Radiation hardened composite layer plate or film

• US 20070166548A1
• Filed: 02/18/2005
• Published: 07/19/2007
• Est. Priority Date: 02/24/2004
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Schwalm, Reinhold, Beck, Erich, Heischkel, Yvonne, Gruber, Nick, Menzel, Klaus
• Granted Patent: US 7,955,538 B2
• Time in Patent Office: Days
• US Class Current: 428/411.100
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 37/0025 Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing moulding on preformed layers as inserts B29C70/68; applying fluent material to surfaces in general B05
• CPC Class Codes: B29C 63/22 using layers or sheathings having a shape adapted to the shape of the article B29C63/26 and B29C63/38 take precedence
• CPC Class Codes: B29L 2031/3005 Body finishings
• CPC Class Codes: B32B 2310/08 by wave energy or particle radiation
• CPC Class Codes: B32B 2327/06 PVC, i.e. polyvinylchloride
• CPC Class Codes: B32B 2327/12 containing fluorine
• CPC Class Codes: B32B 2333/12 Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2375/00 Polyureas; Polyurethanes
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C08G 18/282 Alkanols, cycloalkanols or arylalkanols including terpenealcohols
• CPC Class Codes: C08G 18/3212 containing cycloaliphatic groups
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/7831 : containing biuret groups
• CPC Class Codes: C08G 18/7837 : containing allophanate groups
• CPC Class Codes: C08G 18/792 : formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8175 : with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08J 2475/16 : having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08J 7/0427 : with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/043 : Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/046 : Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C09D 175/16 : having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10T 428/26 : Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/3154 : Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31721 : Of polyimide
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31797 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 : Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31928 : Ester, halide or nitrile of addition polymer

Abstract

The invention relates to a radiation-curable laminated sheet or film comprising at least one substrate layer and a top layer which comprises a radiation-curable material having a glass transition temperature below 50° C. and having a high double bond density, processes for the production thereof and the use thereof.

Claims

1. The method of using a radiation-curable laminated sheet or film comprising at least one substrate layer and a top layer for lamination of shaped articles, wherein the top layer consists of radiation-curable material which comprises a binder having a glass transition temperature below 50°

C. and a content of ethylenically unsaturated groups of more than 2 mol/kg of binder.

2. The method of using a radiation-curable laminated sheet or film according to claim 1, the top layer being transparent.

3. The method of using a radiation-curable laminated sheet or film according to claim 1, the binder comprising at least one urethane (meth)acrylate which comprises at least one cycloaliphatic isocyanate as a component.

4. The method of using according to claim 1, the binder comprising at least one urethane (meth)acrylate which comprises isophorone diisocyanate or hexamethylene diisocyanate as a component.

5. The method of using a radiation-curable laminated sheet or film according to claim 1, a color-imparting intermediate layer also being present between the substrate layer and the top layer.

6. The method of using a radiation-curable laminated sheet or film according to claim 1, a layer of polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-diene-styrene copolymers (A EPDM), polyetherimides, polyetherketones, polyphenylene sulfides, polyphenyl ethers or mixtures thereof also being present between the color-imparting intermediate layer and the top layer.

7. The method of using a radiation-curable laminated sheet or film according to claim 6, the radiation-curable material comprising polymers having ethylenically unsaturated groups and having a molar mass of more than 2000 g/mol, if appropriate as a mixture with ethylenically unsaturated, low molecular weight compounds differing therefrom and having a molar mass of less than 2000 g/mol and/or mixtures of saturated, thermoplastic polymers with ethylenically unsaturated compounds.

8. The method of using a radiation-curable laminated sheet or film according to claim 1, the substrate layer being a layer of thermoplastic polymers selected from the group comprising polymethyl methacrylates, polybutyl methacrylates, polyurethanes, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, polyamides, polycarbonates, acrylonitrile-butadiene-styrene polymers (ABS), acrylate-styrene-acrylonitrile copolymers (ASA), acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyetherimides, polyetherketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof.

9. The method of using according to claim 1, wherein the radiation-curable material comprises not more than 10% by weight of compounds which have only one curable group.

10. A process for the production of laminated shaped articles, in particular automotive parts, wherein the radiation-curable laminated sheet or film according to claim 1 is adhesively bonded to the shaped articles, and the top layer is then cured by radiation.

11. A process for the production of laminated shaped articles comprising plastic, wherein the radiation-curable laminated sheet or film according to claim 1 is thermoformed in a thermoforming mold and the back of the substrate layer is sprayed with the plastics material, the radiation curing of the top layer being effected after the thermoforming process or after the spraying of the back.

12. A laminated shaped article obtainable by a process according to claim 11.

13. A radiation-curable laminated sheet or film comprising at least one substrate layer and a top layer consisting of radiation-curable material which comprises a binder having a glass transition temperature below 50°

C. and a content of ethylenically unsaturated groups of more than 2 mol/kg of binder, wherein a color-imparting intermediate layer is also present between the substrate layer and the top layer.

14. The radiation-curable laminated sheet or film according to claim 13, a layer of polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyetherimides, polyetherketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof also being present between the color-imparting intermediate layer and the top layer.

15. The radiation-curable laminated sheet or film according to either of claim 13, the radiation-curable material comprising polymers having ethylenically unsaturated groups and a molar mass of more than 2000 g/mol, if appropriate as a mixture with ethylenically unsaturated, low molecular weight compounds differing therefrom and having a molar mass of less than 2000 g/mol and/or mixtures of saturated, thermoplastic polymers with ethylenically unsaturated compounds.

16. The radiation-curable laminated sheet or film according to claim 13, wherein the radiation-curable material comprises not more than 10% by weight of compounds which have only one curable group.

17. The radiation-curable laminated sheet or film according to claim 13, the binder comprising at least one urethane (meth)acrylate which comprises at least one cycloaliphatic isocyanate as a component.

18. The radiation-curable laminated sheet or film according to claim 13, the binder comprising at least one urethane (meth)acrylate which comprises isophorone diisocyanate or hexamethylene diisocyanate as a component.