LAMINATE, METHOD FOR MANUFACTURING SAME, AND FLUORORUBBER COMPOSITION

• US 20160288461A1
• Filed: 11/12/2014
• Published: 10/06/2016
• Est. Priority Date: 11/15/2013
• Status: Active Grant

• Current Assignee: Daikin Industries Ltd
• Original Assignee: Daikin Industries Ltd
• Inventors: KUWAJIMA, Yuuki, FUKUOKA, Shoji, KOMAZAWA, Kozue, TERADA, Junpei, TAEDA, Mayuko
• Granted Patent: US 10,421,257 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B32B 1/08 Tubular products
• CPC Class Codes: B32B 2307/714 Inert, i.e. inert to chemical degradation, corrosion
• CPC Class Codes: B32B 2307/7265 Non-permeable
• CPC Class Codes: B32B 25/08 of synthetic resin
• CPC Class Codes: B32B 25/14 comprising synthetic rubber copolymers B32B25/18 and B32B25/20 take precedence
• CPC Class Codes: B32B 2581/00 Seals; Sealing equipment; Gaskets
• CPC Class Codes: B32B 2597/00 Tubular articles, e.g. hoses, pipes
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/322 comprising halogenated polyolefins, e.g. PTFE
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08K 5/29 Compounds containing one or more carbon-to-nitrogen double bonds
• CPC Class Codes: C08L 27/12 containing fluorine atoms

Abstract

The present invention aims to provide a laminate in which a fluororesin layer and a fluororubber layer are firmly bonded even when the fluororesin layer contains a fluororesin having excellently low fuel permeability. The present invention relates to a laminate including a fluororubber layer (A) and a fluororesin layer (B) stacked on the fluororubber layer (A). The fluororubber layer (A) is a layer formed from a fluororubber composition. The fluororubber composition contains a fluororubber (a1) and a basic multifunctional compound having at least two nitrogen atoms in the molecule with a distance between the nitrogen atoms in the molecule of 5.70 Å or greater. The fluororubber (a1) has an absorption coefficient at 1720 cm⁻¹, determined after being brought into contact with triethyl amine, of 0.35 or lower. The fluororesin layer (B) is formed from a fluororesin (b1) having a fuel permeability coefficient of 2.0 g·mm/m²/day or lower.

Claims

1. A laminate comprising:

a fluororubber layer (A); and

a fluororesin layer (B) stacked on the fluororubber layer (A),

the fluororubber layer (A) being a layer formed from a fluororubber composition,

the fluororubber composition containing a fluororubber (a1) and a basic multifunctional compound having at least two nitrogen atoms in the molecule with a distance between the nitrogen atoms in the molecule of 5.70 Å

or greater,

the fluororubber (a1) having an absorption coefficient at 1720 cm<sup>−

1</sup>, determined after being brought into contact with triethyl amine, of 0.35 or lower,

the fluororesin layer (B) being formed from a fluororesin (b1) having a fuel permeability coefficient of 2.0 g·

mm/m²/day or lower.

2. The laminate according to claim 1,

wherein the fluororesin (b1) is at least one selected from the group consisting of polychlorotrifluoroethylene, a chlorotrifluoroethylene-containing copolymer, and a tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer,

the tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer having a copolymerization ratio (mol % ratio) of tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride=(75 to 95)/(0.1 to 10)/(0.1 to 19).

3. The laminate according to claim 1,

wherein the fluororubber composition contains a peroxide vulcanizing agent.

4. The laminate according to claim 1,

wherein the fluororubber (a1) is at least one selected from the group consisting of a vinylidene fluoride/CH₂═

CFRf¹ copolymer (wherein Rf^l is a C1-C12 linear or branched fluoroalkyl group), a tetrafluoroethylene/propylene copolymer, a tetrafluoroethylene/propylene/vinylidene fluoride copolymer, an ethylene/tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer, a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene/perfluoro(alkyl vinyl ether)/ethylene copolymer, a vinylidene fluoride/hexafluoropropylene copolymer, and a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer.

5. The laminate according to claim 1,

wherein the basic multifunctional compound has two or more functional groups selected from —

NH₂, —

NH₃⁺, —

NHCOOH, —

NHCOO⁻

, —

N═

CR¹R² (wherein R¹ and R² are each individually a C0-C 12 organic group), —

NR³R⁴ (wherein R³ and R⁴ are each individually a C0-C12 organic group), and —

NR³R⁴R⁵ (wherein R³, R⁴, and R⁵ are each individually a C0-C12 organic group).

6. The laminate according to claim 1,

wherein the basic multifunctional compound has two or more functional groups selected from —

NH₂, —

NH₃⁺, —

N═

CR¹R² (wherein R¹ and R² are each individually a C0-C12 organic group), and —

NR³R⁴R⁵ (wherein R³, R⁴, and R⁵ are each individually a C0-C12 organic group).

7. The laminate according to claim 1,

wherein the basic multifunctional compound is at least one selected from the group consisting of N,N′

-dicinnamylidene-1,6-hexamethylenediamine and NH₂—

(CH₂)_n—

NH₂ (wherein n is 5 to

     12).

8. The laminate according to claim 1,

wherein the basic multifunctional compound is at least one selected from the group consisting of N,N′

-dicinnamylidene-1,6-hexamethylenediamine and hexamethylenediamine.

9. The laminate according to claim 1, which has an initial interlayer bond strength of 5 N/cm or higher.

10. The laminate according to claim 1,

wherein the fluororubber layer (A) is stacked on both sides of the fluororesin layer (B).

11. The laminate according to claim 1,

wherein the fluororesin layer (B) is stacked on both sides of the fluororubber layer (A).

12. The laminate according to claim 1, further comprising a fluorine-free rubber layer (C1a),

wherein the fluororubber layer (A), the fluororesin layer (B), and the fluorine-free rubber layer (C1a) are stacked in the order set forth.

13. The laminate according to claim 12, further comprising a fluorine-free rubber layer (D1a),

wherein the layers are stacked in the order of the fluorine-free rubber layer (D1a), the fluororubber layer (A), the fluororesin layer (B), and the fluorine-free rubber layer (C1a);

in the order of the fluororubber layer (A), the fluororesin layer (B), the fluorine-free rubber layer (D1a), and the fluorine-free rubber layer (C1a);

or in the order of the fluororubber layer (A), the fluororesin layer (B), the fluorine-free rubber layer (C1a), and the fluorine-free rubber layer (D1a).

14. The laminate according to claim 1,

wherein the fluororubber layer (A) and the fluororesin layer (B) are vulcanization-bonded to each other.

15. A method for manufacturing a laminate comprising:

mixing a fluororubber (a1) and a basic multifunctional compound having at least two nitrogen atoms in the molecule with a distance between the nitrogen atoms in the molecule of 5.70 Å

or greater to provide a fluororubber composition;

stacking an unvulcanized fluororubber layer prepared by molding the fluororubber composition and a fluororesin layer; and

vulcanizing the unvulcanized fluororubber layer and the fluororesin layer stacked,

the fluororubber composition containing the fluororubber (a1) and the basic multifunctional compound,

the fluororubber (a1) having an absorption coefficient at 1720 cm<sup>−

1</sup>, determined after being brought into contact with triethyl amine, of 0.35 or lower,

the fluororesin layer being formed from a fluororesin (b1) having a fuel permeability coefficient of 2.0 g·

mm/m²/day or lower.

16. A fluororubber composition comprising:

a fluororubber (a1); and

a basic multifunctional compound having at least two nitrogen atoms in the molecule with a distance between the nitrogen atoms in the molecule of 5.70 Å

or greater,

the fluororubber (a1) having an absorption coefficient at 1720 cm<sup>−

1</sup>, determined after being brought into contact with triethyl amine, of 0.35 or lower.