Multilayer laminate
View Patent ↗To provide a multilayer laminate excellent in fuel barrier properties, fuel oil resistance, mechanical strength and interlaminar adhesion strength. A multilayer laminate having a layer of a fluororesin containing acid anhydride residue (for example, a tetrafluoroethylene/ethylene/(perfluoroethyl)ethylene/itaconic anhydride copolymer) and a layer of an amine-modified thermoplastic resin (for example, polyphenylene sulfide modified by a silane coupling agent containing an amino group). The multilayer laminate can be produced by co-extrusion and is excellent in the interlaminar adhesion strength, whereby it is suitable for a fuel hose or the like.
1. A multilayer laminate comprising a laminate structure having a layer of a fluororesin comprising acid anhydride residues and a layer of an amine-modified thermoplastic resin, directly laminated; wherein
the fluororesin is a polymer of tetrafluoroethylene, ethylene, CH 2 ═CH(CF 2 ) 2 F and at least one acid anhydride having a polymerizable unsaturated bond selected from the group consisting of itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride;
one or more repeating units based on the at least one acid anhydride are in the main chain of the fluororesin; and
the amine-modified thermoplastic resin is produced by melt-kneading a silane coupling agent having an amino group with a thermoplastic resin, the thermoplastic resin being polyphenylene sulfide.
2. The multilayer laminate according to claim 1 , wherein the content of the acid anhydride residue in the fluororesin is from 0.01 to 3 mol % based on the total polymerized units constituting the fluororesin.
3. The multilayer laminate according to claim 1 , wherein the multilayer laminate is a fuel transfer hose.
4. A method for producing the multilayer laminate as defined in claim 1 , characterized by subjecting the fluororesin containing acid anhydride residue and the amine-modified thermoplastic resin to co-extrusion.
5. The multilayer laminate according to claim 1 , wherein the content of the acid anhydride residue in the fluororesin is from 0.05 to 2 mol % based on the total polymerized units constituting the fluororesin.
6. The multilayer laminate according to claim 1 , wherein the content of the acid anhydride residue in the fluororesin is from 0.1 to 1 mol % based on the total polymerized units constituting the fluororesin.
7. The multilayer laminate according to claim 1 , wherein the fluororesin has a volume flow rate from 0.1 to 1,000 mm 3 /sec.
8. The multilayer laminate according to claim 1 , wherein the fluororesin has a volume flow rate from 5 to 500 mm 3 /sec.
9. The multilayer laminate according to claim 1 , wherein the fluororesin has a volume flow rate from 10 to 200 mm 3 /sec.
10. The multilayer laminate according to claim 3 , wherein the fuel transfer hose comprises an inner surface with a surface resistivity of at most 1×10 9 Ω/□.
11. The multilayer laminate according to claim 3 , wherein the fuel transfer hose comprises an inner surface with a surface resistivity of at most 1×10 5 Ω/□.
12. The multilayer laminate according to claim 1 , wherein the multilayer laminate has an interlaminar adhesion strength of a least 2.0 N/cm.
13. The multilayer laminate according to claim 1 , wherein the multilayer laminate has an interlaminar adhesion strength of a least 3.5 N/cm.
14. The multilayer laminate according to claim 1 , wherein the multilayer laminate has a thickness from 10 μm to 2 cm.
15. The multilayer laminate according to claim 1 , wherein the multilayer laminate has a thickness from 50 μm to 1 cm.
16. The multilayer laminate according to claim 1 , wherein the fluororesin layer has a thickness from 5 μm to 500 μm.
17. The multilayer laminate according to claim 1 , wherein the fluororesin layer has a thickness from 50 μm to 500 μm.
18. The multilayer laminate according to claim 1 , wherein the amine-modified thermoplastic resin layer has a thickness from 5 μm to 1.5 cm.
19. The multilayer laminate according to claim 1 , wherein the amine-modified thermoplastic resin layer has a thickness from 50 μm to 1 cm.