Multi-layer composite materials comprising a plastic or metal foil, corresponding method of production and use thereof

Abstract

Multi-layer composite materials comprising a plastic or metal foil, corresponding method of production and use thereof Multilayered composite materials comprising as components: (A) a plastics or metal foil, (B) optionally at least one bonding layer and (C) a polyurethane layer with capillaries passing through the entire thickness of the polyurethane layer.

Claims

1. A multilayered composite material comprising, in order: a plastic film or metal foil (A); optionally at least one bonding layer (B); and a polyurethane layer (C) with capillaries passing through the entire thickness of the polyurethane layer, wherein polyurethane layer (C) has on average at least 100 capillaries per 100 cm.sup.2, exhibits patterning, and has an average thickness of 15 to 300 m, wherein said patterning corresponds to a velvet surface, in which hairs having an average length of from 20 to 500 m, with an average spacing of from 50 to 350 m from one hair to the next, and wherein when (B) is not present, (A) and (C) are in contact with each other, and when (B) is present, (A) is in contact with (B), and (B) is in contact with (C).

2. The multilayered composite material according to claim 1 wherein (A) is a self-supporting film/sheet of a material selected from the group consisting of polyethylene, polypropylene, polyester, polyamide, polycarbonate, polyvinyl chloride, and polystyrene.

3. The multilayered composite material according to claim 2 wherein said at least one bonding layer (B) comprises a layer of a cured organic adhesive.

4. The multilayered composite material according to claim 1 wherein said at least one bonding layer (B) is present and comprises a layer of a cured organic adhesive.

5. The multilayered composite material according to claim 1 wherein the at least one bonding layer (B) is present and comprises an interrupted layer of a cured organic adhesive.

6. The multilayered composite material according to claim 1 which additionally comprises at least one interlayer (D) disposed between plastic film or metal foil (A) and at least one bonding layer (B), between at least one bonding layer (B) and polyurethane layer (C), or between two bonding layers (B), where interlayer (D) is selected from the group consisting of textile, batt materials, leather, and open-cell foam.

7. The multilayered composite material according to claim 1 wherein plastic film or metal foil (A) has a thickness of 0.5 m to 1 mm, and at least one bonding layer (B), when present, has a maximum thickness of 100 m.

8. The multilayered composite material according to claim 1 wherein the capillaries have an average diameter in the range of from 0.005 to 0.05 mm.

9. The multilayered composite material according to claim 1 wherein the capillaries are nonuniformly distributed over polyurethane layer (C).

10. The multilayered composite material according to claim 1 wherein polyurethane layer (C) comprises pores which do not extend through the entire thickness of said layer.

11. The multilayered composite material according to claim 1 wherein said plastic film or metal foil (A) is bendable by hand.

12. The multilayered composite material according to claim 1 wherein said plastic film or metal foil (A) has a thickness of 0.5 m to 0.15 mm.

13. The multilayered composite material according to claim 1 wherein said plastic film or metal foil (A) is a metal foil.

14. A process for producing a multilayered composite material according to claim 1, which comprises: forming the polyurethane layer (C) with a mold; applying at least one organic adhesive uniformly or partially onto the plastic film or metal foil (A) and/or onto the polyurethane layer (C); and then bonding the polyurethane layer (C) pointwise, stripwise, or areawise to the plastic film or metal foil (A).

15. The process according to claim 14 wherein the plastic film (A) is a self-supporting film/sheet of a material selected from the group consisting of polyethylene, polypropylene, polyester, polyamide, polycarbonate, polyvinyl chloride, and polystyrene.

16. The process according to claim 14 wherein said polyurethane layer (C) is formed with a silicone mold.

17. The process according to claim 14 wherein said silicone mold comprises a silicone mold structured by laser engraving.

18. The process according to claim 14 wherein said silicone mold is structured by a laser to cut wells into the silicone mold which have an average depth in a range from 50 to 250 m and a center-to-center spacing in a range from 50 to 250 m.

19. The process according to claim 14 wherein an interlayer (D) is placed between said plastic film or metal foil (A) and said at least one bonding layer (B), between said bonding layer (B) and polyurethane layer (C), or between a first and second bonding layer (B1) and (B2).

20. A process for manufacturing packaging material, comprising affixing the multilayered composite material according to claim 1 to itself or a substrate.

21. A packaging material comprising or obtained from the multilayered composite material according to claim 1.

22. A process for manufacturing a decorative material, comprising affixing the multilayered composite material according to claim 1 to itself or a substrate.

23. A decorative material comprising or obtained from the multilayered composite material according to claim 1.

24. A decorative material consisting of the multilayered composite material according to claim 1.

Description

(1) Working examples further elucidate the present invention.

(2) I. Production of Starting Materials

(3) I.1 Production of an Aqueous Polyurethane Dispersion Disp. 1

(4) The following were mixed in a stirred vessel:

(5) 7% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (PU1.1) prepared from hexamethylene diisocyanate (a1.1) and isophorone diisocyanate (a1.2) in a weight ratio of 13:10 as diisocyanates and as diols, a polyester diol (b1.1) having a molecular weight M.sub.w of 800 g/mol, prepared by polycondensation of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (isomer mixture) in a molar ratio of 1:1:2, 5% by weight of 1,4-butanediol (b1.2) and also 3% by weight of monomethylated polyethylene glycol (c.1) and also 3% by weight of H2NCH2CH2-NHCH2CH2-COOH, % by weight all based on polyester diol (b1.1), softening point of soft polyurethane (PU1.1): 62 C., softening starts at 55 C., Shore A hardness 54,
65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard Polyurethane (PU2.2), obtainable by reaction of isophorone diisocyanate (a1.2), 1,4-butanediol, 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M.sub.w of 4200 g/mol, softening point of 195 C., Shore A hardness 86,
3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (V.1),

(6) ##STR00003##
6% by weight of a 65% by weight aqueous dispersion of the silicone compound according to Example 2 of EP-A 0 738 747 (f.1)
2% by weight of carbon black,
0.5% by weight of a thickening agent based on polyurethane,
1% by weight of microballoons of polyvinylidene chloride, filled with isobutane, diameter 20 m, commercially obtainable for example as Expancel from Akzo Nobel.

(7) This gave an aqueous dispersion Disp.1 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23 C., determined in accordance with DIN EN ISO 2431, as of May 1996.

(8) I.2 Production of an Aqueous Formulation Disp.2

(9) The following were mixed in a stirred vessel:

(10) 7% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content:

(11) 40%) of a soft polyurethane (PU1.1) prepared from hexamethylene diisocyanate (a1.1) and isophorone diisocyanate (a1.2) in a weight ratio of 13:10 as diisocyanates and as diols, a polyester diol (b1.1) having a molecular weight M.sub.w of 800 g/mol, prepared by polycondensation of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (isomer mixture) in a molar ratio of 1:1:2, 5% by weight of 1,4-butanediol (b1.2), 3% by weight of monomethylated polyethylene glycol (c.1) and also 3% by weight of H2NCH2CH2-NHCH2CH2-COOH, % by weight all based on polyester diol (b1.1), softening point of 62 C., softening starts at 55 C., Shore A hardness 54, 65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (2.2), obtainable by reaction of isophorone diisocyanate (a1.2), 1,4-butanediol (PU1.2), 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M.sub.w of 4200 g/mol (b1.3), polyurethane (PU2.2) had a softening point of 195 C., Shore A hardness 90,
3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (V.1),
NCO content 12%,
2% by weight of carbon black.

(12) This gave a polyurethane dispersion Disp.2 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23 C., determined in accordance with DIN EN ISO 2431, as of May 1996.

(13) II. Production of a Mold

(14) A liquid silicone was poured onto a surface having the pattern of full grain calf leather. The silicone was cured by adding a solution of di-n-butylbis(1-oxoneodecyloxy)-stannane as 25% by weight solution in tetraethoxysilane as an acidic curative to obtain a silicone rubber layer 2 mm in thickness on average, which served as the mold. The mold was adhered onto a 1.5 mm thick aluminum support.

(15) III. Application of Aqueous Polyurethane Dispersions onto Mold from II.

(16) The mold from II. was placed on a heatable surface and heated to 91 C. Disp.1 was then sprayed onto it through a spray nozzle, at 88 g/m.sup.2 (wet). No air was admixed during application, which was done with a spray nozzle having a diameter of 0.46 mm, at a pressure of 65 bar. This was followed by solidification at 91 C. until the surface was no longer tacky.

(17) The spray nozzle was located 20 cm above the surface passing underneath it, and could be moved in the transport direction of the surface, and moved transversely to the transport direction of the surface. The surface took about 14 seconds to pass the spray nozzle and had a temperature of 59 C. After being exposed for about two minutes to a stream of dry hot air at 85 C., the polyurethane film (C.1) thus produced, which had a netlike appearance, was almost water-free.

(18) In an analogous arrangement, Disp.2 was immediately thereafter applied to the mold thus coated, as bonding layer (B.1) at 50 g/m.sup.2 wet, and subsequently allowed to dry.

(19) This gave a mold coated with polyurethane film (C.1) and bonding layer (B.1).

(20) A polycarbonate foil (A.1), based on bisphenol A and having a thickness of 0.1 mm was sprayed with Disp.2, at 30 g/m.sup.2 (wet). The polycarbonate foil thus sprayed was allowed to dry for several minutes.

(21) IV. Production of an Inventive Multilayered Composite Material

(22) Thereafter, polycarbonate foil (A.1) is placed with the sprayed side onto the still hot bonding layer (B.1) which was on the mold together with polyurethane film (C.1), and compressed in a press at 4 bar and 110 C. for 15 seconds. The inventive multilayered composite material MSV.1 thus obtained was subsequently removed from the press and the mold was removed from it.

(23) The inventive multilayered composite material MSV.1 thus obtained is notable for pleasant haptics, an appearance which was identical to a leather surface, and also breathability. In addition, the inventive multilayered composite material MSV.1 is easy to clean of contaminants such as for example dust.

(24) MSV.1 is deep-drawable/thermoformable.