Production of composite materials made of film, solid adhesive polymer, and a polyurethane layer

Abstract

Provided herein is a process for the preparation of multilayered composite materials, and also multilayered composite materials which can be obtained according to this process.

Claims

1. A process for preparation of multilayered composite materials comprising: (A) a film made of polyurethane or polyamide, (B) a tie layer made of thermoplastic adhesive polymer with a melting range from 70 C. to 130 C., and (C) a polyurethane layer, wherein the process comprises: a) forming the polyurethane layer (C) using a mold, b) applying the adhesive polymer in solid form to the film (A) and/or to the polyurethane layer (C), and c) combining the polyurethane layer (C) with the film (A).

2. The process according to claim 1, wherein the film (A) is made of thermoplastic polyurethane or of aliphatic polyamide.

3. The process according to claim 1, wherein the film (A) is made of thermoplastic polyurethane.

4. The process according to claim 1, wherein the film (A) has a thickness of 1 to 500 m.

5. The process according to claim 1, wherein the adhesive polymer in stage b) has a weight per unit area of 5 to 100 g/m.sup.2.

6. The process according to claim 1, wherein the adhesive polymer in stage b) has a melt volume-flow rate MVR of 10 to 100 cm.sup.3/10 min.

7. The process according to claim 1, wherein, in stage b), the adhesive polymer is applied in the form of an adhesive grid, adhesive web, or adhesive film.

8. The process according to claim 1, wherein the adhesive polymer has a melting range of 80 C. to 125 C.

9. The process according to claim 1, wherein the adhesive polymer is based on polyurethanes, polyamides, polyesters or polyolefins.

10. The process according to claim 1, wherein the polyurethane layer (C) exhibits a pattern.

11. The process according to claim 1, wherein the tie layer (B) is a perforated layer of a cured adhesive polymer.

12. The process according to claim 1, wherein the mold is a silicone mold structured using laser engraving.

13. The process according to claim 1, wherein wells are incorporated in the mold in structuring of the mold using a laser, and wherein the wells exhibit an average depth in a range from 50 to 250 m and a center-to-center separation in a range from 50 to 250 m.

Description

EXAMPLES

(1) TPU film 1: colorless transparent film of thermoplastic polyurethane based on aromatic polyester polyurethane, density 1.21 g/cm.sup.3 (DIN 53479), melting range 140 C.-155 C. (Kofler bank at thickness of 50 m), Shore A hardness of raw material ca 86 (DIN 53505), tensile strength longitudinal/transverse 45 MPa, elongation at break longitudinal/transverse 490% (DIN EN ISO 527-1, -3), commercially available as Thermo-plastische Polyurethanfolie 4119 [thermoplastic polyurethane film 4119] from Gerlinger Industries, Nordlingen, Germany. TPU film 2: colorless opaque film of thermoplastic polyurethane based on aromatic polyester polyurethane, density 1.19 g/cm.sup.3 (DIN 53479), melting range 165 C.-175 C. (Kofler bank at thickness of 50 m), Shore A hardness of raw material ca 86 (DIN 53505), tensile strength longitudinal/transverse 40 MPa, elongation at break longitudinal/transverse 500% (DIN EN ISO 527-1, -3), commercially available as Thermo-plastische Polyurethanfolie 4120 [thermoplastic polyurethane film 4120] from Gerlinger Industries, Nordlingen, Germany. TPU film 3: Film of thermoplastic polyurethane, thickness 150 m, melting point ca 120 C., commercially available. Polyamide film 1: colorless polyamide film made of caprolactam, hexamethylenediamine and adipic acid (copolyamide 6/66), melting point approximately 190 C. Adhesive A: White web of a copolyester, weight per unit area 8-60 g/m.sup.2, melting range of 87 C.-97 C., melt volume-flow rate MVR of 51 to 100 cm.sup.3/10 min, commercially available from Protechnic S.A., Cernay, France. Adhesive B: White web of a copolyamide, weight per unit area 8-60 g/m.sup.2, melting range of 98 C.-108 C., melt volume-flow rate MVR of 19 to 50 cm.sup.3/10 min, commercially available from Protechnic S.A., Cernay, France. Adhesive C: White web of an aliphatic thermoplastic polyurethane polyester, weight per unit area 12-70 g/m.sup.2, melting range of 105 C.-115 C., melt volume-flow rate MVR of 51 to 100 cm.sup.3/10 min, commercially available from Protechnic S.A., Cernay, France.

(2) The melting range was determined by means of DSC according to IS011357. The melt volume-flow rate MVR was measured at 160 C. and 2.16 kg according to ISO 1133-1. Velure PToM: aqueous anionic polyurethane dispersion, 31-38 wt % solids content, pH 6-8.5, efflux time 10-20 s (DIN53211, 4 mm at 20 C.). Pigment: aqueous black pigment preparation, commercially available from BASF SE as Luconyl NG Black 0066. Velure Hrter 50-70 wt % solution of polyfunctional oligomeric isocyanate based [curing agent] CI: on 1,6-hexamethylene diisocyanate, commercially available from BASF SE.
General Preparation Process:
Stage a)

(3) A silicone mold with a desired pattern was prepared according to the state of the art.

(4) A polyurethane layer was formed on the mold by spraying the hot mold with the aqueous polyurethane dispersion comprising Valure PToM, Valure Hrter CI and pigment according to the state of the art.

(5) Stage b)

(6) The adhesive A, B or C was cut out to the size of the film and put on the film by hand.

(7) Stage c)

(8) The polyurethane layer was stripped from the mold and combined with the film on which the adhesive lies, so that the adhesive is between polyurethane layer and film.

(9) The composite material thus obtained was compressed at 130 C.-135 C. for 3 or 5 minutes at a pressure of 3 mPa.

Examples 1-9: Composite Material on TPU Films

(10) Multilayered composite material based on TPU film (TPU film 1, TPU film 2 and TPU film 3) was produced according to the general preparation process.

(11) The adhesion of the layers in the composite material was tested manually and qualitatively evaluated. The results are summarized in Table 1.

(12) TABLE-US-00001 TABLE 1 Adhesion at Adhesion at Exam- Adhe- 3 min compres- 5 min compres- ple Film sive sion sion 1 TPU film 1 A very good very good 2 TPU film 1 B very good very good 3 TPU film 1 C very good very good 4 TPU film 2 A very good very good 5 TPU film 2 B very good very good 6 TPU film 2 C very good very good 7 TPU film 3 A very good very good 8 TPU film 3 B very good very good 9 TPU film 3 C very good very good

Example 10: Composite Material on Polyamide Film

(13) Multilayered composite material based on polyurethane film 1 and adhesive A was produced according to the general preparation process and the adhesion was tested as in Examples 1-9. The adhesion was very good.