Gas-barrier polyurethane resin, and adhesive for laminate, gas-barrier film and paint containing the same

• US 20030229194A1
• Filed: 06/04/2003
• Published: 12/11/2003
• Est. Priority Date: 06/04/2002
• Status: Active Grant

• Current Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Original Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Inventors: Nomura, Takeshi, Koyama, Takeshi
• Granted Patent: US 6,887,966 B2
• Time in Patent Office: Days
• US Class Current: 528/59
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/329 containing aromatic groups
• CPC Class Codes: C08G 18/752 containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/7621 being toluene diisocyanate including isomer mixtures
• CPC Class Codes: C08G 18/7642 containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8009 with compounds of C08G18/3203

Abstract

The polyurethane resin produced by reacting a component composed mainly of an active hydrogen-containing compound with a component composed mainly of an organic polyisocyanate compound which contains a backbone structure represented by the formula:

in an amount of 20% by weight or higher, exhibits a high gas-barrier property and a high adhesion property. Accordingly, the present invention provides: (A) a two-part liquid curable polyurethane resin composition having an excellent adhesion property to various polymers, papers, metals, etc., especially after boiling and retort treatments, and an adhesive for gas-barrier laminate containing such a composition; (B) a heat-curing gas-barrier polyurethane resin useful as a packaging material for foodstuffs or drugs for the purpose of preserving contents thereof by preventing various gases from penetrating therethrough, which is capable of maintaining its high gas-barrier property; and (C) a paint having excellent properties such as rust-proofing property, corrosion resistance and aesthetic decorating property that are inherent to polyurethane resin, and being applicable to packaging materials for foodstuffs or drugs that are required to show a high gas-barrier property by shielding various gases.

Claims

1. A polyurethane resin produced by reacting a component comprising mainly (A) an active hydrogen-containing compound and a component comprising mainly (B) an organic polyisocyanate compound, said polyurethane resin containing a backbone structure represented by the formula (1):

2. A two-part liquid curable polyurethane resin composition comprising:

a component comprising mainly (A) an active hydrogen-containing compound; and

a component comprising mainly (B) an organic polyisocyanate compound,

said components (A) and (B) being reacted with each other to form a cured product containing a backbone structure represented by the formula (1);

in an amount of 20% by weight or higher.

3. The two-part liquid curable polyurethane resin composition according to claim 2, wherein said active hydrogen-containing compound (A) is at least one compound selected from the group consisting of alkyleneoxide adducts of polyamine, amido-containing polyols, polyol adducts of polyisocyanate compound, and polyols.

4. The two-part liquid curable polyurethane resin composition according to claim 2, wherein said active hydrogen-containing compound (A) is at least one compound selected from the group consisting of alkyleneoxide adducts of aroaliphatic polyamine, polyol adducts of aroaliphatic polyisocyanate compound, and aroaliphatic polyols.

5. The two-part liquid curable polyurethane resin composition according to claim 2, wherein said active hydrogen-containing compound (A) is an alkyleneoxide adduct of aroaliphatic polyamine.

6. The two-liquid curable polyurethane resin composition according to claim 2, wherein said active hydrogen-containing compound (A) is an alkyleneoxide adduct of xylylenediamine.

7. The two-part liquid curable polyurethane resin composition according to claim 3, wherein said alkyleneoxide adduct is at least one compound selected from the group consisting of C₂ to C₄ alkyleneoxide adducts.

8. The two-part liquid curable polyurethane resin composition according to claim 2, wherein said organic polyisocyanate compound (B) is a reaction product obtained by reacting (a) a polyfunctional isocyanate compound and (b) at least one polyfunctional alcohol selected from the group consisting of C₂ to C₁₀ polyfunctional alcohols, or a reaction product obtained by reacting (a) the polyfunctional isocyanate compound, (b) the at least one polyfunctional alcohol and (c) at least one compound selected from the group consisting of aromatic polyfunctional amines, aroaliphatic polyfunctional amines, alicyclic polyfunctional amines, aliphatic polyfunctional amines, aliphatic alkanol amines, aromatic polyfunctional carboxylic acids, alicyclic polyfunctional carboxylic acids and aliphatic polyfunctional carboxylic acids, and has two or more NCO end groups.

9. The two-part liquid curable polyurethane resin composition according to claim 8, wherein said polyfunctional isocyanate compound (a) is at least one compound selected from the group consisting of xylylenediisocyanate and derivatives of xylylenediisocyanate.

10. The two-part liquid curable polyurethane resin composition according to claim 8, wherein said polyfunctional isocyanate compound (a) is xylylenediisocyanate.

11. An adhesive for gas-barrier laminate comprising the two-part liquid curable polyurethane resin composition as claimed in claim 2.

12. The adhesive according to claim 11, having an initial adhesion strength of 30 g/15 mm or higher as measured by subjecting polymer films laminated through said adhesive to T-peel test immediately after the lamination at a peel velocity of 300 mm/min.

13. An adhesive assistant comprising the adhesive for gas-barrier laminate as claimed in claim 11.

14. A heat-curing gas-barrier polyurethane resin comprising:

a cured resin produced by reacting (A) an active hydrogen-containing compound with (B) an organic polyisocyanate compound, said cured resin containing a backbone structure represented by the formula (1);

in an amount o 20% by weight or higher, and the components (A) and (B) containing tri- or more functional compounds in an amount of 7% by weight or higher based on a total weight of the components (A) and (B).

15. The heat-curing gas-barrier polyurethane resin according to claim 14, wherein said resin has an oxygen permeability of 500 ml/m²-day-MPa or higher as measured at 23°

C. and 60% RH with a resin thickness of 10 μ

m.

16. The heat-curing gas-barrier polyurethane resin according to claim 14, wherein a ratio (R₆₀/R₁₀₀) of an oxygen permeability (R₆₀) as measured at 23°

C. and 60% RH with a resin thickness of 10 μ

m to an oxygen permeability (R₁₀₀) as measured at 23°

C. and 100% RH with a resin thickness of 10 μ

m is 1/1 to 1/3.

17. The heat-curing gas-barrier polyurethane resin according to claim 14, wherein said active hydrogen-containing compound (A) is at least one compound selected from the group consisting of (1) polyamines, (2) alkyleneoxide adducts of polyamine, (3) amido-containing polyols, (4) polycarboxylic acids and (5) polyols.

18. The heat-curing gas-barrier polyurethane resin according to claim 17, wherein said alkyleneoxide adducts of polyamine (2) are alkyleneoxide adducts of aroaliphatic polyamine.

19. The heat-curing gas-barrier polyurethane resin according to claim 18, wherein said alkyleneoxide adduct of aroaliphatic polyamine is xylylenediamine.

20. The heat-curing gas-barrier polyurethane resin according to claim 17, wherein said alkyleneoxide adduct of polyamine (2) is at least one compound selected from C₂ to C₄ alkyleneoxide adducts of polyamine.

21. The heat-curing gas-barrier polyurethane resin according to claim 17, wherein said polyols (5) are C₂ to C₁₀ polyols.

22. The heat-curing gas-barrier polyurethane resin according to claim 14, wherein said organic polyisocyanate compound (B) is at least one compound selected from the group consisting of aromatic, aroaliphatic, alicyclic and aliphatic diisocyanates and derivatives thereof.

23. The heat-curing gas-barrier polyurethane resin according to claim 22, wherein said organic polyisocyanate compound (B) is at least one compound selected from the group consisting of xylenediisocyanate, bis(isocyanatomethyl) cyclohexane and derivatives thereof.

24. The heat-curing gas-barrier polyurethane resin according to claim 23, wherein said organic polyisocyanate compound (B) is at least one compound selected from the group consisting of xylenediisocyanate and derivatives thereof.

25. The heat-curing gas-barrier polyurethane resin according to claim 14, wherein said tri- or more functional compound is at least one compound selected from the group consisting of buret compounds, allophanate compounds and isocyanurate compounds of aromatic, aroaliphatic, alicyclic and aliphatic diisocyanates, C₃ to C₆ polyols, alkyleneoxide adducts of polyamine, and amido-containing polyols.

26. The heat-curing gas-barrier polyurethane resin according to claim 25, wherein said tri- or more functional compound is at least one compound selected from the group consisting of isocyanurate compounds of aroaliphatic and alicyclic diisocyanates, C₃ to C₆ polyols and alkyleneoxide adducts of aroaliphatic polyamine.

27. The heat-curing gas-barrier polyurethane resin according to claim 25, wherein said tri- or more functional compound is at least one compound selected from the group consisting of isocyanurate compounds of xylylenediisocyanate and bis(isocyanatomethyl)cyclohexane, glycerol, trimethylol ethane, tirmethylol propane, pentaerythritol, and alkyleneoxide adducts of xylylenediamine.

28. A gas-barrier film prepared by forming the heat-curing gas-barrier polyurethane resin as claimed in claim 14 into a film shape.

29. A gas-barrier composite film comprising a base film layer, and a layer containing the heat-curing gas-barrier polyurethane resin as claimed in claim 14.

30. A gas-barrier paint comprising as a film-forming component, a gas-barrier paint composition containing (A) an active hydrogen-containing compound and (B) an organic polyisocyanate compound as main components, said composition being cured into a coating film containing a backbone structure represented by the formula (1):

31. The gas-barrier paint according to claim 30, wherein said active hydrogen-containing compound (A) is at least one compound selected from the group consisting of alkyleneoxide adducts of polyamine, amido-containing polyols, polyol adducts of polyisocyanate compound, and polyols.

32. The gas-barrier paint according to claim 30, wherein said active hydrogen-containing compound (A) is at least one compound selected from the group consisting of alkyleneoxide adducts of aroaliphatic polyamine, polyol adducts of aroaliphatic polyisocyanate compound, and aroaliphatic polyols.

33. The gas-barrier paint according to claim 30, wherein said active hydrogen-containing compound (A) is an alkyleneoxide adduct of aroaliphatic polyamine.

34. The gas-barrier paint according to claim 30, wherein said active hydrogen-containing compound (A) is an alkyleneoxide adduct of xylylenediamine.

35. The gas-barrier paint according to claim 31, wherein said alkyleneoxide is at least one compound selected from the group consisting of C₂ to C₄ alkyleneoxides

36. The gas-barrier paint according to claim 30, wherein said organic polyisocyanate compound (B) is a reaction product of (a) a polyfunctional isocyanate compound and (b) at least one polyfunctional alcohol selected from the group consisting of C₂ to C₁₀ polyfunctional alcohols, or a reaction product of the compounds (a) and (b) with (c) at least one compound selected from the group consisting of aromatic polyfunctional amines, aroaliphatic polyfunctional amines, alicyclic polyfunctional amines, aliphatic polyfunctional amines, aliphatic alkanol amines, aromatic polyfunctional carboxylic acids, alicyclic polyfunctional carboxylic acids and aliphatic polyfunctional carboxylic acids, and has two or more NCO end groups.

37. The gas-barrier paint according to claim 36, wherein said polyfunctional isocyanate compound (a) is at least one compound selected from the group consisting of xylylenediisocyanate and derivatives of xylylenediisocyanate.

38. The gas-barrier paint according to claim 36, wherein said polyfunctional isocyanate compound (a) is xylylenediisocyanate.

39. The gas-barrier paint according to claims 30, wherein said paint is a primer.

40. A gas-barrier coating film formed by curing a gas-barrier paint composition containing (A) an active hydrogen-containing compound and (B) an organic polyisocyanate compound as main components, said coating film containing a backbone structure represented by the formula (1):