Multi-layer composite for reusable multi-layer packs

• US 5,418,068 A
• Filed: 10/26/1992
• Issued: 05/23/1995
• Est. Priority Date: 10/31/1991
• Status: Expired due to Fees

• Current Assignee: EMS-Inventa AG (Emesta Holding AG)
• Original Assignee: EMS-Inventa AG (Emesta Holding AG)
• Inventors: Torre, Hans-Dalla, Caluori, Hans-Jorg, Hewel, Manfred
• Primary Examiner(s): Sluby, P. C.
• Assistant Examiner(s): ABRAHAM, DAVID JAMES
• Application Number:
  US07/966,299
• Time in Patent Office: 939 Days
• Field of Search: 428/474.4, 428/475.5, 528/847
• US Class Current: 428/474.4
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: Y10T 428/31725 Of polyamide
• CPC Class Codes: Y10T 428/31739 Nylon type

Abstract

A multi-layer composite made of at least one copolyamide protective layer, and at least one copolyamide barrier layer, with the protective layer placed such that it is between the barrier layer and a source of moisture. The protective copolyamide layer is composed of a partially aromatic, amorphous copolyamide of a specified composition, and the barrier layer is composed of a partially aromatic barrier copolyamide of a specified composition. This multi-layer composite is especially useful in reusable packaging systems, such as beverage bottles or containers of any kind.

Claims

1. A multi-layer composite containing at least one copolyamide protective layer and at least one copolyamide barrier layer laminated therewith, said protective layer being between said barrier layer and a source of moisture, said protective layer comprising a partially aromatic, amorphous protective copolyamide composed of at least one monomer taken from each of the following classes:

(1) 2 to 40 molar parts of (a) at least one long-chain aliphatic monomer having 9 to 40 carbon atoms, (b) at least one lactam having 9 to 12 carbon atoms, (c) at least one ω

-aminocarboxylic acid having 9 to 12 carbon atoms, and (d) at least one dodecane diamine and at least one dodecane diacid in substantially equimolar ratios,

(2) at least one cycloaliphatic diamine having 6 to 26 carbon atoms, and

(3) at least one substituted or unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms,

wherein (1), (2) and (3) total 100 molar parts, and (2), and (3) are present in substantially equimolar amounts;

a barrier layer consisting essentially of at least one partially aromatic barrier copolyamide consisting essentially of at least one monomer taken from each of the following classes;

(4) at least one short-chain aliphatic diamine having 4 to 8 carbon atoms which may be replaced by up to 49% by weight of at least one additional diamine selected from the group consisting of cycloaliphatic diamines having 6 to 26 carbon atoms, and/or by up to 40 molar % of at least one araliphatic diamine having 6 to 26 carbon atoms, and

(5) at least one substituted or unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms, of which 0 to 20 molar parts may be replaced by at least one aliphatic dicarboxylic acid having 4 to 8 carbon atoms,

wherein (4) and (5) total 100 molar parts, and are present in substantially equimolar amounts.

2. The composition of claim 1 comprising a plurality of said protective layers, a plurality of said barrier layers, or both.

3. The composite of claim 1 comprising a plurality of said barrier layers of different copolyamides.

4. The composite of claim 1 wherein said protective copolyamide is composed of at least one monomer taken from each of the following classes:

(1) (b) at least one lactam, (c) at least one ω

-aminocarboxylic acid having 11 or 12 carbon atoms, and (d) at least one dodecane diamine and at least one dodecane diacid, and

(2) unsubstituted or alkyl-substituted 4,4'"'"'-diaminodicyclohexyl-alkane, said alkyl having 1 to 4 carbon atoms and said alkane having 1 to 3 carbon atoms, and

(3) terephthalic acid which may be replaced in whole or part by isophthalic acid and by up to 15 molar %, based on said terephthalic acid and/or said isophthalic acid, by at least one aliphatic dicarboxylic acid having 4 to 8 carbon atoms or at least one cycloaliphatic dicarboxylic acid having 8 to 20 carbon atoms.

5. The composite of claim 1 wherein said protective copolyamide is composed of at least one monomer taken from each of the following classes:

(1) (b) at least one lactam, (c) at least one ω

-aminocarboxylic acid having 11 or 12 carbon atoms, and (d) at least one dodecane diamine and at least one dodecane diacid, and

(2) (a) at least one 4,4'"'"'-diaminodicyclohexylalkane, and (b) at least one alkyl-substituted 4,4'"'"'-diaminodicyclohexyl alkane, wherein said alkyl has 1 to 4 carbon atoms and said alkane has 1 to 3 carbon atoms, and

(3) terephthalic acid which may be replaced in whole or part by isophthalic acid and up to 15 molar %, based on said terephthalic acid and/or said isophthalic acid, by at least one aliphatic dicarboxylic acid having 4 to 8 carbon atoms or at least one cycloaliphatic dicarboxylic acid having 8 to 20 carbon atoms.

6. The composite of claim 1 wherein said protective copolyamide is composed of at least one monomer taken from each of the following classes:

(1) 2 to 40 molar parts of (b) at least one lactam and (c) at least one ω

-aminocarboxylic acid having 9 to 12 carbon atoms, and

(2) at least one bis-(amino-cyclohexyl)-alkane or at least one alkylated derivative thereof having 6 to 24 carbon atoms, and

(3) at least one aromatic dicarboxylic acid having 8 to 12 carbon atoms which may be replaced by up to 15 molar % of at least one aliphatic dicarboxylic acid having 4 to 8 carbon atoms.

7. The composite of claim 5 wherein (1) is laurin lactam, (2) is 4,4'"'"'-diamino-3,3'"'"'-dimethyl-dicyclohexyl-methane, and (3) is terephthalic acid, isophthalic acid, or a mixture thereof.

8. The composite of claim 6 wherein (1) is laurin lactam, (2) is 4,4'"'"'-diamino-3,3'"'"'-dimethyl-dicyclohexyl-methane, and (3) is terephthalic acid, isophthalic acid, or a mixture thereof.

9. The composite of claim 1 wherein (1) is a dimeric fatty acid having 28 to 40 carbon atoms, and (2) is 4,4'"'"'-diamino-3,3'"'"'dimethyldicyclohexyl-methane, 3-aminomethyl-3,5,5'"'"'-trimethyl-1-cyclohexylamine, or a mixture thereof, and (3) is terephthalic acid, isophthalic acid, or a mixture thereof, (1) and (2) being present in substantially equimolar amounts.

10. The composite of claim 1 wherein (5) is selected from the group consisting of hexamethylene diamine, diamine-3,3'"'"'dimethyl-dicyclohexyl methane, and xylylene diamine.

11. The composite of claim 10 wherein (5) comprises hexamethylene diamine.

12. The composite of claim 1 wherein said barrier copolyamide diamine and cycloaliphatic diamine in a molar ratio of 1:

49 to 50;

0.

13. The composite of claim 1 wherein said barrier copolyamide comprises as building blocks:

(4) 50 molar parts of a composition comprising 25 to 48 molar parts hexamethylene diamine and 2 to 25 molar parts, 4,4'"'"'-diamino-3,3'"'"'-dimethyldicyclohexyl methane and

(5) a mixture of isophthalic acid and terephthalic acid in a molar ratio of 1;

4 to 4;

1.

14. The composite of claim 1 wherein said barrier copolyamide comprises as building blocks:

(4) 50 molar parts of a composition comprising 10 to 40 molar parts hexamethylene diamine, 5 to 20 molar parts m-xylylene diamine, and 5 to 20 molar parts 4,4'"'"'-diamino-3,3'"'"'-dimethylcyclohexyl methane, and

(5) isophthalic acid, terephthalic acid, or a mixture thereof.

15. The composite of claim 1 wherein said barrier copolyamide comprises as building blocks:

(4) 50 molar parts of a composition comprising 5 to 45 molar parts hexamethylene diamine, 5 to 45 molar parts m-xylylene diamine, and

(5) isophthalic acid, terephthalic acid, or a mixture thereof.

16. The composite of claim 1 wherein said barrier copolyamide is composed of

(4) hexamethylene diamine and

(5) isophthalic acid, terephthalic acid, or a mixture thereof.

17. The composite of claim 1 wherein said barrier copolyamide is composed of at least one monomer taken from each of the following classes:

(4) 30 to 50 molar parts of at least one short-chain aliphatic diamine having 4 to 8 carbon atoms, which may be replaced by up to 49% by weight of at least one cycloaliphatic diamine and/or up to 40 molar % of at least one araliphatic diamine, and

(5) terephthalic acid, isophthalic acid, or a mixture thereof, which may be replaced by up to 20 molar % of at least one aliphatic dicarboxylic acid having 4 to 8 carbon atoms.

18. The composite of claim 1 wherein said barrier copolyamide is composed of 70 to 95 molar parts of (4) hexamethylene diamine and 4,4'"'"'-diamino-3,3'"'"'-dimethylcyclohexyl methane in a molar ratio of 1:

5 to 5;

1, and

(5) isophthalic acid, terephthalic acid, or a mixture thereof.

19. The composite of claim 1 wherein said barrier copolyamide is composed of

(4) 15 to 40 molar parts hexamethylene diamine and 4,4'"'"'-diamino-3,3'"'"'-dimethyl-cyclohexyl methane, in a molar ratio of 4:

1 to 1;

4, and

(5) 15 to 40 molar parts of isophthalic acid, terephthalic acid, or a mixture thereof.

20. The composite of claim 1 wherein said barrier copolyamide is composed of 98 to 70 molar parts of:

(4) 35 to 49 molar parts hexamethylene diamine, and

(5) 5 to 20 molar parts adipic acid and 29 to 44 molar parts isophthalic acid, terephthalic acid, or a mixture thereof.

21. The composite of claim 1 comprising at least one additional layer of additional polymers, said additional layer being laminated with said composite.

22. The composite of claim 16 wherein said additional polymers are selected from the group consisting of polyethylenes, polypropylenes, polyvinyl chlorides, polycarbonates, polyethylene terephthalates, polyethylene styrenes, polyvinyl acetates, polyacrylic nitriles, polyvinyl alcohols, polysulfides, polysulfones, polyketones, and polystyrenes.

23. The composite of claim 16 wherein said additional layer is between a plurality of said protective layers or said barrier layers.