# US 2017/0283556 A1 · Polyamide-based thermoplastic elastomer composition and molded article thereof

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- Number: US 2017/0283556 A1
- Document ID: US20170283556A1
- Status: Published application
- Kind: A1
- Application number: 15/101,808
- Filed: 2014-12-05
- Published: 2017-10-05
- Earliest claimed: 2013-12-06
- Assignees: Mitsui Chemicals, Inc.
- Applicants: Mitsui Chemicals, Inc.
- Inventors: Hiroki EBATA; Tatsuya ENOMOTO; Isao WASHIO; Fumio KAGEYAMA; Atsushi TAKEISHI; Yuji ISHII; Akinori AMANO
- Web page: https://patentgrep.com/patent/US20170283556A1

## CPC

- C08G 69/26: derived from polyamines and polycarboxylic acids
- C07C 63/24: 1,3 - Benzenedicarboxylic acid
- C07C 63/26: 1,4 - Benzenedicarboxylic acid
- C08J 3/246: {Intercrosslinking of at least two polymers}
- C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence)
- F16L 11/04: made of rubber or flexible plastics
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- C08J 2377/00: Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J 2423/08: Copolymers of ethene (C08J2423/16 takes precedence)
- C08J 2477/00: Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08L 2312/04: with phenolic resin
- G01N 25/20: by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity (calorimeters per se G01K)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- F16L: PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)

## Abstract

The present invention relates to a polyamide-based thermoplastic elastomer composition [Y] in which a rubber composition [X] and a phenol resin-based crosslinking agent [IV] are dynamically crosslinked, the rubber composition [X] comprising a polyamide [I] including 30 to 100% by mole of a terephthalic acid structural unit and having a melting point of 220 to 290° C.; an ethylene-α-olefin-unconjugated polyene copolymer rubber [II] including structural units of ethylene, an α-olefin having 3 to 20 carbon atoms and an unconjugated polyene, respectively; and an olefin-based polymer [III] including 0.3 to 5.0% by mass of a functional group structural unit, (the total of [I] to [IV]: 100% by mass).

## Claims

### Claim 1

A polyamide-based thermoplastic elastomer [Y], in which a rubber composition [X] and a phenol resin-based crosslinking agent [IV] are dynamically crosslinked,
wherein the rubber composition [X] comprises:
a polyamide [I] comprising a structural unit derived from terephthalic acid with 30 to 100% by mole in total structural units of dicarboxylic acids and a melting point (Tm) determined by differential scanning calorimetry (DSC) of the polyamide being 220 to 290° C.,
an ethylene-α-olefin-unconjugated polyene copolymer rubber [II] comprising structural units derived from ethylene [a], an α-olefin [b] having 3 to 20 carbon atoms, and an unconjugated polyene [c] having at least one carbon-carbon double bond in one molecule, respectively, and
an olefin-based polymer [III] comprising 0.3 to 5.0% by mass of a functional group structural unit in a molecule.

### Claim 2 (depends on 1)

The polyamide-based thermoplastic elastomer composition [Y] according to claim 1, wherein the polyamide [I] further comprises a structural unit derived from isophthalic acid as a component of the dicarboxylic acid, and a structural unit derived from an aliphatic diamine having 4 to 15 carbon atoms as a diamine component.

### Claim 3 (depends on 2)

The polyamide-based thermoplastic elastomer composition [Y] according to claim 2, wherein a molar ratio of the structural unit derived from isophthalic acid/the structural unit derived from terephthalic acid in the polyamide [I] is 65/35 to 50/50.

### Claim 4 (depends on 1)

The polyamide-based thermoplastic elastomer composition [Y] according to claim 1, wherein 40 to 100% by mole of a total of a diamine component comprised in the polyamide [I] is a structural unit derived from 1,6-hexanediamine.

### Claim 5 (depends on 1)

The polyamide-based thermoplastic elastomer composition [Y] according to claim 1, wherein the functional group structural unit in the olefin-based polymer [III] comprises a functional group selected from the group consisting of a carboxylic acid group, an ester group, an ether group, an aldehyde group and a ketone group.

### Claim 6 (depends on 5)

The polyamide-based thermoplastic elastomer composition [Y] according to claim 5, wherein the functional group structural unit in the olefin-based polymer [III] is a maleic anhydride structural unit.

### Claim 7

A polyamide-based thermoplastic elastomer composition comprising:
a polyamide [I] comprising a structural unit derived from terephthalic acid with 30 to 100% by mole in total structural units of dicarboxylic acids and a melting point (Tm) determined by differential scanning calorimetry (DSC) of the polyamide being 220 to 290° C. as a matrix component; and
a dispersion component dispersed in the matrix component, the dispersion component being a particle comprising an ethylene-α-olefin-unconjugated polyene copolymer rubber [II] comprising structural units derived from ethylene [a], an α-olefin [b] having 3 to 20 carbon atoms and an unconjugated polyene [c] having at least one carbon-carbon double bond in one molecule, respectively, and an olefin-based polymer [III] comprising 0.3 to 5.0% by mass of a functional group structural unit in a molecule, and the dispersion component being satisfied the following (1):
(1) a cross sectional area of the particle, in which a particle size is 5 μm or more, of the dispersion component is measured, and a proportion of a cumulative cross sectional area of the area of the particle to an entire cross sectional area analyzed is 10% or less.

### Claim 8

A polyamide-based thermoplastic elastomer composition [Y1], in which
a rubber composition [X] comprising:
10 to 60% by mass of a polyamide [I] comprising a structural unit derived from terephthalic acid with 30 to 100% by mole in total structural units of dicarboxylic acids and a melting point (Tm) determined by differential scanning calorimetry (DSC) of the polyamide being 220 to 290° C.;
30 to 86% by mass of an ethylene-α-olefin-unconjugated polyene copolymer rubber [II] comprising structural units derived from ethylene [a], an α-olefin [b] having 3 to 20 carbon atoms and an unconjugated polyene [c] having at least one carbon-carbon double bond in one molecule, respectively; and
3 to 30% by mass of an olefin-based polymer [III] comprising 0.3 to 5.0% by mass of a functional group structural unit in a molecule, and
1 to 10% by mass of a phenol resin-based crosslinking agent [IV] are dynamically crosslinked, provided that a total amount of [I], [II], [III] and [IV] is 100% by mass.

### Claim 9 (depends on 8)

The polyamide-based thermoplastic elastomer composition [Y1] according to claim 8, wherein a mass ratio ([II]/[III]) of the ethylene-α-olefin-unconjugated polyene copolymer rubber [II] to the olefin-based polymer [III] in the rubber composition [X] is 95/5 to 60/40.

### Claim 10 (depends on 8)

The polyamide-based thermoplastic elastomer composition [Y1] according to claim 8, wherein 10% or more of an end group of a molecular chain of the polyamide [I] is terminated by an end-terminating agent, and an amount of a terminal amino group of the molecular chain is 0.1 to 100 mmol/kg.

### Claim 11 (depends on 8)

A molded article obtained from the polyamide-based thermoplastic elastomer composition [Y1] according to claim 8.

### Claim 12

A polyamide-based thermoplastic elastomer composition [Y2] in which
a rubber composition [X] comprising:
30 to 87.7% by mass of a polyamide [I] comprising a structural unit derived from terephthalic acid with 30 to 100% by mole in total structural units of dicarboxylic acids and a melting point (Tm) determined by differential scanning calorimetry (DSC) of the polyamide being 220 to 290° C.;
10 to 45% by mass of an ethylene-α-olefin-unconjugated polyene copolymer rubber [II] comprising structural units derived from ethylene [a], an α-olefin [b] having 3 to 20 carbon atoms and an unconjugated polyene [c] having at least one carbon-carbon double bond in one molecule, respectively; and
2 to 20% by mass of an olefin-based polymer [III] comprising 0.3 to 5.0% by mass of a functional group structural unit in a molecule, and
0.3 to 5.0% by mass of a phenol resin-based crosslinking agent [IV] are dynamically crosslinked, provided that a total amount of [I], [II], [III] and [IV] is 100% by mass.

### Claim 13 (depends on 12)

An industrial tube having at least a layer comprising the polyamide-based thermoplastic elastomer composition [Y2] according to claim 12.

### Claim 14 (depends on 13)

The industrial tube according to claim 13, which is a tube for automobile piping, a pneumatic tube, a hydraulic tube, a paint spray tube or a medical tube.

### Claim 15 (depends on 13)

The industrial tube according to claim 13, having an outer diameter of 2 mm to 50 mm and a thickness of 0.2 mm to 10 mm.

### Claim 16 (depends on 13)

The industrial tube according to claim 13, further comprising a layer comprising at least one resin selected from the group consisting of a fluororesin, a high density polyethylene resin, a polybutylene naphthalate resin (PBN), an aliphatic polyamide resin, an aromatic polyamide resin, a metaxylene group-containing polyamide resin, an ethylene-vinyl acetate copolymer saponified product (EVOH) and a polyphenylene sulfide resin (PPS).

### Claim 17 (depends on 12)

A polyamide-based thermoplastic elastomer composition [Z] comprising 10 to 35% by mass of a polyamide [Z1] having a melting point (Tm) determined by differential scanning calorimetry (DSC) of 210 to 270° C. and a molten heat capacity (ΔH) determined by DSC of 45 to 80 mJ/mg, and 65 to 90% by mass of a polyamide-based resin composition [Z2], provided that a total amount of [Z1] and [Z2] is 100% by mass, wherein
the polyamide-based resin composition [Z2] is the polyamide-based thermoplastic elastomer composition [Y2] according to claim 12.

### Claim 18 (depends on 17)

A molded article obtained from the polyamide-based thermoplastic elastomer composition [Z] according to claim 17 by injection molding or blow molding.

### Claim 19 (depends on 17)

An automobile constant velocity joint boot comprising the polyamide-based thermoplastic elastomer composition [Z] according to claim 17.