Classifications

• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
  • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
• • 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
  • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer

Definitions

• the present invention relates to polyamide block copolymers.
• Thermoplastic elastomers can be melt-molded, and are used in a wide range of fields such as automobile interior and exterior parts, electronic equipment parts, and sporting goods.
• Thermoplastic elastomers contain soft segments exhibiting flexibility and hard segments exhibiting cross-linking points, and are classified into, for example, olefinic, amide, urethane, ester, acrylic, and styrene.
• Thermoplastic elastomers can exhibit physical properties such as good mechanical strength, abrasion resistance, heat resistance, and oil resistance according to the above classification.
• thermoplastic elastomers such as amide, urethane, and ester tend to exhibit relatively good heat resistance.
• thermoplastic elastomers such as amide, urethane, and ester tend to exhibit relatively good heat resistance.
• Patent Document 1 discloses a polyamide block copolymer obtained by polymerizing a dicarboxylic acid, a diamine, and a polyetherdiamine and/or a polyetherdicarboxylic acid for the purpose of exhibiting excellent heat resistance and low temperature properties.
• Patent Document 2 discloses a polyetherdiamine compound (A-1) having a specific structure of a diamine constitutional unit and xyloxy, for the purpose of exhibiting excellent heat resistance, melt moldability, crystallinity and flexibility.
• a polyether polyamide elastomer which is derived from diamine (A-2) and whose dicarboxylic acid constitutional unit is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• A-2 diamine
• US Pat. No. 6,200,000 discloses copolymers of rigid polyamide blocks and flexible polyether or polyester blocks with the aim of exhibiting excellent optical and mechanical properties.
• the polyamide block is semi-crystalline and X. X'/Y. Z-type copolyamide, (i) X. X' is an aliphatic diamine.
• a pair of diacids (ii) Y is a cycloaliphatic diamine, and (iii) Z is an aliphatic and/or aromatic dicarboxylic acid.
• Y is a cycloaliphatic diamine
• Z is an aliphatic and/or aromatic dicarboxylic acid.
• Patent Document 4 for the purpose of demonstrating thermoforming stability and hydrolysis stability, a linear aliphatic diamine having 6 to 12 carbon atoms and a linear aliphatic or aromatic diamine having 6 to 12 carbon atoms Molding compositions are disclosed which contain polyetheramides based on dicarboxylic acids and polyetherdiamines.
• an object of the present invention is to provide a polyamide block copolymer that is excellent in heat resistance and flexibility.
• the present invention is as follows.
• the polymer block (B) has a glass transition temperature of 20° C. or lower, a melting point of 230° C. or higher; Polyamide block copolymer.
• the semi-aromatic polyamide is a dicarboxylic acid derived from at least one selected from the group consisting of terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
• unit means "a structural unit derived from”
• dicarboxylic acid unit means "to a dicarboxylic acid.
• a "structural unit derived from a diamine” means a “structural unit derived from a diamine”.
• the polyamide block copolymer of this embodiment is A polymer block (A) containing 50 mol% or more of structural units derived from a polyamide, and a polymer block (A) containing 50 mol% or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters ( B), wherein the polymer block (B) has a glass transition temperature of 20°C or lower, and the polyamide block copolymer has a melting point of 230°C or higher.
• the polyamide block copolymer of this embodiment is a copolymer containing polyamide as the polymer block (A) and polyether and/or polyester as the polymer block (B).
• the polyamide block copolymer of the present embodiment contains a specific polyamide and polyether and/or polyester as polymer blocks, respectively, so that the excellent heat resistance of polyamide and the excellent heat resistance of polyether and/or polyester Both excellent flexibility can be exhibited.
• the polyamide block copolymer of Patent Literature 1 cannot provide sufficient heat resistance and mechanical strength. This is probably because the monomers and oligomers constituting the hard segment and soft segment are collectively polymerized, so that polymer blocks sufficient to sufficiently exhibit the physical properties of the hard segment and soft segment are not formed.
• the polymer block (A) contains 50 mol % or more of constitutional units derived from polyamide. From the viewpoint of easily obtaining even better heat resistance, the polymer block (A) preferably contains 70 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol% of structural units derived from polyamide. You can also In the polymer block (A), structural units other than the polyamide-derived structural units are not limited as long as the effects of the present invention can be obtained. Polyamides that can be used in this embodiment are not limited as long as the effects of the present invention can be obtained, and examples thereof include semi-aromatic polyamides, wholly aromatic polyamides, and aliphatic polyamides.
• semi-aromatic polyamides and aliphatic polyamides are exemplified as polyamides with which the effects of the present invention are exhibited more remarkably. It is particularly preferable to use a semi-aromatic polyamide as the polyamide from the viewpoint that even more excellent heat resistance can be easily obtained.
• the aliphatic polyamide include polytetramethylene adipamide (polyamide 46) and polyhexamethylene adipamide (polyamide 66).
• the semi-aromatic polyamide that can be preferably used in this embodiment will be described in detail below.
• a semi-aromatic polyamide is a polyamide containing a diamine unit mainly composed of an aliphatic diamine unit and a dicarboxylic acid unit mainly composed of an aromatic dicarboxylic acid unit, or a polyamide mainly composed of an aliphatic dicarboxylic acid unit.
• "mainly composed” means to constitute 50 to 100 mol %, preferably 60 to 100 mol %, of all units.
• the semi-aromatic polyamide may contain diamine units mainly composed of aliphatic diamine units and dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units. preferable.
• aliphatic diamine unit Semi-aromatic polyamides are derived from aliphatic diamines having 4 to 18 carbon atoms with respect to all diamine units from the viewpoint that the polymerization reaction with dicarboxylic acid proceeds well and is advantageous for improving physical properties such as heat resistance and flexibility. It is preferable to contain 30 mol% or more diamine units, more preferably 30 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, and 90 to 100 mol%. Preferably, it may be contained in an amount of 100 mol %.
• the aliphatic diamine used in the diamine unit is more preferably an aliphatic diamine having 4 to 16 carbon atoms, more preferably an aliphatic diamine having 4 to 12 carbon atoms, and more preferably an aliphatic diamine having 6 to 12 carbon atoms. More preferred are aliphatic diamines having 6 to 10 carbon atoms.
• Aliphatic diamines having 4 to 18 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7-heptanediamine, and 1,8-octane.
• the aliphatic diamine is preferably at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines, and linear aliphatic diamines and branched aliphatic diamines. It is more preferable to use a diamine together.
• Semi-aromatic polyamides are 1,4-butanediamine, 1,6-hexanediamine, 1,9-nonanediamine, and 2-propyl, from the viewpoint that the effects of the present invention are exhibited more remarkably and raw material availability is also excellent.
• -1,6-hexanediamine 2-ethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecane
• It preferably contains a diamine unit derived from at least one selected from the group consisting of diamines, and a diamine derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. It is more preferable to contain units, and from the viewpoint of moldability, it is even more preferable to use both 1,9-nonanediamine and 2-methyl-1,8-octanediamine in combination.
• the content of 1,9-nonanediamine units and/or 2-methyl-1,8-octanediamine units in the total amount of diamine units constituting the semi-aromatic polyamide is preferably 50 to 100 mol%, preferably 60 to 100 mol. %, more preferably 75 to 100 mol %, even more preferably 90 to 100 mol %.
• the heat resistance is further improved. and excellent chemical resistance can be expected.
• the molar ratio of 1,9-nonanediamine:2-methyl-1,8-octanediamine is 99:1 to 1:99. preferably 95:5 to 5:95, more preferably 90:10 to 10:90, even more preferably 85:15 to 15:85, even more preferably 80:20 to 20:80, 70: 30 to 30:70 is even more preferred, and 65:35 to 35:65 is particularly preferred.
• the semi-aromatic polyamide may contain, as diamine units, structural units derived from other than aliphatic diamines such as aromatic diamines, as long as the effects of the present invention are not impaired. 1 type of structural units derived from other than these aliphatic diamines may be contained, and 2 or more types may be contained.
• the content of structural units derived from other than the aliphatic diamine in the diamine unit is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and even more preferably 5 mol% or less.
• aromatic dicarboxylic acid unit As the aromatic dicarboxylic acid unit, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6- Aromatics derived from naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, etc.
• a dicarboxylic acid unit may be mentioned.
• the semi-aromatic polyamide is a group consisting of terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid from the viewpoint that the effects of the present invention are exhibited more remarkably. It preferably contains a dicarboxylic acid unit derived from at least one selected from, and from the viewpoint of further improving heat resistance, derived from at least one selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid. More preferably, it contains a dicarboxylic acid unit. These aromatic dicarboxylic acid units may be used singly or in combination of two or more.
• the dicarboxylic acid units derived from at least one selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid are included in the total amount of dicarboxylic acid units constituting the semi-aromatic polyamide.
• the content 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 100 It may be mol %.
• the semi-aromatic polyamide may contain, as dicarboxylic acid units, structural units derived from other than aromatic dicarboxylic acids such as aliphatic dicarboxylic acids, as long as the effects of the present invention are not impaired. 1 type of structural units derived from other than these aromatic dicarboxylic acids may be contained, and 2 or more types may be contained.
• Examples of aliphatic dicarboxylic acids include direct acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and dimethylmalonic acid.
• the content of structural 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, still more preferably 10 mol% or less, and even more preferably 5 mol% or less. preferable.
• the content of units derived from the aliphatic diamine having 4 to 18 carbon atoms is preferably 15 to 55 mol%, more preferably 25 to 55 mol%, based on all structural units constituting the semiaromatic polyamide.
• the content of units derived from an aromatic dicarboxylic acid is preferably 15 to 55 mol %, more preferably 25 to 55 mol %, relative to all structural units constituting the semiaromatic polyamide.
• the total content of units derived from the aliphatic diamine having 4 to 18 carbon atoms and the aromatic dicarboxylic acid is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, with respect to all structural units constituting the semiaromatic polyamide. is more preferable, 70 to 100 mol% is more preferable, and it may be 90 mol% or more, or even 100 mol%.
• the semi-aromatic polyamide may contain structural units other than the diamine unit and the dicarboxylic acid unit as long as the effects of the present invention are not impaired.
• Other structural units include, for example, polycarboxylic acid units, aminocarboxylic acid units and lactam units.
• polyvalent carboxylic acid units include structural units derived from trivalent or higher polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid. These polyvalent carboxylic acid units can be contained within a range in which melt molding is possible.
• aminocarboxylic acid units include structural units derived from lactams such as caprolactam and lauryllactam; aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
• lactam units include structural units derived from ⁇ -caprolactam, enantholactam, undecanelactam, lauryllactam, ⁇ -pyrrolidone, ⁇ -piperidone, and the like.
• the content of other structural units is preferably 30 mol % or less, more preferably 10 mol % or less, relative to all structural units constituting the semi-aromatic polyamide.
• Typical 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), poly Pentamethylene terephthalamide (polyamide 5T), polyhexamethylene terephthalamide (polyamide 6T), polynonamethylene terephthalamide (polyamide 9T), poly(2-methyloctamethylene) terephthalamide (polyamide M8T), polynonamethylene terephthalamide/ Poly(2-methyloctamethylene) terephthalamide copolymer (polyamide 9T/M8T), polynonamethylene naphthalene dicarboxamide (polyamide 9N), poly(2-methyloctamethylene) naphthalene dicarboxamide (polyamide M8N), polynonamethylene naphthalene Carboxamide/poly(2-methyloctam
• the polyamide contained in the polymer block (A) may contain structural units derived from a terminal blocking agent.
• the content of the structural unit derived from the terminal blocking agent is preferably 1.0 to 10 mol%, more preferably 2.0 to 7.5 mol%, and 2.5 to 6.5 mol% with respect to the diamine unit. is more preferred.
• the content of the structural unit derived from the terminal blocker can be adjusted by adjusting the amount of the terminal blocker charged relative to the diamine when charging the polymerization raw material. Considering that the monomer component volatilizes during polymerization, the amount of the terminal blocker charged when charging the polymerization raw material is adjusted so that the desired amount of structural units derived from the terminal blocker is introduced into the resulting resin.
• the terminal blocking agent can be charged in the above desired range.
• the polymer constituting the polymer block (A) may be charged with a terminal functionalizing agent described later and a terminal blocking agent within the above desired range.
• the solution viscosity is measured, and the relationship between this and the number average molecular weight.
• a method of calculating the total amount of terminal groups from the formula and subtracting the amount of amino groups and the amount of carboxyl groups obtained by titration from the formula can be exemplified.
• a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used as the terminal blocking agent. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines.
• monocarboxylic acid is preferable as the terminal blocking agent for the terminal amino group
• monoamine is preferable as the terminal blocking agent for the terminal carboxyl group.
• monocarboxylic acids are more preferable as terminal blocking agents.
• the monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with amino groups.
• monocarboxylic acids include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
• cyclopentanecarboxylic acid cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids
• benzoic acid toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids and any mixture thereof.
• acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, and stearic acid are preferred in terms of reactivity, stability of blocked ends, and price.
• benzoic acid are preferred.
• the monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with the carboxyl group.
• monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; arbitrary mixtures thereof; Among these, at least one selected from butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferable from the viewpoints of reactivity, high boiling point, stability of capped ends, price, and the like.
• the semi-aromatic polyamide can be obtained, for example, by using a dicarboxylic acid and a diamine as raw materials and using a melt polymerization method, a solid phase polymerization method, or a melt extrusion polymerization method. It can be produced by a method such as Specifically, a semi-aromatic polyamide can be produced as follows. First, a diamine, a dicarboxylic acid, and optionally an aminocarboxylic acid, a lactam, a catalyst, a terminal blocking agent, etc. are mixed to produce a nylon salt.
• the produced nylon salt is heated to a temperature of 200 to 250° C. and heat-polymerized to obtain a semi-aromatic polyamide as a prepolymer.
• the molecular weight of the semi-aromatic polyamide can be adjusted to a desired value by solid-phase polymerizing the prepolymer or increasing the degree of polymerization using a melt extruder.
• the step of increasing the degree of polymerization is performed by a solid phase polymerization method, it is preferably performed under reduced pressure or under inert gas flow. and can effectively suppress coloring and gelation.
• the polymerization temperature is preferably 370° C. or less, and when the polymerization is carried out under such conditions, a semi-aromatic polyamide can be obtained with almost no decomposition and little deterioration.
• catalysts that can be used in producing semi-aromatic polyamides include phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof, and the like.
• examples of the above salts or esters include phosphoric acid, phosphorous acid, or hypophosphorous acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, and the like.
• the amount of the catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to 100% by mass of the total mass of the raw materials for the semi-aromatic polyamide.
• the amount of catalyst used is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. If the amount of catalyst used is at least the above lower limit, the polymerization proceeds more favorably.
• the polyamide can be adjusted to have a desired functional group or functional group amount at the end of the polyamide by using a terminal functionalizing agent described later.
• terminal amino group content refers to the terminal amino group content in the polyamide before terminal conversion with a terminal functionalizing agent.
• the polyamide before terminal conversion has a terminal amino group content ([NH 2 ]), which is the content of terminal amino groups, of preferably 1 to 4,000 ⁇ mol/g, more preferably 1 to 3,000 ⁇ mol/g, More preferably 1 to 2,500 ⁇ mol/g, still more preferably 1 to 2,000 ⁇ mol/g.
• the terminal amino group content ([NH 2 ]) as used herein refers to the amount of terminal amino groups contained in 1 g of the polyamide (unit: ⁇ mol), and can be determined by a neutralization titration method using an indicator. .
• the polyamide before 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, and further It is preferably 50 to 3,000 ⁇ mol/g, and even more preferably 75 to 2,500 ⁇ mol/g.
• the terminal carboxyl group content ([COOH]) as used herein refers to the amount (unit: ⁇ mol) of terminal carboxyl groups contained in 1 g of polyamide, and can be obtained by potentiometric titration.
• the melting point of the polyamide is preferably 230°C or higher, more preferably 240°C or higher, and even more preferably 250°C or higher. If the melting point of the polyamide is 230°C or higher, the heat resistance of the polyamide block copolymer can be further improved.
• the upper limit of the melting point of the polyamide is not particularly limited, it is preferably 320° C. or less from the viewpoint of moldability and the like. That is, the melting point of the polyamide is preferably 230°C or higher and 320°C or lower.
• the melting point can be obtained as the peak temperature of the melting peak that appears when the temperature is raised at a rate of 10° C./min using a differential scanning calorimetry (DSC) apparatus. More specifically, it can be obtained by the method described in the examples below.
• DSC differential scanning calorimetry
• the number average molecular weight of the polymer block (A) is preferably 300 to 12,000, more preferably 300 to 11,000, still more preferably 350 to 10,000, even more preferably 400 to 9,000, and even more preferably is 400 to 8,000, may be 400 to 7,000, and may be 400 to 6,000. Within the above numerical range, the compatibility between the polymer block (A) and the polymer block (B) is excellent, and the heat resistance of the polyamide block copolymer can be further improved.
• the weight average molecular weight of the polymer block (A) is preferably from 1,000 to 50,000, more preferably from 1,100 to 45,000, still more preferably from 1,200 to 40,000, still more preferably 1,000 to 40,000.
• the compatibility between the polymer block (A) and the polymer block (B) is excellent, and the heat resistance of the polyamide block copolymer can be further improved.
• the number average molecular weight and weight average molecular weight can be measured by gel permeation chromatography, and more specifically, they are values measured by the method described in Examples.
• a terminal functionalizing agent can be used to form a polymer block (A) having a desired functional group or functional group amount at the terminal of the polyamide.
• the end of the polyamide can be converted by reacting the above-described polyamide prepolymer with a terminal functionalizing agent. It is also possible to convert the end of the polyamide by making either one of the dicarboxylic acid units and the diamine units excessive at the stage of charging the raw materials.
• the terminal of the polymer block (A) By adjusting the terminal of the polymer block (A) to have a desired functional group or amount of functional groups, the polymer block (A) and the polymer block (B) can be better bonded. Units derived from the terminal functionalizing agent shall be included in the polymer block (A).
• the terminal functionalizing agent may not be used. That is, in this case, the polymer block (A) and the polymer block (B) are formed by reacting the polyamide with at least one selected from the group consisting of polyethers and polyesters without using a terminal functionalizing agent. can obtain a polyamide block copolymer in which is well bonded.
• the adjustment of the active terminal functional group content of the polyamide which will be described later, can be performed, for example, by adjusting the carboxyl group content and the amino group content in the reaction raw materials in the production of the polyamide.
• the terminal functionalizing agent is not limited as long as it does not impair the effects of the present invention, and hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, sulfonyl group, halogen atom, vinyl group, vinylidene group at the end of polyamide. and those into which a functional group can be introduced.
• Dicarboxylic acids that can be used as end-functionalizing agents include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• Examples of aliphatic dicarboxylic acids include direct acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and dimethylmalonic acid.
• 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
• Diamines that can be used as end-functionalizing agents include aliphatic diamines and aromatic diamines.
• aliphatic diamines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane Diamine, 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, 1,18-octadecanediamine and other linear aliphatic diamines; 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine
• aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4 '-diaminodiphenyl ether, 4,4'-methylenedi-2,6-diethylaniline and the like.
• the terminal functionalizing agent may be used alone or in combination of two or more.
• the "active terminal functional group content” is the content of the active terminal functional groups 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 , is the active terminal functional group content of the polymer block (A).
• the "active terminal functional group” is a functional group that exhibits reactivity with the terminal functional group of the polymer block (B), and examples thereof include an amino group and a carboxyl group.
• the “active terminal functional group content” is the content of the active terminal functional group after the terminal functional group is converted.
• the total content of terminal carboxyl groups after conversion and terminal amino groups that have not been converted is the polymer block (A ) is the active terminal functional group content.
• the active terminal functional group content of the polymer block (A) is preferably 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. If the active terminal functional group content is 50 ⁇ 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. can. Further, when the active terminal functional group content is 5,000 ⁇ mol/g or less, the heat resistance of the polyamide block copolymer can be further improved.
• Active terminal functional group content refers to the amount of active terminal functional groups (unit: ⁇ mol) contained in 1 g of polyamide (polyamide after conversion when a terminal functionalizing agent is used), and an indicator is used. It can be determined by the neutralization titration method and the potentiometric titration method used. Specifically, it can be calculated by the method described in Examples described later.
• the polymer block (B) contains 50 mol% or more of structural units derived from at least one selected from the group consisting of polyethers and polyesters. From the viewpoint of easily obtaining even better flexibility, the polymer block (B) contains preferably 70 mol% or more, more preferably 70 mol% or more, of structural units derived from at least one selected from the group consisting of polyethers and polyesters. contains 90 mol % or more, and may contain 100 mol %. In the polymer block (B), structural units other than structural units derived from at least one selected from the group consisting of polyethers and polyesters are not limited as long as the effects of the present invention can be obtained.
• the glass transition temperature of polymer block (B) is 20° C.
• the glass transition temperature of the polymer block (B) is preferably 0.degree.
• the glass transition temperature can be obtained as the temperature at the point of inflection that appears when the temperature is raised at a rate of 2° C./min using a differential scanning calorimetry (DSC) apparatus. More specifically, it can be obtained by the method described in the examples below. Alternatively, for the glass transition temperature, literature values or manufacturer's measurement results can be adopted.
• polyether for example, polyetherdiamine, polyetherdicarboxylic acid, and the like can be used. Among them, it can be expected that a polyamide block copolymer having a polymer block (A) as a hard segment will be given more excellent flexibility, and that the polyamide block copolymer will exhibit excellent chemical resistance. From this point of view, polyetherdiamine is preferred. 1 type(s) or 2 or more types can be used for polyether.
• the polyether diamine may have amino groups at both ends of the polyether.
• polyether diamines include polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (PO3G), poly(oxybutylene) glycol, polytetramethylene ether glycol (PTMG), poly(3-alkyl tetrahydrofuran), especially poly(3-methyltetrahydrofuran) (poly(3MeTHF)), polypentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, etc., and copolymers thereof with amino groups at the two ends and polyether diamine having These can use 1 type(s) or 2 or more types.
• Such polyether diamines can be obtained, for example, by cyanoacetylation of polyether diols.
• the polyether dicarboxylic acid may have carboxyl groups at both ends of the polyether.
• polyether dicarboxylic acids include polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (PO3G), poly(oxybutylene) glycol, polytetramethylene ether glycol (PTMG), poly(3- alkyltetrahydrofuran), especially poly(3-methyltetrahydrofuran) (poly(3MeTHF)), polypentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, etc., and copolymers thereof with carboxyl at two ends. group-containing polyether dicarboxylic acid, and the like. These can use 1 type(s) or 2 or more types.
• polyesters include aliphatic polyesters, aromatic polyesters, copolymers thereof, and the like.
• a polyester produced by polycondensation of a dicarboxylic acid and a diol can be used.
• Dicarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; 1,3-cyclopentanedicarboxylic acid, 1,4- Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid , 1,3-phenylenedioxydiacetic acid, diphenic acid,
• diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol.
• neopentyl glycol 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 - Aliphatic diols such as dodecanediol; 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), and their Number of moles 2 or more and 12 or less) Alicyclic diols other than 1,4-cyclohexanedimethanol such as adducts; hydroquinone, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 1 , 5-dihydroxynaphthalene and other aromatic diols.
• polyesters can use 1 type(s) or 2 or more types.
• the polyamide block copolymer having the polymer block (A) as a hard segment imparts excellent flexibility and is expected to further improve the heat resistance of the polyamide block copolymer.
• aliphatic polyesters are preferred.
• the polymer block (B) preferably contains a structural unit derived from a polyether from the viewpoint of easily exhibiting excellent flexibility in the polyamide block copolymer, and contains a structural unit derived from a polyetherdiamine. is more preferable.
• the number average molecular weight of the polymer block (B) is preferably 200 to 5,000, more preferably 230 to 4,000, still more preferably 300 to 2,000, and may be 350 to 1,500. , 350 to 1,000. Within the above numerical range, the polymerization reaction with the polymer block (A) proceeds favorably, and the flexibility of the polyamide block copolymer can be further improved.
• the method for producing a polyamide block copolymer of the present embodiment consists of a polymer constituting the polymer block (A) containing 50 mol% or more of the structural units derived from the above-mentioned polyamide, and the above-mentioned polyether and polyester. It is characterized by mixing and polymerizing with a polymer constituting a polymer block (B) containing 50 mol % or more of structural units derived from at least one selected from the group.
• the method for producing a polyamide block copolymer of the present embodiment may use the terminal functionalizing agent and/or the terminal blocking agent.
• the polymer constituting the polymer block (A) and the polymer constituting the polymer block (B) are dry-blended in the presence of the terminal functionalizing agent and/or the terminal blocking agent.
• a polyamide block copolymer can be produced by melt-kneading the mixture.
• the semi-aromatic polyamide which is a polymer constituting the polymer block (A)
• the semi-aromatic polyamide which is a polymer constituting the polymer block (A)
• the polymer constituting the polymer block (B) is added and dry-blended, and the mixture is melt-kneaded.
• the semi-aromatic polyamide which is the polymer constituting (A)
• the terminal functionalizing agent and/or the terminal blocking agent are charged from the upper hopper of the melt kneader and reacted with each other.
• the polymer block (B) may be added from the side feed port on the downstream side of the extruder to melt and knead in stages.
• Methods such as a melt polymerization method, a solid phase polymerization method, a melt extrusion polymerization method, and the like can usually be employed.
• a melt polymerization method or a melt extrusion polymerization method may be combined with a solid phase polymerization method.
• melt extrusion polymerization method a method of melt-kneading using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like is preferably employed.
• the melt-kneading conditions are not particularly limited, for example, a method of melt-kneading for about 1 to 120 minutes at a temperature range higher than the melting point of the polyamide by about 0 to 60 ° C. is from the viewpoint that the effects of the present invention are more likely to be expressed. preferable.
• the polyamide block copolymerization of the present embodiment Coalescing is difficult to manufacture.
• the polymer block (A) is not completely formed and becomes a randomized copolymer, and the physical properties exhibited by the polymer block (A) cannot be sufficiently exhibited, and excellent heat resistance is imparted. I can't.
• the mass ratio (A)/(B) of polymer block (A) to polymer block (B) is in the range of 1/99 to 99/1. If the mass ratio (A)/(B) is outside the above range, the polyamide block copolymer cannot be imparted with excellent flexibility.
• the mass ratio (A)/(B) is preferably 5/95 to 95/5, more preferably 10/90 to 95/5, and still more preferably 20/80 to 95/5, may be 30/70 to 95/5, may be 40/60 to 95/5, may be 40/60 to 90/10, may be 45/55 to 90 /10, or 50/50 to 90/10.
• Number average molecular weight of the polyamide block copolymer is preferably 3,000 to 40,000, more preferably 4,000 to 30,000, still more preferably 4,500 to 25,000, still more preferably 5,000 ⁇ 20,000.
• the weight average molecular weight of the polyamide block copolymer is preferably 40,000 to 200,000, more preferably 43,000 to 200,000, still more preferably 45,000 to 200,000, still more preferably 50,000. ⁇ 200,000 and may be between 50,000 and 150,000.
• the polyamide block copolymer can be expected to exhibit tougher material properties and good moldability.
• the molecular weight distribution (weight average molecular weight/number average molecular weight) of the polyamide block copolymer is preferably 2.0 to 15.0, more preferably 3.0 to 12.0. If 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 melting point of the polyamide block copolymer is 230° C. or higher. When the melting point of the polyamide block copolymer is less than 230°C, the heat resistance is poor. For example, there is a possibility that the heat stability of a molded article obtained using a polyamide block copolymer may be insufficient.
• the melting point of the polyamide block copolymer is preferably 235°C or higher, more preferably 240°C or higher.
• the upper limit of the melting point of the polyamide block copolymer is not particularly limited, it is preferably 315° C. or less from the viewpoint of moldability and the like.
• the polyamide block copolymer of this embodiment preferably has a tensile strength at break measured according to JIS K 7161-1:2014 of 5 MPa or more, more preferably 10 MPa or more, and still more preferably 15 MPa or more.
• tensile properties are a measure of mechanical strength and flexibility. If the tensile strength at break is 5 MPa or more, it can be said that the polyamide block copolymer has excellent mechanical strength. More specifically, the tensile strength at break can be determined by the method described in the examples below.
• the polyamide block copolymer of the present embodiment has a tensile elongation at break measured according to JIS K 7161-1:2014, preferably 30% or more, more preferably 50% or more, still more preferably 100% or more, It can also be 200% or more.
• tensile properties are a measure of flexibility. If the tensile elongation at break is 30% or more, it can be said that the polyamide block copolymer has excellent flexibility. More specifically, the tensile elongation at break can be determined by the method described in the examples below.
• polyamide block copolymer composition As one of the present embodiments, a polyamide block copolymer composition containing the above polyamide block copolymer can be provided.
• the polyamide block copolymer composition is produced by adding components other than the polyamide block copolymer to the above polyamide block copolymer. Examples of such components include antioxidants, antiozonants, weather stabilizers, ultraviolet absorbers, hydrolysis stabilizers, fillers, crystal nucleating agents, reinforcing agents, carbon black, pigments, inorganic dyes, and organic dyes.
• the content of the additive is not particularly limited as long as it does not impair the effects of the present invention, but it can be 0.02 to 200 parts by mass with respect to 100 parts by mass of the polyamide block copolymer.
• Examples of the method of adding the additive include a method of adding during polymerization of the polyamide block copolymer, a method of dry blending with the polyamide block copolymer, and melt kneading.
• the method for producing the polyamide block copolymer composition is not particularly limited, and a method capable of uniformly mixing the polyamide block copolymer and the above additives can be preferably employed.
• a method of melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like is preferably adopted.
• the melt-kneading conditions are not particularly limited, for example, a method of melt-kneading for about 1 to 120 minutes at a temperature range higher than the melting point of the polyamide block copolymer by about 0 to 60° C. can be mentioned.
• a molded article made of the above polyamide block copolymer or the above polyamide block copolymer composition can be used.
• the molded article of this embodiment can be used as electrical and electronic parts, automobile parts, industrial parts, fibers, films, sheets, household goods, and various other molded articles of any shape and purpose.
• the polyamide block copolymer and polyamide block copolymer composition of the present embodiment exhibit flexibility and excellent heat resistance, and therefore can be used in a wide range of fields where these physical properties are required.
• the polyamide block copolymer and polyamide block copolymer composition of this embodiment can be It can be widely used as a material for various parts such as medical parts. Particularly complex-shaped parts by injection molding, hollow-molded parts by blow molding, hose- and tube-shaped parts, films and sheets by extrusion, lightweight parts and insulation materials by injection and/or extrusion foam molding, and additives for resin modification. It is applicable.
• the material for mobile phone and game machine hinges can be used as a material for mobile phone and game machine hinges, camera grips, printer tractor belts, electric wire coatings, tubes for home electric appliances, and the like.
• automobile parts more specifically, 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, inner liners for tires, etc.
• resistor rods fire hoses, conveyor belts, pulleys, wire cables, etc. More specifically, it can be used as a material for hair dryer brushes, manicure cases, hot curlers, fastener pulls, bobbin cases, console shutters, corrugated tubes, corrugated hoses, etc. among daily necessities and/or household goods.
• sports parts more specifically, it can be used as a material for running shoes, spike shoes, ski boots, and the like.
• medical parts more specifically, it can be used as a material for medical catheters, wearable devices, optical products, eye care parts, and the like.
• Each functional group amount [NH 2 ] and [COOH] of the semi-aromatic polyamide obtained from the measurement of the terminal amino group content and the terminal carboxyl group content, and the mass parts of the semi-aromatic polyamide shown in Table 3 ([PA Parts by mass]) and parts by mass of the terminal functionalizing agent ([parts by mass of terminal functionalizing agent]) were used to calculate the active terminal functional group content of the polymer block (A) from the following ⁇ formula>. It was confirmed that the terminal amino groups of the semi-aromatic polyamide were quantitatively converted to carboxyl groups by the terminal functionalizing agent (dicarboxylic acid monomer) described later.
• ⁇ formula>: Active terminal functional group content ( ⁇ mol/g) ([NH 2 ]+[COOH]) ⁇ ([PA parts by mass] ⁇ ([PA parts by mass]+[terminal functional agent parts by mass])))
• the peak temperature of the melting peak that appears when the temperature is again raised to 340°C at a rate of 10°C/min is the melting point (°C), and if there are multiple melting peaks, the peak temperature of the highest melting peak is the melting point (°C). bottom.
• 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 increased to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the reaction was allowed to proceed while removing steam gradually. Further reacting for 1 hour, a prepolymer was obtained. The resulting prepolymer was dried at 120° C. under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-6".
• 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 increased to 2.0 MPa. Heating was continued for 2 hours while maintaining the pressure at 2.0 MPa, and the reaction was allowed to proceed while removing steam gradually. Further reacting for 1 hour, a prepolymer was obtained. The resulting prepolymer was dried at 120° C. under reduced pressure for 24 hours and pulverized to a particle size of 1 mm or less. This prepolymer is abbreviated as "PA-8".
• Terminal functionalizing agent Moreover, the following dicarboxylic acid monomer was used as a terminal functionalizing agent as a constituent of the polymer block (A).
• Adipic acid abbreviated as “AA”
• TA Terephthalic acid
• PA-1 to PA-9 were evaluated for various physical properties as described above. The results are shown in Table 1 together with the physical properties of the end-functionalizing agents. Note that the notations in Table 1 are as follows. “n/i” indicates the molar ratio of linear diamine units/branched diamine units. In the columns of PA-8 and PA-9, “n/i” indicates the molar ratio of 1,10-decanediamine/hexamethylenediamine. “[ NH2 ]” indicates the terminal amino group content. “[COOH]” indicates terminal carboxyl group content.
• PE-1 Polyether diamine, manufactured by Sigma-Aldrich, Jeffamine (registered trademark) ED-600 ⁇
• PE-2 Polyether diamine, manufactured by Sigma-Aldrich, Jeffamine (registered trademark) ED-900 ⁇
• PE-3 Polyoxypropylene diamine, manufactured by Sigma-Aldrich, D-400 ⁇
• PE-4 Polyoxyethylenediamine, manufactured by Koei Chemical Co., Ltd.
• PE-5 Polyoxyethylenediamine, manufactured by Koei Chemical Co., Ltd.
• PE-6 Polyoxytetramethylenediamine, manufactured by Koei Chemical Co., Ltd., PTMGPA-1000
• Table 2 shows the physical properties of the polymer block (B). Note that the notations in Table 2 are as follows. “[ NH2 ]” indicates the terminal amino group content. “Tg” indicates the glass transition temperature measured by the following [method for measuring glass transition temperature]. “ ⁇ 70” indicates that the glass transition temperature is below ⁇ 70° C., since no inflection point was observed in the range of ⁇ 70° C. or above, which is the measurement limit of the apparatus. Also, as a reference value, the glass transition temperature (based on literature values) of polyetherdiol is described. “ ⁇ -70” indicates between -80 and -60°C, and “ ⁇ -85” indicates between -95 and -75°C.
• the polymer block (B) was used as a sample, and the glass transition temperature thereof was measured using a differential scanning calorimeter "DSC25" manufactured by TA Instruments.
• the glass transition temperature was determined by cooling the sample from 25°C to -90°C at a rate of 2°C/min under a nitrogen atmosphere, holding the sample at -90°C for 10 minutes to completely cool the sample, and then measuring the temperature by 2°C/min. The temperature at the point of inflection that appeared when the temperature was raised to 25°C at a rate of 10 minutes was defined as the glass transition temperature (°C).
• Examples 1 to 16 Comparative Example 1> Each component was premixed in the ratio (mass part) shown in Table 3. Solid samples were mixed by dry blending, and liquid samples were mixed by swelling into solid samples. 5 to 20 g of the prepared mixed sample is melted for 1 to 120 minutes at a cylinder temperature 0 to 60 ° C. higher than the melting point of polyamide using a desktop small kneader / injection molding machine ("Xplore MC15”) manufactured by Xplore Instruments. The mixture was kneaded, extruded, cooled and cut to produce a polyamide block copolymer in the form of pellets.
• Xplore MC15 desktop small kneader / injection molding machine
• the test piece for tensile evaluation was prepared by melting and kneading the mixed sample prepared in the same manner as above, and then tensile under the conditions of a mold temperature of 50 to 200 ° C. and an injection pressure of 0.1 to 7.0 bar in the T runner mold of the injection molding machine.
• a small test piece type 1BA (thickness of 2 mm, total length of 75 mm, length of parallel portion of 30 mm, width of parallel portion of 5 mm) for evaluation was prepared.
• the polyamide block copolymers obtained in Examples 1 to 16 were excellent in heat resistance and flexibility.
• the polyamide block copolymer obtained in Comparative Example 1 was difficult to melt-process, had poor heat resistance, and was a hard and brittle material, and therefore could not be measured in a tensile test.
• the polyamide block copolymer obtained by reacting the polymer block (A) and the polymer block (B) of this embodiment exhibits flexibility and excellent heat resistance. Therefore, the polyamide block copolymer and polyamide block copolymer composition of the present embodiment can be used, for example, in electrical and electronic parts, automobile parts, industrial material parts, industrial parts, daily necessities, household goods, sports parts, and leisure goods. It can be widely used as a material for various parts such as parts and medical parts. Particularly complex-shaped parts by injection molding, hollow-molded parts by blow molding, hose- and tube-shaped parts, films and sheets by extrusion, lightweight parts and insulation materials by injection and/or extrusion foam molding, and additives for resin modification. It is applicable.

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