Patent US5157756A successfully refreshed from Google Patents.
Patent US4393094A successfully refreshed from Google Patents.
US4393094A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Stabilization of electron beam curable compositions for improved exterior durability
Assignee: EIDP Inc
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Filing: 1982-04-19
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Granted: 1983-07-12
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Expires: 2002-04-19
Abstract
Abstract A low dosage electron beam radiation polymerizable protective and decorative coating composition or paint with improved weatherability, coated articles bearing such a protective coating and processes for preparing such articles. The radiation polymerizable coating composition comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, characterized in that said vinyl monomers include N-vinyl-2-pyrrolidone in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR1## where R 1 or R 2 =H or an alkyl group of C 1 -C 25 , preferably C 3 -C 9 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR2## wherein R=H methyl, preferably H. The flexible coating exhibits excellent physical qualities including improved weatherability and good adhesion to a variety of substrates being particularly suitable for use on polyvinyl chloride fabric, wherein it is discoloration resistant after heat aging.
Inventors
- 👤 David L. Garrett, Jr.
- 👤 Joseph C. Cassatta
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 19:50
CPC Classifications
C; C09; C09D; C09D4/00
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
166 words
A coating composition polymerizable by low dosage ionizing radiation, which comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers including N-vinyl-2-pyrrolidone in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR11## wherein R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amine having the formula: ##STR12## wherein R=H or methyl.
Claim 2
Dependent Claim
166 words
A coating composition polymerizable by low dosage ionizing radiation, which comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers including N-vinyl-2-pyrrolidone in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR11## wherein R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amine having the formula: ##STR12## wherein R=H or methyl.
Claim 3
Dependent Claim
27 words
A coating composition according to claim 1, wherein said R 1 or R 2 of said benzotriazole is an alkyl group of C 3 -C 9 .
Claim 4
Dependent Claim
18 words
A coating composition according to claims 1 or 2, wherein said R of said hindered amine is hydrogen.
Claim 5
Dependent Claim
15 words
A coating composition according to claim 1, wherein said benzotriazole is a mixture of benzotriazoles.
Claim 6
Dependent Claim
19 words
A coating composition according to claims 1 or 4, wherein said hindered amine is a mixture of hindered amines.
Claim 7
Dependent Claim
34 words
A coating composition according to claim 1, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine.
Claim 8
Dependent Claim
34 words
A coating composition according to claim 1, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene.
Claim 9
Dependent Claim
28 words
A coating composition according to claim 1, wherein said resin contains between about 0.5 and about 3 vinyl unsaturation units per 1000 units molecular weight of said resin.
Claim 10
Dependent Claim
32 words
A coating composition according to claim 1, wherein said resin comprises a urethane acrylic oligomer having the formula: ##STR13## wherein R' is hydrogen or methyl and Y is a divalent urethane residue.
Claim 11
Dependent Claim
33 words
A coating composition according to claim 1, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B).
Claim 12
Dependent Claim
21 words
A coating composition according to claim 9, wherein said vinyl monomers other than said N-vinyl-2-pyrrolidone consist essentially of acrylic ester monomers.
Claim 13
Dependent Claim
17 words
A coating composition according to claim 9 or 11, wherein said R' of said oligomer is hydrogen.
Claim 14
Dependent Claim
20 words
A coating composition according to claim 9, wherein said oligomer has a molecular weight between about 400 and about 10,000.
Claim 15
Dependent Claim
23 words
A coating composition according to claim 11, wherein said acrylic ester monomers comprise at least 70 weight percent of monovinyl acrylic ester monomers.
Claim 16
Dependent Claim
23 words
A coating composition according to claim 14, wherein said acrylic ester monomers comprise greater than 80 weight percent of monovinyl acrylic ester monomers.
Claim 17
Dependent Claim
34 words
A coating composition according to claim 14, wherein said monovinyl acrylic ester monomers are selected from the group consisting essentially of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate and mixtures thereof.
Claim 18
Dependent Claim
39 words
A coating composition according to claim 14 or 16, wherein said acrylic ester monomer, other than said monovinyl acrylic ester monomer, is selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylol propane triacrylate and mixtures thereof.
Claim 19
Dependent Claim
211 words
A 100% solids coating composition polymerizable by low dosage ionizing radiation adapted to coat flexible substrates, which exclusive of pigments, initiators and other non-reactive components, consists essentially of an oligomer/monomer mixture of: (A) between about 90 and about 10 weight percent oligomer having the formula: ##STR14## wherein R' is hydrogen or methyl; and Y is a divalent urethane residue; and said oligomer has between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said oligomer; and (B) between about 10 and about 90 weight percent vinyl monomers polymerizable with said oligomer upon exposure to radiation, said vinyl monomers consisting essentially of (i) acrylic ester monomers and (ii) N-vinyl-2-pyrrolidone, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B), and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR15## where R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR16## wherein R=H or methyl.
Claim 20
Dependent Claim
211 words
A 100% solids coating composition polymerizable by low dosage ionizing radiation adapted to coat flexible substrates, which exclusive of pigments, initiators and other non-reactive components, consists essentially of an oligomer/monomer mixture of: (A) between about 90 and about 10 weight percent oligomer having the formula: ##STR14## wherein R' is hydrogen or methyl; and Y is a divalent urethane residue; and said oligomer has between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said oligomer; and (B) between about 10 and about 90 weight percent vinyl monomers polymerizable with said oligomer upon exposure to radiation, said vinyl monomers consisting essentially of (i) acrylic ester monomers and (ii) N-vinyl-2-pyrrolidone, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B), and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR15## where R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR16## wherein R=H or methyl.
Claim 21
Dependent Claim
29 words
A 100% solids coating composition according to claim 18, wherein said R 1 or R 2 of said benzotriazole is an alkyl group of C 3 -C 9 .
Claim 22
Dependent Claim
20 words
A 100% solids coating composition according to claims 18 or 19, wherein said R of said hindered amine is hydrogen.
Claim 23
Dependent Claim
17 words
A 100% solids coating composition according to claim 18, wherein said benzotriazole is a mixture of benzotriazoles.
Claim 24
Dependent Claim
21 words
A 100% solids coating composition according to claims 18 or 21, wherein said hindered amine is a mixture of hindered amines.
Claim 25
Dependent Claim
36 words
A 100% solids coating composition according to claim 18, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine.
Claim 26
Dependent Claim
36 words
A 100% solids coating composition according to claim 18, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene.
Claim 27
Dependent Claim
35 words
A 100% solids coating composition according to claim 24, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B).
Claim 28
Dependent Claim
17 words
A 100% solids coating composition according to claim 24, wherein said R' of said oligomer is hydrogen.
Claim 29
Dependent Claim
25 words
A 100% solids coating composition according to claim 24 or 16, wherein said oligomer has a molecular weight of between about 400 and about 5000.
Claim 30
Dependent Claim
24 words
A 100% solids coating composition according to claim 24, wherein said acrylic ester monomers comprise at least 70 weight percent monovinyl acrylic ester monomers.
Claim 31
Dependent Claim
24 words
A 100% solids coating composition according to claim 28, wherein said acrylic ester monomers comprise greater than 80 weight percent monovinyl acrylic ester monomers.
Claim 32
Dependent Claim
36 words
A 100% solids coating composition according to claim 28, wherein said monovinyl acrylic ester monomers are selected from the group consisting essentially of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate and mixtures thereof.
Claim 33
Dependent Claim
40 words
A 100% solids coating composition according to claim 24 or 30, wherein said acrylic ester monomers, other than said monovinyl acrylic ester monomers, are selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate and mixtures thereof.
Claim 34
Independent Claim
267 words
A method for coating a substrate, the coating composition polymerizable by low dosage ionizing radiation, which comprises: (A) applying a first coating composition comprising up to about 60 weight percent pigment to the surface of a prepared substrate; (B) curing said first coating composition by exposure to an electron beam until an adherent dry coating is formed; (C) applying a second coating composition comprising 0-10 weight percent pigment to the coated surface of said substrate; and (D) curing said second coating composition by exposure to an electron beam until an adherent dry coating is formed; wherein said first coating composition and said second coating composition comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers comprising N-vinyl-2-pyrrolidone which is included in said composition in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR17## where R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR18## wherein R=H or methyl.
Claim 35
Independent Claim
267 words
A method for coating a substrate, the coating composition polymerizable by low dosage ionizing radiation, which comprises: (A) applying a first coating composition comprising up to about 60 weight percent pigment to the surface of a prepared substrate; (B) curing said first coating composition by exposure to an electron beam until an adherent dry coating is formed; (C) applying a second coating composition comprising 0-10 weight percent pigment to the coated surface of said substrate; and (D) curing said second coating composition by exposure to an electron beam until an adherent dry coating is formed; wherein said first coating composition and said second coating composition comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers comprising N-vinyl-2-pyrrolidone which is included in said composition in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR17## where R 1 or R 2 =H or an alkyl group of C 1 -C 25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR18## wherein R=H or methyl.
Claim 36
Dependent Claim
30 words
A method for coating a substrate according to claim 32, wherein said R 1 or R 2 of said benzotriazole is an alkyl group of C 3 -C 9 .
Claim 37
Dependent Claim
21 words
A method for coating a substrate according to claim 32 or 33, wherein said R of said hindered amine is hydrogen.
Claim 38
Dependent Claim
18 words
A method for coating a substrate according to claim 32, wherein said benzotriazole is a mixture of benzotriazoles.
Claim 39
Dependent Claim
22 words
A method for coating a substrate according to claim 32 or 35, wherein said hindered amine is a mixture of hindered amines.
Claim 40
Dependent Claim
37 words
A method for coating a substrate according to claim 32, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine.
Claim 41
Dependent Claim
34 words
A coating composition according to claim 32, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene.
Claim 42
Dependent Claim
35 words
A method for coating a substrate according to claim 32, wherein said resin comprises a urethane acrylic oligomer having the formula: ##STR19## wherein R' is hydrogen or methyl and Y is a divalent urethane residue.
Claim 43
Dependent Claim
38 words
A method for coating a substrate according to claim 32 or 39, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B).
Claim 44
Dependent Claim
18 words
A method for coating a substrate according to claim 39, wherein said R' of said oligomer is hydrogen.
Claim 45
Dependent Claim
24 words
A method for coating a substrate according to claim 39, wherein said oligomer has a molecular weight of between about 400 and about 10,000.
Claim 46
Dependent Claim
24 words
A method for coating a substrate according to claim 39, wherein said vinyl monomers other than said N-vinyl-2-pyrrolidone consist essentially of acrylic ester monomers.
Claim 47
Dependent Claim
26 words
A method for coating a substrate according to claim 43, wherein said acrylic ester monomers comprise at least 70 weight percent of a monovinyl acrylic ester.
Claim 48
Dependent Claim
40 words
A method for coating a substrate according to claim 44, wherein said monovinyl acrylic ester monomers are selected from the group consisting of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate, ethoxyethyl methacrylate, glycidyl methacrylate and mixtures thereof.
Claim 49
Dependent Claim
39 words
A method for coating a substrate according to claim 45, wherein said acrylic ester monomers other than said monovinyl acrylic ester monomers, are selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate and mixtures thereof.
Claim 50
Dependent Claim
18 words
A method for coating a substrate according to claim 32, wherein said substrate is comprised of polyvinyl chloride.
Claim 51
Dependent Claim
18 words
A method for coating a substrate according to claim 45, wherein said substrate is flexible polyvinyl chloride fabric.
Claim 52
Dependent Claim
23 words
A method for coating a substrate according to claim 47, wherein said first coating composition and said second coating composition are 100% solids.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-07-11 | 1987-01-10 | 1987-07-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-07-11 | 1991-01-10 | 1991-07-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-07-11 | 1995-01-10 | 1995-07-12 | $7700.00 | Window Closed / Lapsed |