Polymers adherent to polyolefins

• US 4,288,499 A
• Filed: 05/08/1979
• Issued: 09/08/1981
• Est. Priority Date: 05/08/1979
• Status: Expired due to Term

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Kielbania, Andrew J. Jr.
• Primary Examiner(s): HERBERT JR, THOMAS
• Application Number:
  US06/037,069
• Time in Patent Office: 854 Days
• Field of Search: 428/516, 428/500, 428/518, 260/29.6 R, 260/29.6 SQ
• US Class Current: 428/518
• CPC Class Codes: B05D 7/02 to macromolecular substances, e.g. rubber treatment or coating of shaped articles made of macromolecular substances C08J7/00
• CPC Class Codes: B32B 37/12 characterised by using adhesives
• CPC Class Codes: C08J 2323/02 not modified by chemical after treatment
• CPC Class Codes: C08J 2433/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• 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 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 133/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: Y10T 428/31855 Of 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

Abstract

This invention is concerned with an article comprising a polyolefin substrate and adherent thereto a vinyl addition polymer of monomers comprising at least 5% by weight a primary monomer selected from

(a) monomers having the formula ##STR1## wherein X is --O--, --NH-- or --NR⁵ --;

R¹ and R⁷, individually, are H, methyl or ethyl;

R² is H or an organic radical, preferably --COOH, --CONH₂ or --COOR⁶ ;

R³ is H or an organic radical, preferably methyl, other alkyl having up to about five carbon atoms, --CH₂ COOR⁶, --COOR⁶ or --CH₂ COOH;

R⁴ and R⁵, individually, are monocyclic alkyl having six or more carbon atoms, acyclic alkyl having nine or more carbon atoms, or alkaryl having nine or more carbon atoms;

R⁶ is hydrocarbyl, preferably alkyl;

n has a value from zero to about ten;

(b) vinyl esters of alkanoic acids having at least eight carbon atoms;

(c) substituted styrenes wherein the substituent group or groups have a total of three or more carbon atoms;

and mixtures thereof; said polymer having surface energy properties such as to form a stable bond with said substrate.

The polymer, used alone or in a blend, serves as a coating, a tiecoat, an adhesive or a binder.

Claims

1. An article comprising an untreated polyolefin substrate and adherent thereto a vinyl addition polymer of ( 1) monomers comprising at least 5% by weight a primary monomer selected from

(a) monomers having the formula ##STR6## wherein X is --O--, --NH-- or --NR⁵ --;

R¹ and R⁷, individually, are H, methyl or ethyl;

R² is H, --COOH, --CONH₂, or --COOR⁶,

R³ is H, alkyl having up to 5 carbon atoms, --CH₂ COOR⁶, --COOR⁶ or --CH₂ COOH;

R⁴ and R⁵, individually, are monocyclic alkyl having 6 to 20 carbon atoms, acyclic alkyl having 9 to 20 carbon atoms, or alkaryl having 9 to 18 carbon atoms;

R⁶ is hydrocarbyl; and

n having a value from zero to about ten;

(b) vinyl esters of alkanoic acids having 8 to 20 carbon atoms;

(c) Alkyl substituted styrene wherein the substituent group or groups have a total of 3 to 15 carbon atoms;

and mixtures thereof and optionally (2) or more substituted ethylene supplementary monomers;

said polymer having surface energy properties such as to form a stable bond, having a 180°

peel strength greater than 2 pounds per inch, with said substrate.

2. The article of claim 1 wherein the polymer has a total surface energy between about 22 and 42 dynes per cm, said energy having a nonpolar dispersive component between about 20 and about 38 dynes per cm and a polar component up to about 15 dynes per cm, the polar component being not over about 36% of the total surface energy.

3. The article of claim 2, the polymer having an average solubility greater than 0.25 gm. per 100 ml. in isoctane, n-pentane, 1-hexene, diisobutylene and cyclohexane.

4. The article of claim 3 the monomers consisting of primary and supplementary monomers wherein the supplementary monomer or monomers have an average solubility parameter, by weight, of 8.8 or less.

5. The article of claim 3 wherein the primary monomer comprises at least 50% by weight of (a), (b), or (c);

or a mixture thereof.

6. The article of claim 3 wherein the primary monomer is a decyl methacrylate, a decyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, vinyl decanoate, tertiarybutyl styrene or a mixture thereof and wherein the supplementary monomer is an acrylic or methacrylic acid or ester, styrene or a mixture thereof.

7. The article of claim 3 wherein the vinyl addition polymer comprises crosslinkable mer units.

8. The article of claim 3 wherein the vinyl addition polymer comprises carboxylic acid units or salts thereof.

9. The article of claim 3 wherein the vinyl addition polymer is a latex polymer and the peel strength is greater than 4 pounds per inch.

10. The article of claim 3 wherein the primary monomer comprises at least 25% by weight of (a), (b) or (c);

or a mixture thereof.

11. The article of claim 10 the monomers consisting of primary and supplementary monomers wherein the supplementary monomer or monomers have an average solubility parameter, by weight, of 9.2 or less.

12. The article of claim 3 wherein the primary monomer has the formula ##STR7## wherein X is --O--, --NH-- or --NR⁵ --;

R¹ and R⁷, individually, are H, methyl or ethyl;

R² is H, --COOH, --CONH₂, or --COOR⁶,

R³ is H, alkyl having up to 5 carbon atoms, --CH₂ COOR⁶, --COOR⁶ or --CH₂ COOH;

R⁴ and R⁵, individually, are monocyclic alkyl having 6 to 20 carbon atoms, acyclic alkyl having 9 to 20 carbon atoms, or alkaryl having 9 to 18 carbon atoms;

R⁶ is hydrocarbyl; and

n having a value from zero to about ten.

13. The article of claim 12 wherein the primary monomer is a decyl acrylate, a decyl methacrylate or a mixture thereof.

14. The article of claim 12 wherein the primary monomer is cyclohexyl methacrylate, cyclohexyl acrylate or a mixture thereof.

15. The article of claim 3 wherein the primary monomer is a vinyl ester of an alkanoic acid having 8 to 20 carbon atoms.

16. The article of claim 1 wherein the alkanoic acid has 9 to 11 carbon atoms.

17. The article of claim 3 wherein the primary monomer is an alkyl substituted styrene wherein the substituent group or groups have a total of 3 to 15 carbon atoms.

18. The article of claim 17 wherein the primary monomer is tertiary-butyl styrene.

19. The article of claim 3 wherein the total surface energy is between 26 and 38 dynes per centimeter, having a nonpolar dispersive component between about 22 to about 36 dynes per centimeter and a polar component up to about 14 dynes per centimeter.

20. The article of claim 19 wherein the average solubility is greater than 0.50 gm per 100 ml.

21. The article of claim 3 wherein the polyolefin is polypropylene.

22. The article of claim 21 wherein the polymer is free of halogen atoms.

23. The article of claim 1 wherein the vinyl addition polymer comprises crosslinkable mer units.

24. The article of claim 21 wherein the vinyl addition polymer comprises carboxylic acid mer units or salts thereof.

25. The article of claim 21 wherein the vinyl addition polymer is a latex polymer and the peel strength is greater than 4 pounds per inch.

26. The article of claim 21 wherein the primary monomer has the formula ##STR8## wherein X is --O--, --NH-- or --NR⁵ --;

R¹ and R⁷, individually, are H, methyl or ethyl;

R² is H, --COOH, --CONH₂, or --COOR⁶,

R³ is H, alkyl having up to 5 carbon atoms, --CH₂ COOR⁶, --COOR⁶ or --CH₂ COOH;

R⁴ and R⁵, individually, are monocyclic alkyl having 6 to 20 carbon atoms, acyclic alkyl having 9 to 20 carbon atoms, or alkaryl having 9 to 18 carbon atoms;

R⁶ is hydrocarbyl; and

n having a value from zero to about ten.

27. The article of claim 26 wherein the primary monomer is a decyl acrylate, a decyl methacrylate or a mixture thereof.

28. The article of claim 26 wherein the primary monomer is cyclohexyl methacrylate, cyclohexyl acrylate or a mixture thereof.

29. The article of claim 21 wherein the primary monomer is a vinyl ester of an alkanoic acid having 8 to 20 carbon atoms.

30. The article of claim 29 wherein the alkanoic acid has 9 to 11 carbon atoms.

31. Tthe article of claim 21 wherein the primary monomer is an alkyl substituted styrene wherein the substituent group or groups have a total of 3 to 15 carbon atoms.

32. The article of claim 31 wherein the primary monomer is tertiary-butyl styrene.

33. The article of claim 21 wherein the primary monomer is a decyl methacrylate, a decyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, vinyl decanoate, tertiary-butyl styrene or a mixture thereof and wherein the supplementary monomer is an acrylic or methacrylic acid or ester, styrene or a mixture thereof.

35. The article of claim 24 the polymer being crosslinkable by means of the quaternary ammonium groups.

36. An article comprising an untreated polyolefin substrate and adherent thereto a vinyl addition polymer of monomers comprising at least 5% by weight a primary monomer selected from

(a) monomers having the formula ##STR9## wherein X is --O--, --NH-- or --NR⁵ --;

R¹ and R⁷, individually, are H, methyl or ethyl;

R² is H, --COOH, --CONH₂, or --COOR⁶,

R³ is H, alkyl having up to 5 carbon atoms, --CH₂ COOR⁶, --COOR⁶ or --CH₂ COOH;

R⁴ and R⁵, individually, are monocyclic alkyl having 6 to 20 carbon atoms, acyclic alkyl having 9 to 20 carbon atoms, or alkaryl having 9 to 18 carbon atoms;

R⁶ is hydrocarbyl; and

n having a value from zero to about ten;

(b) vinyl esters of alkanoic acids having 8 to 20 carbon atoms;

(c) alkyl substituted styrene wherein the substituent group or groups have a total of 3 to 15 carbon atoms;

and mixtures thereof;

said polymer having surface energy properties such as to form a stable bond, having a 180°

peel strength greater than 2 pounds per inch, with said substrate;

said polymer having been polymerized in an inert atmosphere.

34. The article of claim 36 having supplementary monomers containing quaternary ammonium groups or salts thereof.