  • the small test piece type 1BA of the obtained polyamide block copolymer was left to stand in a dryer at 140 ° C. for 6 hours, and then a tensile test was performed at 23 ° C. in accordance with JIS K 7161-1:2014 using an Instron universal testing machine "5566 type" manufactured by Instron.
  • the tensile break strength and tensile break elongation were measured.
  • the chuck distance 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 region of 0 to 0.3% strain
  • the test speed was 50 mm/min in the region of 0.3% strain or more.
  • test force [N] and stroke value [mm] were obtained every 0.1 seconds.
  • S-S curve stress-strain curve showing the relationship between the stress value [GPa] and the strain value [%].
  • the breaking point was the strain value obtained just before the strain value could no longer be obtained.
  • the tensile breaking elongation was the nominal strain value according to Method A of JIS K 7161-1:2014.
  • strain energy [mJ] from the start of the tensile test (strain 0%) to the breaking point was calculated using the test force [N] and stroke value [mm] obtained every 0.1 seconds in the tensile test.
  • the difference between the stroke value obtained at that time and the stroke value obtained immediately before was calculated as the stroke difference [mm]
  • the integrated value of the test force for each stroke difference was calculated up to the breaking point.
  • both the first strain energy in the region of 0 to 0.3% strain and the second strain energy in the region of 0.3% strain or more were calculated according to the test speed.
  • the fracture energy [mJ/mm 3 ] was calculated from the calculated strain energy [mJ] and the mounting volume [mm 3 ] of the test piece.
  • the fracture energy calculated in this manner corresponds to the integral value [mJ/mm 3 ] of the stress value [GPa] from the start of the tensile test (strain 0%) to the fracture point in a stress-strain curve (S- S curve) that can be created as a result of the tensile test.
  • 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 removed to allow the reaction. The reaction was allowed to continue for another 1 hour to obtain a prepolymer which is a semi-aromatic polyamide.
  • 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-1".
  • the semi-aromatic ratio (unit: %) is shown in Table 1.
  • 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 2.0MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0MPa, and the water vapor was gradually removed to allow the reaction. The reaction was allowed to continue for another 1 hour to obtain a prepolymer which is a semi-aromatic polyamide.
  • 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.
  • 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 removed to allow the reaction. The reaction was allowed to continue for another 1 hour to obtain a prepolymer which is a semi-aromatic polyamide.
  • 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.
  • 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 removed to allow the reaction. The reaction was allowed to continue for another 1 hour to obtain a prepolymer.
  • the obtained prepolymer was dried at 120° C. under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as “PA-6”.
  • the semi-aromatic ratio is shown in Table 1.
  • Polyether Block (B) As the polymer block (B), the following oxygen atom-containing polymer was used.
  • PE-1 Polyether diamine (diamine of polyethylene glycol and polypropylene glycol copolymer), manufactured by Sigma-Aldrich, Jeffamine (registered trademark) ED-900
  • PE-2 Polyether diamine (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 Polyoxypropylenediamine, poly(propylene glycol) bis(2-aminopropyl ether) manufactured by Sigma-Aldrich (number average molecular weight: 400, product number: 406678; measured number average molecular weight: 430)
  • the physical properties of the polymer block (B) are shown in Table 2.
  • the notations in Table 2 are as follows: "[NH 2 ]” indicates the terminal amino group content.
  • Tg indicates the glass transition temperature measured by the following [Method of Measuring Glass Transition Temperature]. Note that “ ⁇ -70” indicates that the glass transition temperature was below -70°C because no inflection point was confirmed in the range of -70°C or higher, which is the measurement limit of the device.
  • glass transition temperatures (based on literature values) for corresponding polyether diols are also shown in Table 2 as reference values. "Up to -70” indicates a range of -80 to -60°C, and "up to -85” indicates a range of -95 to -75°C.
  • the polymer block (B) was used as a sample, and the glass transition temperature of each sample was 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.
  • Example 1 The raw materials used in the reaction were used in the mass ratios shown in Table 3. Specifically, "PA-1" of Synthesis Example 1 and adipic acid as a terminal functionalizing agent were added to a flask with an internal volume of 200 mL equipped with an instrument capable of distilling off the generated volatile components and a vacuum pump, and the temperature was raised to 280°C while stirring under a nitrogen gas flow of 200 mL/min, and this temperature was maintained for 30 minutes. Then, "PE-1” was added, and the mixture was stirred for another hour at a resin temperature of 280°C, and the distillate was removed.
  • PA-1 of Synthesis Example 1 and adipic acid as a terminal functionalizing agent
  • Example 1 To explain the mass ratio (A)/(B) shown in Table 3 as an example, in Example 1, it means that 32 parts by mass (e.g., 31.5 g) of polyether PE-1 was used relative to 68 parts by mass (e.g., 68.5 g) of polyamide PA-1 functionalized with a terminal functionalizing agent.
  • 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 a polyamide block copolymer.
  • Example 4 The raw materials used in the reaction were used 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 stirred at room temperature to become uniform in a glass beaker with an internal volume of 5 L.
  • the polyamide block copolymers obtained in Examples 1 to 9 had a high fracture energy value of 30 mJ/ mm3 or more, and thus had an excellent balance between strength and flexibility. This is believed to be because the T0 value was -60°C or more and the temperature width (T2-T1) value was 170°C or less, thereby maintaining the properties such as strength expected of the polymer block (A) and allowing the polymer block (B) to fully exhibit properties such as flexibility.
  • the polyamide block copolymers obtained in Comparative Examples 1 and 2 all had fracture energy values of less than 30 mJ/ mm3 , and therefore were inferior in balance between strength and flexibility to the polyamide block copolymers obtained in the Examples.
  • T0 value of less than -60°C and a temperature width (T2-T1) value of more than 170°C were factors that resulted in an impairment of the balance between strength and flexibility.
  • T2-T1 value of more than 170°C was also considered to be a factor that resulted in an impairment of the balance between strength and flexibility.
  • the polyamide block copolymer of this embodiment has an excellent balance between strength and flexibility. Therefore, the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be widely used as various parts materials such as electric and electronic parts, automobile parts, industrial material parts, industrial parts, daily necessities, clothing, household goods parts, sports parts, leisure parts and medical parts.
  • it can be applied to complex shaped parts by injection molding, hollow molded parts by blow molding, hose and tube shaped parts, films and sheets by extrusion molding, lightweight members and heat insulating materials by injection and/or extrusion foam molding, and additives for resin modification.
  • It can also be applied to foams by injection molding, blow molding, press molding, extrusion molding, calendar molding, vacuum molding, compressed air molding, bead molding or batch foam molding.

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PCT/JP2024/016237 2023-04-27 2024-04-25 ポリアミドブロック共重合体、ポリアミドブロック共重合体組成物、及び成形体 Ceased WO2024225376A1 (ja)

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EP24797121.1A EP4703408A1 (en) 2023-04-27 2024-04-25 Polyamide block copolymer, polyamide block copolymer composition, and molded article
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228690A (ja) 1993-12-24 1995-08-29 Kuraray Co Ltd ポリアミド
JP2000154248A (ja) * 1998-11-20 2000-06-06 Kuraray Co Ltd ポリアミドブロック共重合体およびその製造方法
JP2010534256A (ja) 2007-07-25 2010-11-04 エーエムエス−パテント アクチェンゲゼルシャフト 透明なポリアミドエラストマー
WO2013105607A1 (ja) 2012-01-12 2013-07-18 三菱瓦斯化学株式会社 ポリエーテルポリアミドエラストマー
WO2023074726A1 (ja) * 2021-10-26 2023-05-04 株式会社クラレ ポリアミドブロック共重合体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228690A (ja) 1993-12-24 1995-08-29 Kuraray Co Ltd ポリアミド
JP2000154248A (ja) * 1998-11-20 2000-06-06 Kuraray Co Ltd ポリアミドブロック共重合体およびその製造方法
JP2010534256A (ja) 2007-07-25 2010-11-04 エーエムエス−パテント アクチェンゲゼルシャフト 透明なポリアミドエラストマー
WO2013105607A1 (ja) 2012-01-12 2013-07-18 三菱瓦斯化学株式会社 ポリエーテルポリアミドエラストマー
WO2023074726A1 (ja) * 2021-10-26 2023-05-04 株式会社クラレ ポリアミドブロック共重合体

Non-Patent Citations (1)

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Title
See also references of EP4703408A1

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