Thermoplastic polyolefin composite structure

• US 4,902,557 A
• Filed: 01/25/1988
• Issued: 02/20/1990
• Est. Priority Date: 01/25/1988
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Rohrbacher, Frank
• Primary Examiner(s): Ives, P. C.
• Application Number:
  US07/147,971
• Time in Patent Office: 757 Days
• Field of Search: 428/516, 428/520, 428/215, 428/216, 428/31
• US Class Current: 428/215
• CPC Class Codes: B29K 2995/0022 Bright, glossy or shiny surface
• CPC Class Codes: B32B 2307/4026 within the layer by addition of a colorant, e.g. pigments, dyes
• CPC Class Codes: B32B 2307/546 Flexural strength; Flexion stiffness
• CPC Class Codes: B32B 2333/12 Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• CPC Class Codes: B32B 2605/08 Cars
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/20 using fillers, pigments, thixotroping agents
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: C08J 2323/02 not modified by chemical after treatment
• CPC Class Codes: C08J 2467/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08J2467/06 takes precedence
• 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: Y10T 428/24967 Absolute thicknesses specified
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer

Abstract

A thermoplastic polyolefin composite that is useful as an exterior auto or truck body part has the following layers of components:

a. a layer of a glossy clear thermoplastic finish bonded firmly to

b. a layer of a thermoplastic pigment containing paint firmly bonded to

c. a thin size layer of a thermoplastic chlorinated polyolefin that is firmly bonded to

d. a flexible sheet of a thermoplastic polyolefin resin.

A thermoformable composite sheet structure that can be made into the above laminate having the layers a.-d. of the above structure also is part of this invention.

Claims

1. A three dimensional thermoplastic polyolefin composite useful as an exterior auto or truck body part consisting essentially of the following components:

1. a multilayer coating consisting essentially of

a. a 10-125 micron thick layer of a glossy clear thermoplastic finish formed from a clear coating composition bonded firmly to

b. a 5-75 micron thick layer of a thermoplastic pigment containing paint firmly bonded to

c. a 1-25 micron thick size layer of a thermoplastic chlorinated polyolefin containing 15-50% by weight chlorine;

said multilayer coating formed by applying a layer of a clear coating composition to a polymeric film, applying a paint layer to the layer of clear coating composition and then applying a layer of the thermoplastic chlorinated polyolefin to the paint layer and curing the multilayer coating;

said multilayer being firmly bonded by lamination to

2. a 250-1250 micron thick layer of a flexible extruded sheet of a thermoplastic polyolefin having a flexural modulus of about 175-2100 MPa and a melt flow rate of about 0.5-2.0 g/10 min.;

wherein the chlorinated polyolefin layer of the multilayer coating is in contact with the sheet of thermoplastic polyolefin and the polymeric sheet is removed after lamination to leave a smooth glossy surface on the clear layer and the resulting flexible sheet having the multilayer coating is thermoformed into a three dimensional structure that is bonded to

3. a 500-25,000 micron thick rigid layer of a thermoplastic polyolefin resin having a modulus of about 175-2100 MPa and a melt flow rate of about 4.0-8.0 g/10 min. formed by injection molding said resin to the flexible sheet having a three dimensional structure;

wherein layers a. and b. of the multilayer form the exterior surface of the composite and have a gloss of at least 60 measured at 20° and

a distinctness of image of at least 60.

2. The composite of claim 1 in which the chlorinated polyolefin consists essentially of a propylene/maleic acid copolymer containing about 15-50% by weight chlorine.

3. The composite of claim 1 in which the chlorinated polyolefin consists essentially of a chlorinated polyethylene containing about 15-50% by weight chlorine.

4. The composite of claim 1 in which the size layer consists essentially of a chlorinated polypropylene and maleic anhydride polymer containing about 18-35% by weight chlorine.

5. The composite of claim 1 in which the size layer of the chlorinated polyolefin comprises a mixture of the chlorinated polyolefin and a thermoplastic polymer selected from the group consisting of ethylene vinyl acetate polymer, alkyd resin, and acrylic polymers.

6. The composite of claim 1 in which the clear layer comprises a layer of a polymer selected from the group consisting of methyl methacrylate polymer and copolymers thereof.

7. The composite of claim 1 in which the clear layer comprises polymethyl methacrylate and a graft copolymer having a backbone of polymerized monomers of esters of acrylic acid or methacrylic acid and allyl methacrylate or allyl acrylate grafting sites having grafted thereto polymeric segments of alkyl acrylate or alkyl methacrylate units.

8. The composite of claim 7 in which the pigment containing layer comprises polymethyl methacrylate and a graft copolymer having a backbone of polymerized monomers of ester of acrylic acid or methacrylic acid and allyl methacrylate or allyl acrylate grafting sites having grafted thereto polymeric segments of alkyl acrylate or alkyl methacrylate units and contains pigment in a pigment to binder weight ratio of about 1/100-100/100.

9. The composite of claim 1 in which the pigment containing layer comprises a layer of a polymer selected from the group consisting of methyl methacrylate polymer and copolymers thereof and contains pigment in a pigment to binder weight ratio of about 1/100-100/100.

10. The composite of claim 1 in which the clear composite a mixture of about 50-80% by weight of polyvinylidene fluoride and correspondingly 50-20% by weight of polymethyl methacrylate or polyethyl methacrylate.

11. The composite of claim 10 in which the pigment containing paint layer comprises a mixture of about 50-80% by weight of polyvinylidine fluoride and correspondingly 50-20% by weight of polymethyl methacrylate or polyethyl methacrylate and pigment in a pigment to binder weight ratio of about 1/100-100/100.

12. The composite of claim 1 in which the flexible sheet of thermoplastic polyolefin comprises an extruded sheet of a compounded mixture of polypropylene, a synthetic elastomeric resin, pigments and additives.

13. The composite of claim 1 in which the rigid layer of thermoplastic polyolefin comprises a compounded mixture of polypropylene, a synthetic elastomeric resin, pigments and additives.

14. A thermoformable sheet structure useful for forming the composite of claim 1 consisting essentially of the following components:

1. a multilayer coating consisting essentially of

a. a 10-125 micron layer thick layer of a glossy clear thermoplastic finish formed from a clear coating composition bonded firmly to

b. a 5-75 micron thick layer of a thermoplastic pigment containing paint firmly bonded to

c. a 1-25 micron thick layer of a thermoplastic chlorinated polyolefin containing 15-50% by weight chlorine;

said multilayer coating formed by applying a layer of a clear coating composition to a polymeric film, applying a paint layer to the layer of clear coating composition and then applying a layer of the thermoplastic chlorinated polyolefin to the paint layer and curing the multilayer coating;

said multilayer coating being firmly bonded by lamination to

2. a 250-1250 thick layer of flexible extruded sheet of a thermoplastic polyolefin having a flexural modulus of about 175-2100 MPa and a melt flow rate of about 0.5-2.0 g/10 min.;

wherein the chlorinated polyolefin layer of the multilayer coating is in contact with the sheet of thermoplastic polyolefin sheet.

15. The thermoformable sheet structure of claim 14 in which the chlorinated polyolefin consists essentially of a propylene/maleic acid copolymer.

16. The thermoformable sheet structure of claim 14 in which the chlorinated polyolefin consists essentially of chlorinated polyethylene.

17. The thermoformable sheet structure of claim 14 in which the size layer consists essentially of a chlorinated polypropylene and maleic anhydride polymer containing about 18-35% by weight chlorine.

18. The thermoformable sheet structure of claim 14 in which the size layer of the chlorinated polyolefin comprises a mixture containing a thermoplastic polymer selected from the group consisting of ethylene vinyl acetate polymer, alkyd resin, and acrylic polymers.

19. The thermoformable sheet structure of claim 14 in which the clear layer comprises a layer of a polymer selected from the group consisting of methyl methacrylate polymer and copolymers thereof.

20. The thermoformable sheet structure of claim 14 in which the clear layer comprises polymethyl methacrylate and a graft copolymer having a backbone of polymerized monomers of ester of acrylic acid or methacrylic acid and allyl methacrylate of allyl acrylate grafting sites having grafted thereto polymeric segments of alkyl acrylate of alkyl methacrylate units.

21. The thermoformable sheet structure of claim 14 in which the pigment containing layer comprises a layer of a polymer selected from the group consisting of methyl methacrylate polymer and copolymers thereof and contains pigment in a pigment to binder weight ratio or about 1/100-100/100.

22. The thermoformable sheet structure of claim 14 in which the pigment containing layer comprises polymethyl methacrylate and a graft copolymer having a backbone of polymerized monomers of ester of acrylic acid or methacrylic acid and allyl methacrylate or allyl acrylate grafting sites having grafted thereto polymeric segments of alkyl acrylate or alkyl methacrylate units and contains pigment in a pigment to binder weight ratio of about 1/100-100/100.

23. The thermoformable sheet structure of claim 14 in which the clear comprises a mixture of about 50-80% by weight of polyvinylidine fluoride and correspondingly 50-20by weight of polymethyl methacrylate.

24. The thermoformable sheet structure of claim 14 in which the pigment containing paint layer comprises a mixture of about 50-80% by weight of polyvinylidene fluoride and correspondingly 50-20% by weight of polymethyl methacrylate and pigment in a pigment to binder weight ratio of about 1/100-100/100.

25. The thermoformable sheet structure of claim 14 in which the flexible sheet of thermoplastic polyolefin comprises an extruded sheet of a compounded mixture of polypropylene, a synthetic elastomeric resin, pigments and additives.