Hot melt adhesive compositions comprising low molecular weight ethylene copolymers

• US 5,391,434 A
• Filed: 05/12/1994
• Issued: 02/21/1995
• Est. Priority Date: 03/13/1992
• Status: Expired due to Fees

• Current Assignee: Alliedsignal Inc.
• Original Assignee: Alliedsignal Inc.
• Inventors: Krutzel, Lawrence
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): SZEKELY, PETER A
• Application Number:
  US08/241,539
• Time in Patent Office: 285 Days
• Field of Search: 428/412, 428/463, 428/483, 428/516, 428/518, 428/520
• US Class Current: 428/412
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 91/06 Waxes
• CPC Class Codes: C08L 93/04 Rosin
• CPC Class Codes: C09J 123/08 Copolymers of ethene C09J123/16 takes precedence
• CPC Class Codes: C09J 123/0853 Vinylacetate
• CPC Class Codes: C09J 123/0869 Acids or derivatives thereof
• CPC Class Codes: C09J 173/00 Adhesives based on macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C09J159/00 - C09J171/00; Adhesives based on derivatives of such polymers
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31797 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/3192 Next to vinyl or vinylidene chloride polymer
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer

Abstract

Hot melt adhesive compositions which include a base polymer constituent, a tackifying constituent, a wax constituent, and which further includes a low molecular weight polyethylene copolymer constituent which includes ketone functional moieties and/or hydroxyl functional moieties wherein the hot melt adhesive composition may be further characterized as providing improved adhesive strength to polar and non-polar substrates.

Claims

1. A laminar structure comprising:

(I) a first substrate;

(II) a second substrate; and

(III) a hot melt adhesive comprising;

(a) a base polymer constituent having a melt index of 0.2 to 3000g/10min as measured by ASTM D-1238;

(b) a tackifying constituent;

(c) optionally a wax constituent; and

(d) a low molecular weight constituent having a melt index of greater than 3000g/10 min as measured by ASTM D-1238, said low molecular weight constituent being selected from the group consisting of;

(i) random ethylene/carbon monoxide copolymers;

(ii) random ethylene/vinyl alcohol copolymers consisting of less than about 10 mol percent vinyl alcohol;

(iii) random ethylene/vinyl alcohol/vinyl acetate terpolymers consisting of less than about 10 mol percent vinyl alcohol;

(iv) random polymers of (i), (ii), and (iii) with additional recurring monomeric units derived from monomers selepted from the group consisting of alkyl acrylates, acrylic acid, methacrylic acid, maleic anhydride, and vinyl acetate; and

(v) at least partially oxidized said (i), (ii), (iii), and (iv)

wherein said first substrate (I) and said second substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said low molecular weight constituent (d) is present in an amount sufficient to provide greater adhesion to said substrates than a comparative composition in which said low molecular weight constituent is absent.

2. The laminar structure of claim 1 wherein said low molecular weight constituent (d) is an ethylene/carbon monoxide copolymer which consists of about 0.01 to about 99.99 weight percent ethylene and about 0.01 to about 99.99 weight percent carbon monoxide.

3. The laminar structure of claim 1 wherein said low molecular weight constituent (d) is an ethylene/carbon monoxide copolymer which consists of about 50 to about 99.99 weight percent ethylene and about 0.01 to about 50 weight percent carbon monoxide.

4. The laminar structure of claim 1 wherein said hot melt adhesive (III) further comprises a wax.

5. The laminar structure of claim 4 wherein said wax is selected from the group consisting of paraffin waxes, microcrystalline waxes, low molecular weight polyethylene waxes, and Fischer-Tropsch waxes.

6. The laminar structure of claim 1 wherein said low molecular weight constituent (d) is at least partially oxidized.

7. The laminar structure of claim 1 wherein said ethylene/vinyl alcohol/vinyl acetate terpolymer (iii) is at least 25 percent saponified.

8. The laminar structure of claim 1 wherein said first substrate (I) and said second substrate (II) are selected from the group consisting of aluminum foil, polycarbonate, polyethylene terephthalate, polypropylene, and polyvinyl chloride.

9. The laminar structure of claim 1 wherein said low molecular weight constituent (d) has a Brookfield viscosity, measured at 140°

C., of about 165 to about 725 centipoises.

10. A laminar structure comprising:

(I) a first substrate;

(II) a second substrate; and

(III) a hot melt adhesive comprising;

(a) about 1 to about 98 weight percent of a base

polymer constituent having a melt index of 0.2 to 3000g/10min as measured by ASTM D-1238;

(b) about 1 to about 98 weight percent of a tackifying constituent;

(c) optionally a wax constituent; and

(d) a low molecular weight constituent having a melt index of greater than 3000g/10 min as measured by ASTM D-1238, said low molecular weight constituent being selected from the group consisting of;

(i) random ethylene/carbon monoxide copolymers;

(ii) random ethylene/vinyl alcohol copolymers;

(iii) random ethylene/vinyl alcohol/vinyl acetate terpolymers;

(iv) random polymers of (i), (ii), and (iii) with additional recurring monomeric units derived from monomers selected from the group consisting of alkyl acrylates, acrylic acid, methacrylic acid, maleic anhydride, and vinyl acetate; and

(v) at least partially oxidized said (i), (ii), (iii), and (iv)

wherein said first substrate (I) and said second substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said low molecular weight constituent (d) is present in an amount sufficient to provide greater adhesion to said substrates than a comparative composition in which said low molecular weight constituent is absent.

11. The laminar structure of claim 10 wherein said hot melt adhesive (III) further comprises a wax.

12. The laminar structure of claim 10 wherein said low molecular weight constituent (d) has a Brookfield viscosity, measured at 140°

C., of about 165 to about 725 centipoises.

13. A laminar structure comprising:

(I) a first aluminum foil substrate;

(II) a second aluminum foil substrate; and

(III) a hot melt adhesive comprising;

(a) about 35 weight percent of an ethylene/n-butyl acrylate/carbon monoxide terpolymer having a melt index of about 100g/10 min as measured by ASTM D-1238;

(b) about 40 weight percent of a tackifying constituent;

(c) about 0 to about 20 weight percent of a wax constituent; and

(d) about 5 to about 25 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 165 to about 385 centipoises,

wherein said first aluminum foil substrate (I) and said second aluminum foil substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 3 lb./in. and a T-Peel Adhesion of at least about 3 lb./in. following aging of said substrates for 7 days at 56.5°

C.

14. The laminar structure of claim 13 wherein said hot melt adhesive (III) comprises:

(a) about 35 weight percent of said ethylene/n-butyl acrylate/carbon monoxide terpolymer;

(b) about 40 weight percent of said tackifying constituent; and

(c) about 25 weight percent of an oxidized low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 217 centipoises,

wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 3.5 lb./in. and a T-Peel Adhesion of at least about 4.4 lb./in. following aging of said substrates for 7 days at 56.5°

C.

15. The laminar structure of claim 13 wherein said hot melt adhesive (III) comprises:

(a) about 35 weight percent of said ethylene/n-butyl acrylate/carbon monoxide terpolymer;

(b) about 40 weight percent of said tackifying constituent; and

(c) about 25 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 230 to about 245 centipoises and a carbon monoxide content of about 13.7 to about 30 percent by weight,

wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 4.1 lb./in. and a T-Peel Adhesion of at least about 5 lb./in. following aging of said substrates for 7 days at 56.5°

C.

16. The laminar structure of claim 15 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 4.7 lb./in. and a T-Peel Adhesion of at least about 5 lb.in. following aging of said substrates for 7 days at 56.5°

C.

17. A laminar structure comprising:

(I) a first polyvinyl chloride substrate;

(II) a second polyvinyl chloride substrate; and

(III) a hot melt adhesive comprising;

(a) about 35 weight percent of an ethylene/n-butyl acrylate/carbon monoxide terpolymer having a melt index of about 100g/10 min as measured by ASTM D-1238;

(b) about 40 weight percent of a tackifying constituent; and

(c) about 25 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 230 centipoises, and a carbon monoxide content of about 13.7 weight percent,

wherein said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II), measured according to ASTM D-1876, of at least about 6.3 lb./in. and a T-Peel Adhesion of at least about 0.32 lb./in. following aging of said substrates for 7 days at 56.5°

C.

18. A laminar structure comprising:

(I) a first polypropylene substrate;

(II) a second polypropylene substrate; and

(III) a hot melt adhesive comprising;

(a) about 43 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 365 to about 440g/10 min as measured by ASTM D-1238, and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent;

(c) about 0 to about 20 weight percent of a wax constituent; and

(d) about 5 to about 25 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 230 to about 245 centipoises, and a carbon monoxide content of about 13.7 to about 30 weight percent,

wherein said first polypropylene substrate (I) and said second polypropylene substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polypropylene substrate (I) and said second polypropylene substrate (II), measured according to ASTM D-1876, of at least about 3.8 lb./in. and a T-Peel Adhesion of at least about 4.1 lb./in. following aging of said substrates for 7 days at 56.5°

C.

19. The laminar structure of claim 18 wherein said hot melt adhesive (III) comprises:

(a) about 43 weight percent of said ethylene/vinyl acetate copolymer;

(b) about 32 weight percent of said tackifying constituent;

(c) about 0 to about 20 weight percent of said wax constituent; and

(d) about 5 to about 25 weight percent of said low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 230 centipoises, wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polypropylene substrate (I) and said second polypropylene substrate (II), measured according to ASTM D-1876, of at least about 4.7 lb./in. and a T-Peel Adhesion of at least about 4.4 lb./in. following aging of said substrates for 7 days at 56.5°

C.

20. A laminar structure comprising:

(I) a first polycarbonate substrate;

(II) a second polycarbonate substrate; and

(III) a hot melt adhesive comprising;

(a) about 43 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 365 to about 440g/10 min as measured by ASTM D-1238, and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent;

(c) about 20 weight percent of a wax constituent; and

(d) about 5 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 725 centipoises, and a carbon monoxide content of about 13.7 to about 30 weight percent,

wherein said first polycarbonate substrate (I) and said second polycarbonate substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 5.4 lb./in. and a T-Peel Adhesion of at least about 5.3 lb./in. following aging of said substrates for 7 days at 56.5°

C.

21. The laminar structure of claim 20 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 5.6 lb./in. and a T-Peel Adhesion of at least about 5.6 lb./in. following aging of said substrates for 7 days at 56.5°

C.

22. A laminar structure comprising:

(I) a first polyethylene terephthalate substrate;

(II) a second polyethylene terephthalate substrate; and

(III) a hot melt adhesive comprising;

(a) about 43 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 365 to about 440g/10 min as measured by ASTM D-1238, and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent;

(c) about 20 weight percent of a wax constituent; and

(d) about 5 weight percent of a low molecular weight ethylene/vinyl alcohol constituent with a Brookfield viscosity, measured at 140°

C., of about 725 centipoises, and a number average molecular weight, measured by vapor phase osmometry, of about 2400,

wherein said first polyethylene terephthalate substrate (I) and said second polyethylene terephthalate substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polyethylene terephthalate substrate (I) and said second polyethylene terephthalate substrate (II), measured according to ASTM D-1876, of at least about 5.0 lb./in. and a T-Peel Adhesion of at least about 4.6 lb./in. following aging of said substrates for 7 days at 56.5°

C.

23. A laminar structure comprising:

(I) a first polycarbonate substrate;

(II) a second polycarbonate substrate; and

(III) a hot melt adhesive comprising;

(a) about 38 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 38 to about 48g/10 min as measured by ASTM D-1238, and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent;

(c) about 15 weight percent of a wax constituent; and

(d) about 15 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 165 to about 385 centipoises, and a carbon monoxide content of about 1.4 to about 11 weight percent,

wherein said first polycarbonate substrate (I) and said second polycarbonate substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 5.3 lb./in. and a T-Peel Adhesion of at least about 4.7 lb./in. following aging of said substrates for 7 days at 56.5°

C.

24. The laminar structure of claim 23 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 5.7 lb./in. and a T-Peel Adhesion of at least about 5.1 lb./in. following aging of said substrate for 7 days at 56.5°

C.

25. The laminar structure of claim 23 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 6 lb./in. and a T-Peel Adhesion of at least about 6 lb./in. following aging of said substrate for 7 days at 56.5°

C.

26. The laminar structure of claim 23 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polycarbonate substrate (I) and said second polycarbonate substrate (II), measured according to ASTM D-1876, of at least about 6.3 lb./in. and a T-Peel Adhesion of at least about 6.2 lb./in. following aging of said substrate for 7 days at 56.5°

C.

27. A laminar structure comprising:

(I) a first aluminum foil substrate;

(II) a second aluminum foil substrate; and

(III) a hot melt adhesive comprising;

(a) about 38 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 38 to about 48g/10 min as measured by ASTM D-1238 , and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent;

(c) about 25 weight percent of a wax constituent; and

(d) about 5 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 165 to about 385 centipoises, and a carbon monoxide content of about 1.4 to about 4.5 weight percent,

wherein said first aluminum foil substrate (I) and said second aluminum foil substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 2.5 lb./in. and a T-Peel Adhesion of at least about 1.9 lb./in. following aging of said substrates for 7 days at 56.5°

C.

28. The laminar structure of claim 27 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 2.7 lb./in. and a T-Peel Adhesion of at least about 2.3 lb./in. following aging of said substrates for 7 days at 56.5°

C.

29. The laminar structure of claim 27 wherein said hot melt adhesive (III) has an initial T-Peel Adhesion to said first aluminum foil substrate (I) and said second aluminum foil substrate (II), measured according to ASTM D-1876, of at least about 3.0 lb./in. and a T-Peel Adhesion of at least about 2.3 lb./in. following aging of said substrates for 7 days at 56.5°

C.

30. A laminar structure comprising:

(I) a first polyvinyl chloride substrate;

(II) a second polyvinyl chloride substrate; and

(III) a hot melt adhesive comprising;

(a) about 43 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 365 to about 440g/10 min as measured by ASTM D-1238 , and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent; and

(c) about 25 weight percent of a low molecular weight ethylene/carbon monoxide constituent with a Brookfield viscosity, measured at 140°

C., of about 230 centipoises, and a carbon monoxide content of about 13.7 weight percent,

wherein said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II), measured according to ASTM D-1876, of at least about 2.5 lb./in. and a T-Peel Adhesion of at least about 0.06 lb./in. following aging of said substrates for 7 days at 56.5°

C.

31. A laminar structure comprising:

(I) a first polyvinyl chloride substrate;

(II) a second polyvinyl chloride substrate; and

(III) a hot melt adhesive comprising;

(a) about 43 weight percent of an ethylene/vinyl acetate copolymer having a melt index of about 365 to about 440g/10 min as measured by ASTM D-1238 , and a vinyl acetate content of about 27.2 to about 28.8 weight percent;

(b) about 32 weight percent of a tackifying constituent; and

(c) about 25 weight percent of a low molecular weight ethylene/vinyl alcohol copolymer constituent with a Brookfield viscosity, measured at 140°

C., of about 725 centipoises, and a number average molecular weight, measured by vapor phase osmometry, of about 2400,

wherein said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II) are joined by an intermediate layer of said hot melt adhesive (III) in interfacial contact therewith and said hot melt adhesive (III) has an initial T-Peel Adhesion to said first polyvinyl chloride substrate (I) and said second polyvinyl chloride substrate (II), measured according to ASTM D-1876, of at least about 3.0 lb./in. and and a T-Peel Adhesion of at least about 0.06 lb./in. following aging of said substrates for 7 days at 56.5°

C.