MULTI-LAYERED FILM AND THE USE THEREOF

Abstract

The present invention relates to a multi-layered film for the application to a metal or plastic surface, comprising a protective layer (A) as a first layer, which is a poly(alkyl methacrylate) film comprising at least one hindered amine light stabilizer and at least two different ortho-hydroxy tris-aryl triazine UV absorbers selected from compounds of formulae (7) and (8); a barrier layer (B), a base layer (C), an adhesive layer (D) as last layer, and wherein barrier layer (B) and/or base layer (C) comprise at least one pigment. The multi-layered films are especially suitable for the application to the surface of automobiles.

Claims

1. A multi-layered film for application to a metal or plastic surface, the multi-layered film comprising: (A) a protective layer (A) as a first layer; (B) a barrier layer (B); (C) a base layer (C); and (D) an adhesive layer (D) as a last layer, wherein: the protective layer (A) is a poly(alkyl methacrylate) film comprising at least one hindered amine light stabilizer and at least two different ortho-hydroxy tris-aryl triazine UV absorbers selected from the group consisting of a compound of formula (7) and a compound of formula (8): ##STR00030## wherein G.sub.1 is hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl substituted by 1, 2 or 3 radicals selected from the group consisting of OH, C.sub.2-C.sub.18 alkenyloxy, C(O)OL.sub.1 and OC(O)L.sub.2, L.sub.1 and L.sub.2 being independently C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.50alkyl interrupted by oxygen or C.sub.3-C.sub.50hydroxyalkyl interrupted by oxygen, G.sub.2, G.sub.3, G.sub.4 and G.sub.5 are independently hydrogen, C.sub.1-C.sub.18alkyl, phenyl or phenyl substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl; ##STR00031## wherein Q.sub.1, Q.sub.2, Q.sub.3 and Q.sub.4 are independently hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl substituted by 1, 2 or 3 radicals selected from the group consisting of OH, C.sub.2-C.sub.18alkenyloxy, C(O)OY.sub.1 and OC(O)Y.sub.2 with Y.sub.1 and Y.sub.2 being independently C.sub.1-C.sub.18alkyl; C.sub.3-C.sub.50alkyl interrupted by oxygen or C.sub.3-C.sub.50hydroxyalkyl interrupted by oxygen, and R.sub.14, R.sub.15 and R.sub.16 are independently from each other hydrogen or C.sub.1-C.sub.18alkyl; and the barrier layer (B), the base layer (C), or both, comprise at least one pigment.

2. The multi-layered film according to claim 1, wherein the barrier layer (B) the base layer (C), or both, comprise at least one hindered amine light stabilizer.

3. The multi-layered film according to claim 1, wherein the hindered amine light stabilizer is a compound of formula (1): ##STR00032## wherein A.sub.1 is hydrogen or C.sub.1-C.sub.4alkyl, A.sub.2 is a direct bond or C.sub.1-C.sub.10alkylene, and n.sub.1 is a number from 2 to 50; or a compound of the formula (2): ##STR00033## wherein E.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup., OH, CH.sub.2CN, C.sub.1-C.sub.18alkoxy, hydroxyl-substituted C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl, m.sub.1 is 1, 2 or 4, if m.sub.1 is 1, E.sub.2 is C.sub.1-C.sub.25alkyl, a group of the formula C(CH.sub.3)CH.sub.2, or a group of the formula (2a): ##STR00034## E.sub.3 is as defined for E.sub.1, if m.sub.1 is 2, E.sub.2 is C.sub.1-C .sub.4alkylene or a group of the formula (2b): ##STR00035## wherein E.sub.4 is C.sub.1-C.sub.10alkyl or C.sub.2-C.sub.10alkenyl, E.sub.5 is C.sub.1-C.sub.10alkylene, and E.sub.6 and E.sub.7 independently of one another are C.sub.1-C.sub.4alkyl, cyclohexyl or methylcyclohexyl, and if m.sub.1 is 4, E.sub.2 is C.sub.4-C.sub.10alkanetetrayl; or a compound of the formula (3): ##STR00036## wherein R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4-alkyl-substituted C.sub.5-C.sub.12cycloalkyl, phenyl, phenyl which is substituted by OH and/or C.sub.1-C.sub.10alkyl; C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl radical by OH and/or C.sub.1-C.sub.10alkyl; or a group of the formula (3a) ##STR00037## R.sub.2 is C.sub.2-C.sub.18alkylene, C.sub.5-C.sub.7cycloalkylene or C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene), or the radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen atoms to which they are bonded, form a 5- to 10-membered heterocyclic ring, or R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R.sub.6 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup., OH CH.sub.2CN, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl, and b.sub.1 is a number from 2 to 50, with the proviso that at least one of the radicals R.sub.1, R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (3a); or a compound of the formula (4), (5) or (6): ##STR00038## wherein R.sub.7 and R.sub.11 independently of one another are hydrogen or C.sub.1-C.sub.12alkyl, R.sub.8, R.sub.9 and R.sub.10 independently of one another are C.sub.2-C.sub.10alkylene, and X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 independently of one another are a group of the formula (4a): ##STR00039## R.sub.12 is hydrogen, C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, phenyl, OH and/or C.sub.1-C.sub.10alkyl-substituted phenyl, C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl radical by OH and/or C.sub.1-C.sub.10alkyl; or a group of the formula (3a) as defined above, and R.sub.13 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup., OH, CH.sub.2CN, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl.

4. The multi-layered film according to claim 3, wherein the hindered amine light stabilizer is the compound of formula (3).

5. The multi-layered film according to claim 1, wherein the protective layer (A) comprises the at least one orthohydroxy tris-aryl triazine UV absorber of formula (7) and the at least one ortho-hydroxy trisaryl triazine UV absorber of formula (8).

6. The multi-layered film according to claim 1, wherein the protective layer (A) further comprises a diene-based polymer.

7. The multi-layered film according to claim 1, wherein the barrier layer (B) is a polyvinylidene chloride film, a cyclo olefin copolymer film, a polyethylenenaphthalate film, a polyethylene film or a polypropylene film.

8. The multi-layered film according to claim 1, wherein the barrier layer (B) is a polyethylene film or a polypropylene film.

9. The multi-layered film according to claim 1, wherein the base layer (C) is a thermoplastic polyurethane film.

10. The multi-layered film according to claim 1, wherein the adhesive layer (D) is a coating based on a polyurethane.

11. The multi-layered film according to claim 1, wherein the barrier layer (B) the base layer (C), or both, comprises at least one plasticizer.

12. The multi-layered film according to claim 1, wherein the multi-layered film is attached to a metal or plastic surface of a transportation device, a package, an apparatus, a construction part, an electric device or an electronic device.

13. The multi-layered film according to claim 1, wherein the multi-layered film is attached to a surface of an automobile.

14. A method, comprising attaching the multi-layered film of claim 1 to a surface of an automobile.

15. The method according to claim 14, wherein the surface of the automobile is not lacquered.

Description

EXAMPLE 1

[0205] A composite film is prepared comprising the following layers in the stated order: [0206] a protective layer (A) [0207] a barrier layer (B) [0208] a base layer (C), and [0209] an adhesive layer (D)

[0210] Protective layer (A): The protective layer (A) is prepared by dry-blending of a poly(methyl methacrylate) resin (rubber copolymerized PMMA, Acrypet IRG304 001 available from Mitsubishi Rayon) with 1% TINUVIN 1577+1% TINUVIN 460+0.1% TINUVIN NOR 371. The blend is placed into an extruder hopper and then extruded at a temperature of 280 C. using conventional methods to obtain a film having a thickness of 50 microns.

[0211] Barrier layer (B): The barrier layer (B) is prepared by dry-blending of a polyvinylidene chloride resin (available as Ixan PVS 815 from Solvay S.A.) with 6% of the pigment DAP-4050 White and 6% of the pigment DAP-4443 Yellow (both available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and then extruded using conventional methods to obtain a film having a thickness of 50 microns.

[0212] Base layer (C): The base layer (C) is a thermoplastic polyurethane film having 150 micron thickness (available as NY585 white thermo polyurethane film from Sheedom Co., Ltd.) with 10% of the pigment Dymic SZ 7030 white (available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

[0213] Adhesive layer (D): The adhesive layer (D) is composed of a polyurethane adhesive as described for adhesive layer D) in Example 1 on page 26 of WO-A-2012/065966.

[0214] The composite film is prepared by laminating the protective layer (A) with the barrier layer (B), and then laminating on the barrier layer (B) the base layer (C). Lamination is carried out by use of adhesives according to conventional processes, like dry and wet lamination. The outer part of base layer (C) is then coated with the adhesive to form layer (D) having a thickness of 10-15 microns.

[0215] TINUVIN 1577 is the compound of formula (7-C).

[0216] TINUVIN 460 is the compound of formula (8-B).

[0217] TINUVIN NOR 371 is the compound of formula (3-B), wherein R.sub.6 is OC.sub.3H.sub.7.

[0218] The resulting composite film is tested according to DIN EN ISO 527 by use of the measuring machine Toyo Boldwin (Tensilon, UTM-III-200), and the following measuring conditions:

[0219] Sample size: rectangular specimen, width 10 mmlength 70 mm

[0220] Inter-chuck distance: 40 mm

[0221] Testing speed: 100 mm/minute

[0222] Testing temperature: 20 C.

[0223] The following properties are obtained for the composite film of this Example 1:

[0224] Young's modulus: 1014 megapascal

[0225] Tensile strength at break: 44.9 megapascal

[0226] Elongation at break: 626% gauge length

EXAMPLE 2

[0227] A composite film is prepared comprising the following layers in the stated order: [0228] a protective layer (A) [0229] a barrier layer (B) [0230] a base layer (C), and [0231] an adhesive layer (D)

[0232] Protective layer (A): The protective layer (A) is prepared by dry-blending of a poly(methyl methacrylate) resin (rubber copolymerized PMMA, Acrypet IRG304 001 available from Mitsubishi Rayon) with 1% TINUVIN 1577+1% TINUVIN 460+0.1% TINUVIN NOR 371. The blend is placed into an extruder hopper and then extruded at a temperature of 280 C. using conventional methods to obtain a film having a thickness of 50 microns.

[0233] Barrier layer (B): The barrier layer (B) is prepared by dry-blending of polypropylene with 0.1% CHIMASSORB 2020 and 3.7% of the pigment HCM SMB 429 Yellow (available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and then extruded using conventional methods to obtain a film having a thickness of 100 microns.

[0234] Base layer (C): The base layer (C) is a thermoplastic polyurethane film comprising 0.1% CHIMASSORB 2020 and having 100 micron thickness, which is obtained according to conventional methods by dry-blending of thermoplastic polyurethane (available as NY585 white thermo polyurethane film from Sheedom Co., Ltd.) and extrusion with 10% of the pigment Dymic SZ 7030 white (available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

[0235] Adhesive layer (D): The adhesive layer (D) is composed of a polyurethane adhesive as described for adhesive layer D) in Example 1 on page 26 of WO-A-2012/065966.

[0236] The composite film is prepared by laminating the protective layer (A) with the barrier layer (B), and then laminating on the barrier layer (B) the base layer (C). Lamination is carried out by use of adhesives according to conventional processes, like dry and wet lamination. The outer part of base layer (C) is then coated with the adhesive to form layer (D) having a thickness of 10-15 microns.

[0237] The resulting composite film is tested according to DIN EN ISO 527 by use of the measuring machine Toyo Boldwin (Tensilon, UTM-III-200), and the following measuring conditions:

[0238] Sample size: rectangular specimen, width 10 mmlength 70 mm

[0239] Inter-chuck distance: 40 mm

[0240] Testing speed: 100 mm/minute

[0241] Testing temperature: 20 C.

[0242] The following properties are obtained for the composite film of this Example 2:

[0243] Young's modulus: 622 megapascal

[0244] Tensile strength at break: 36.1 megapascal

[0245] Elongation at break: 684% gauge length

EXAMPLE 3

Application of the Composite Film of Example 1 to a Car Body

[0246] The car body is composed of steel and first coated by electrodeposition coating with an epoxy resin in order to prevent corrosion. Then the composite film of Example 1 is attached with the side of the adhesive layer (D) to the car body. The temperature of the film is increased to 50 C. and the film becomes soft and has higher elongation. The film enwraps the surface of the steel. The temperature of the film is then increased to 80-100 C. and the adhesive layer is completely melted, reacted, cured and adhered.