Patent US4059016A successfully refreshed from Google Patents.
Patent US4288499A successfully refreshed from Google Patents.
US4288499A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polymers adherent to polyolefins
Assignee: Rohm and Haas Co
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Filing: 1979-05-08
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Granted: 1981-09-08
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Expires: 1999-05-08
Abstract
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 --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H or an organic radical, preferably --COOH, --CONH 2 or --COOR 6 ; R 3 is H or an organic radical, preferably methyl, other alkyl having up to about five carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 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.
Inventors
- 👤 Andrew J. Kielbania, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 13:01
CPC Classifications
B; B05; B05D; B05D7/00; B05D7/02; B32; B32B; B32B27/00; B32B27/32; B32B37/00; B32B37/12; C; C08; C08J; C08J7/00; C08J7/04; C08J7/0427; C08J7/043; C08J7/046; C09; C09D; C09D133/00; C09D133/04; C09D133/14; C09D133/24; C09D133/26; C08J2323/00; C08J2323/02; C08J2433/00; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31855; Y10T428/31909; Y10T428/31913; Y10T428/3192
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
206 words
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 --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 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.
Claim 2
Dependent Claim
206 words
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 --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 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.
Claim 3
Dependent Claim
61 words
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.
Claim 4
Dependent Claim
25 words
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.
Claim 5
Dependent Claim
30 words
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.
Claim 6
Dependent Claim
24 words
The article of claim 3 wherein the primary monomer comprises at least 50% by weight of (a), (b), or (c); or a mixture thereof.
Claim 7
Dependent Claim
46 words
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.
Claim 8
Dependent Claim
14 words
The article of claim 3 wherein the vinyl addition polymer comprises crosslinkable mer units.
Claim 9
Dependent Claim
17 words
The article of claim 3 wherein the vinyl addition polymer comprises carboxylic acid units or salts thereof.
Claim 10
Dependent Claim
25 words
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.
Claim 11
Dependent Claim
24 words
The article of claim 3 wherein the primary monomer comprises at least 25% by weight of (a), (b) or (c); or a mixture thereof.
Claim 12
Dependent Claim
30 words
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.
Claim 13
Dependent Claim
114 words
The article of claim 3 wherein the primary monomer has the formula ##STR7## wherein X is --O--, --NH-- or --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 is hydrocarbyl; and n having a value from zero to about ten.
Claim 14
Dependent Claim
20 words
The article of claim 12 wherein the primary monomer is a decyl acrylate, a decyl methacrylate or a mixture thereof.
Claim 15
Dependent Claim
18 words
The article of claim 12 wherein the primary monomer is cyclohexyl methacrylate, cyclohexyl acrylate or a mixture thereof.
Claim 16
Dependent Claim
23 words
The article of claim 3 wherein the primary monomer is a vinyl ester of an alkanoic acid having 8 to 20 carbon atoms.
Claim 17
Dependent Claim
15 words
The article of claim 1 wherein the alkanoic acid has 9 to 11 carbon atoms.
Claim 18
Dependent Claim
29 words
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.
Claim 19
Dependent Claim
12 words
The article of claim 17 wherein the primary monomer is tertiary-butyl styrene.
Claim 20
Dependent Claim
43 words
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.
Claim 21
Dependent Claim
17 words
The article of claim 19 wherein the average solubility is greater than 0.50 gm per 100 ml.
Claim 22
Dependent Claim
10 words
The article of claim 3 wherein the polyolefin is polypropylene.
Claim 23
Dependent Claim
13 words
The article of claim 21 wherein the polymer is free of halogen atoms.
Claim 24
Dependent Claim
14 words
The article of claim 1 wherein the vinyl addition polymer comprises crosslinkable mer units.
Claim 25
Dependent Claim
18 words
The article of claim 21 wherein the vinyl addition polymer comprises carboxylic acid mer units or salts thereof.
Claim 26
Dependent Claim
25 words
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.
Claim 27
Dependent Claim
114 words
The article of claim 21 wherein the primary monomer has the formula ##STR8## wherein X is --O--, --NH-- or --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 is hydrocarbyl; and n having a value from zero to about ten.
Claim 28
Dependent Claim
20 words
The article of claim 26 wherein the primary monomer is a decyl acrylate, a decyl methacrylate or a mixture thereof.
Claim 29
Dependent Claim
18 words
The article of claim 26 wherein the primary monomer is cyclohexyl methacrylate, cyclohexyl acrylate or a mixture thereof.
Claim 30
Dependent Claim
23 words
The article of claim 21 wherein the primary monomer is a vinyl ester of an alkanoic acid having 8 to 20 carbon atoms.
Claim 31
Dependent Claim
15 words
The article of claim 29 wherein the alkanoic acid has 9 to 11 carbon atoms.
Claim 32
Dependent Claim
29 words
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.
Claim 33
Dependent Claim
12 words
The article of claim 31 wherein the primary monomer is tertiary-butyl styrene.
Claim 34
Dependent Claim
46 words
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.
Claim 35
Dependent Claim
15 words
The article of claim 36 having supplementary monomers containing quaternary ammonium groups or salts thereof.
Claim 36
Dependent Claim
16 words
The article of claim 24 the polymer being crosslinkable by means of the quaternary ammonium groups.
Claim 37
Dependent Claim
204 words
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 --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 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.
Claim 38
Dependent Claim
204 words
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 --NR 5 --; R 1 and R 7 , individually, are H, methyl or ethyl; R 2 is H, --COOH, --CONH 2 , or --COOR 6 , R 3 is H, alkyl having up to 5 carbon atoms, --CH 2 COOR 6 , --COOR 6 or --CH 2 COOH; R 4 and R 5 , 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; R 6 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.
References Cited (Backward Citations)
US3258443A
Cited
US3241662A
Cited
US3394029A
Cited
US3519531A
Cited
GB1177199A
Cited
US3887738A
Cited
US3931087A
Cited
US4012560A
Cited
US4014645A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-09-07 | 1985-03-09 | 1985-09-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-09-07 | 1989-03-09 | 1989-09-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-09-07 | 1993-03-09 | 1993-09-08 | $7700.00 | Window Closed / Lapsed |