IP Library Granted Patent US 10,933,615
Granted Patent B2
US 10,933,615 · App. 16/651,494 · Granted Mar 2, 2021

Multilayer tubes

Inventors: Kazutoshi Tsuboi (Ube, JP); Koji Nakamura (Ube, JP); Takaaki Kusumoto (Ube, JP); Daisuke Douyama (Ube, JP)
Assignee: UBE INDUSTRIES, LTD.
B32B27/34B29C48/022B29C48/18B32B1/08B32B27/08B32B27/304B32B27/322F02M37/0011B29K2077/00B32B2597/00
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Quick Facts
Patent No.
US 10,933,615
App. No.
16/651,494
Granted
Mar 2, 2021
Kind
B2
Abstract

It is provided a multilayer tube having a layer containing a specific aliphatic polyamide composition and a layer containing a semi-aromatic polyamide composition which contains a semi-aromatic polyamide having a specific structure or a mixture thereof, and the both layers being disposed adjacent to each other, wherein the aliphatic polyamide composition contains an aliphatic polyamide having a melting point of a specific value or less, and a ratio of the number of the methylene groups to the number of the amide groups is a specific value or more, an aliphatic polyamide having an absolute value of a difference in solubility parameter SP values to that of the aliphatic polyamide being a specific range, and an elastomer polymer containing a constitutional unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group.

Claims (35)

1. A multilayer tube which comprises two or more layers containing Layer (a) and Layer (b), wherein

at least one pair of Layer (a) and Layer (b) are disposed adjacent to each other,

the Layer (a) contains an aliphatic polyamide composition (A),

the Layer (b) contains a semi-aromatic polyamide composition (B),

the aliphatic polyamide composition (A) contains a polyamide (A1), a polyamide (A2) and an elastomer polymer (A3),

the polyamide (A1) is an aliphatic polyamide having a melting point measured in accordance with ISO 11357-3 of 210° C. or lower, and having a ratio of methylene groups to amide groups of 8.0 or more, and contained in the aliphatic polyamide composition (A) in an amount of 40% by mass or more and 85% by mass or less,

the polyamide (A2) is a polyamide other than the polyamide (A1) and contained in the aliphatic polyamide composition (A) in an amount of 10% by mass or more and 30% by mass or less,

the elastomer polymer (A3) contains a constitutional unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group, and contained in the aliphatic polyamide composition (A) in an amount of 5% by mass or more and 30% by mass or less,

an absolute value of a difference in solubility parameter SP values of the polyamide (A1) and the polyamide (A2) [|(SP value of polyamide (A1))−(SP value of polyamide (A2))|] is 1.8 (MPa) 1/2 or more and 5.5 (MPa) 1/2 or less,

the semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) and/or a semi-aromatic polyamide (B2),

the semi-aromatic polyamide (B1) and/or the semi-aromatic polyamide (B2) is/are contained in an amount(s) of 60% by mass or more,

the semi-aromatic polyamide (B1) contains 60% by mass or more and 100% by mass or less of a semi-aromatic polyamide (B11) and 0% by mass or more and 40% by mass or less of a semi-aromatic polyamide (B12),

the semi-aromatic polyamide (B11) contains 50 mol % or more of an aliphatic diamine unit having 4 or more and 8 or less carbon atoms based on whole diamine units of the semi-aromatic polyamide (B11), and contains 50 mol % or more of a dicarboxylic acid unit which contains at least one kind selected from the group consisting of a terephthalic acid unit, an isophthalic acid unit and a naphthalene dicarboxylic acid unit based on whole dicarboxylic acid units of the semi-aromatic polyamide (B11),

the semi-aromatic polyamide (B12) contains 50 mol % or more of an aliphatic diamine unit having 9 or more and 12 or less carbon atoms based on whole diamine units of the semi-aromatic polyamide (B12), and contains 50 mol % or more of a dicarboxylic acid unit which contains at least one kind selected from the group consisting of a terephthalic acid unit, an isophthalic acid unit and a naphthalene dicarboxylic acid unit based on whole dicarboxylic acid units of the semi-aromatic polyamide (B12),

the semi-aromatic polyamide (B2) contains 60% by mass or more and 100% by mass or less of a semi-aromatic polyamide (B21) and 0% by mass or more and 40% by mass or less of a semi-aromatic polyamide (B22),

the semi-aromatic polyamide (B21) contains 50 mol % or more of a xylylene diamine unit and/or a bis(aminomethyl)naphthalene unit based on whole diamine units of the semi-aromatic polyamide (B21), and contains 50 mol % or more of an aliphatic dicarboxylic acid unit having 4 or more and 8 or less carbon atoms based on whole dicarboxylic acid units of the semi-aromatic polyamide (B21), and

the semi-aromatic polyamide (B22) contains 50 mol % or more of a xylylene diamine unit and/or a bis(aminomethyl)naphthalene unit based on whole diamine units of the semi-aromatic polyamide (B22), and contains 50 mol % or more of an aliphatic dicarboxylic acid unit having 9 or more and 12 or less carbon atoms based on whole dicarboxylic acid units of the semi-aromatic polyamide (B22).

2. The multilayer tube according to claim 1 , wherein the polyamide (A1) is at least one kind of a homopolymer selected from the group consisting of polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecamide (polyamide 1212), polyundecanamide (polyamide 11) and polydodecanamide (polyamide 12), and/or at least one kind of a copolymer using several kinds of raw material monomers forming the homopolymer.

3. The multilayer tube according to claim 1 , wherein the polyamide (A2) is at least one kind of a homopolymer selected from the group consisting of polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610) and polyhexamethylene dodecamide (polyamide 612), and/or at least one kind of a copolymer using several kinds of raw material monomers forming the homopolymer, or at least one kind of a copolymer comprising a raw material monomer(s) forming at least one kind selected from the group consisting of the polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610) and polyhexamethylene dodecamide (polyamide 612) as a main component, and using several kinds of raw material monomers forming at least one kind selected from the group consisting of polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecamide (polymide 1212), polyundecanamide (polyamide 11) and polydodecanamide (polyamide 12).

4. The multilayer tube according to claim 1 , wherein when the terminal amino group concentration which is summed values of the respective terminal amino group concentrations (μeq/g) of the polyamide (A1) and the polyamide (A2) per 1 g of the aliphatic polyamide composition (A) multiplying a mixing mass ratio is made [A] (μeq/g), and when the terminal carboxyl group concentration which is summed values of the respective terminal carboxyl group concentrations (μeq/g) of the polyamide (A1) and the polyamide (A2) per 1 g of the aliphatic polyamide composition (A) multiplying a mixing mass ratio is made [B] (μeq/g), then [A]>[B]+10.

5. The multilayer tube according to claim 1 , wherein the semi-aromatic polyamide composition (B) contains an elastomer polymer (B3), and the elastomer polymer (B3) contains a constitutional unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group.

6. The multilayer tube according to claim 1 , wherein, in at least one pair of the adjacent Layer (a) and Layer (b), the Layer (b) is disposed inside the Layer (a) and adjacent thereto.

7. The multilayer tube according to claim 1 , wherein the innermost layer is a conductive layer containing a thermoplastic resin composition in which a conductive tiller is contained.

8. The multilayer tube according to claim 1 , wherein it is produced by co-extrusion molding.

9. The multilayer tube according to claim 1 , wherein it is used as a fuel tube.

10. The multilayer tube according to claim 1 , which further comprises Layer (c),

at least one pair of the Layer (b) and the Layer (c) are disposed adjacent to each other,

the Layer (c) contains a polyamide composition (C), and

the polyamide composition (C) contains a polyamide (C1) and an elastomer polymer (C2),

the polyamide (C1) is a polyamide other than the “aliphatic polyamide having a melting point measured in accordance with ISO 11357-3 of 210° C. or lower, and the ratio of the number of the methylene groups to the number of the amide groups of 8.0 or more”, and is contained in an amount of 70% by mass or more and 95% by mass or less based on 100% by mass of the polyamide (C1) and the elastomer polymer (C2) in total, and

the elastomer polymer (C2) contains a constitutional unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group, and is contained in an amount of 5% by mass or more and 30% by mass or less based on 100% by mass of the polyamide (C1) and the elastomer polymer (C2) in total.

11. The multilayer tube according to claim 10 , wherein the Layer (c) is disposed inside the Layer (b).

12. The multilayer tube according to claim 1 , which further comprises Layer (d), and

the Layer (d) contains a fluorine-containing polymer (D) into which a functional group having reactivity to an amino group is introduced in its molecular chain.

13. The multilayer tube according to claim 12 , wherein the Layer (d) is disposed inside the Layer (b).

Assignments (2)
CHANGE OF NAME Recorded Jul 14, 2023
From: UBE INDUSTRIES, LTD.
To: UBE CORPORATION
Reel/Frame 064275/0021 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 27, 2020
From: TSUBOI, KAZUTOSHI; NAKAMURA, KOJI; KUSUMOTO, TAKAAKI; DOUYAMA, DAISUKE
To: UBE INDUSTRIES, LTD.
Reel/Frame 052248/0212 →