Patent US4233362A successfully refreshed from Google Patents.
US4233362A
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Water-soluble air-oxidizing acrylic coatings
Assignee: Rohm and Haas Co
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Filing: 1978-12-18
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Granted: 1980-11-11
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Expires: 1998-12-18
Abstract
Abstract The specification discloses a polymer and the method of using the same to prepare articles of manufacture, the composition comprising a water-soluble salt of a polymer containing pendant groups derived from an unsaturated drying oil fatty acid hydroxyamide, carboxy groups, carboxy ester groups and optionally the residues of other unsaturated addition polymerizable monomers, the carboxy units being present in a critical amount and the polymer having a critical glass transition temperature, molecular weight and the like. Aqueous coating compositions are disclosed in which the soluble polymer is either the sole polymeric vehicle or is combined with a water-insoluble polymer latex.
Inventors
- 👤 Ronald W. Novak
- 👤 Benjamin B. Kine
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 06:34
CPC Classifications
B; B05; B05D; B05D7/00; B05D7/24; B05D7/26; C; C08; C08F; C08F220/00; C08F220/02; C08F220/10; C08F220/12; C09; C09D; C09D133/00; C09D133/04; C09D133/06; C09D133/062; C09D133/14; Y; Y10; Y10T; Y10T428/00; Y10T428/26; Y10T428/31504; Y10T428/31551; Y10T428/31645; Y10T428/31649; Y10T428/31652; Y10T428/31678; Y10T428/31692; Y10T428/31699; Y10T428/31855; Y10T428/3188
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
508 words
In a method of coating an article with a paint containing an aqueous alkaline solution of an addition polymer solubilized in said solution by a volatile amine or ammonia, said solubilized polymer having the structure: ##STR11## wherein R 1 is H, a lower alkyl radical having one to five carbon atoms, halogen, --CN, or --CH 2 COOR, --COOR, or --CH 2 COOH, R being a lower alkyl radical having from one to eight carbon atoms; R 2 is (CR 7 2 ) n wherein R 7 is --H or --CH 3 and n is 1 or 2; R 3 is H, or a lower alkyl radical having from one to 8 carbon atoms; R 4 is an unsaturated, air-curable alkyl radical; R 5 is H, --COOH, --CONH 2 , or --COOR, wherein R is as above; R 6 is H, or an aliphatic or cycloaliphatic radical having from one to 20 carbon atoms; and X is optional and when present is derived from at least one vinyl monomer different than the residues depicted; the units in brackets being in any order, portions of the R 6 radicals being as hereinafter defined in units of the formula: ##STR12## R 6 being H in a sufficient number of units of Formula II to provide the polymer with a carboxy content of 0.5-6 meq/g. of polymer, the quantity of carboxy groups being sufficient, when in the form of salt groups with said amine or ammonia, to confer water solubility upon the polymer, the amount of carboxy-containing units of Formula II wherein R 6 is H being between 5 and 40 parts by weight of the total polymer; optionally a portion of the radical R 6 in the units of Formula II being at least one aliphatic or cycloaliphatic radical and being selected so that the units are derived from at least one ester which when homopolymerized gives a high molecular weight polymer having a T g of between -80° C. and 120° C., said ester units forming up to 90 parts by weight of the polymer; the polymer having between about 5 and 60 parts by weight of units of the formula: ##STR13## wherein R 1 , R 2 , R 3 , R 4 , and R 5 are as identified above, any balance of the polymer being the units of --X-- of addition polymerized ethylenically unsaturated monomers other than said units of Formulas II and V, the total parts of all said units being 100, the Mv of the polymer being between about 5,000 and 200,000, the T g of a cured film of the polymer being between about -20° C. and 80° C., the Tukon Hardness of the cured film being between about 0.2 and about 15, in which the composition optionally includes a metal compound drier in an amount up to 0.5%, on a metal basis, of the total polymer weight in the composition, applying a thin uniform coating of the aqueous solution to a substrate, and drying and curing said coating in the presence of air.
Claim 2
Dependent Claim
508 words
In a method of coating an article with a paint containing an aqueous alkaline solution of an addition polymer solubilized in said solution by a volatile amine or ammonia, said solubilized polymer having the structure: ##STR11## wherein R 1 is H, a lower alkyl radical having one to five carbon atoms, halogen, --CN, or --CH 2 COOR, --COOR, or --CH 2 COOH, R being a lower alkyl radical having from one to eight carbon atoms; R 2 is (CR 7 2 ) n wherein R 7 is --H or --CH 3 and n is 1 or 2; R 3 is H, or a lower alkyl radical having from one to 8 carbon atoms; R 4 is an unsaturated, air-curable alkyl radical; R 5 is H, --COOH, --CONH 2 , or --COOR, wherein R is as above; R 6 is H, or an aliphatic or cycloaliphatic radical having from one to 20 carbon atoms; and X is optional and when present is derived from at least one vinyl monomer different than the residues depicted; the units in brackets being in any order, portions of the R 6 radicals being as hereinafter defined in units of the formula: ##STR12## R 6 being H in a sufficient number of units of Formula II to provide the polymer with a carboxy content of 0.5-6 meq/g. of polymer, the quantity of carboxy groups being sufficient, when in the form of salt groups with said amine or ammonia, to confer water solubility upon the polymer, the amount of carboxy-containing units of Formula II wherein R 6 is H being between 5 and 40 parts by weight of the total polymer; optionally a portion of the radical R 6 in the units of Formula II being at least one aliphatic or cycloaliphatic radical and being selected so that the units are derived from at least one ester which when homopolymerized gives a high molecular weight polymer having a T g of between -80° C. and 120° C., said ester units forming up to 90 parts by weight of the polymer; the polymer having between about 5 and 60 parts by weight of units of the formula: ##STR13## wherein R 1 , R 2 , R 3 , R 4 , and R 5 are as identified above, any balance of the polymer being the units of --X-- of addition polymerized ethylenically unsaturated monomers other than said units of Formulas II and V, the total parts of all said units being 100, the Mv of the polymer being between about 5,000 and 200,000, the T g of a cured film of the polymer being between about -20° C. and 80° C., the Tukon Hardness of the cured film being between about 0.2 and about 15, in which the composition optionally includes a metal compound drier in an amount up to 0.5%, on a metal basis, of the total polymer weight in the composition, applying a thin uniform coating of the aqueous solution to a substrate, and drying and curing said coating in the presence of air.
Claim 3
Dependent Claim
159 words
The method of claim 1 in which the polymer composition contains units of: (a) 0-50 parts by weight of a monomer selected from esters of acrylic acid or methacrylic acid, which when homopolymerized gives a polymer having a T g of between about 0° C. and -80° C. (b) 20-70 parts by weight of a monomer selected from esters of acrylic acid or methacrylic acid, vinyl aromatic hydrocarbons and unsaturated nitriles which when homopolymerized gives a polymer having a T g between about 20° C. and 120° C., (c) 5-30 parts of an ethylenically unsaturated carboxylic acid, optionally with up to 30 parts of a different ethylenically unsaturated monomer which confers hydrophilicity to the polymer and enhances its solubility in aqueous liquids, the quantity of ethylenically unsaturated acid being between about 0.6 and 4.5 meq/g. of polymer, and (d) 10-50 parts by weight of units of Formula V, and the total of (a), (b), (c), and (d) being 100.
Claim 4
Dependent Claim
128 words
The method of claim 2 in which the polymer composition contains mer units wherein: (a) is at least 10 parts and is selected from one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate, and isopropyl acrylate, (b) is selected from one or more of methyl methacrylate, styrene, ethyl methacrylate, acrylonitrile, butyl methacrylate, isobutyl methacrylate, and vinyl toluene, (c) is selected from one or more of acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and is present in an amount of from 8 to 15 parts, with 0-20 parts of one or more of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, and (d) is present in the amount of between about 20 and 50 parts, the polymer consisting essentially of (a), (b), (c), and (d).
Claim 5
Dependent Claim
93 words
The method of claim 3 in which the units of Formula V are such that n is 2, R 3 is --H, --CH 3 , or CH 3 CH 2 --, and R 4 is the residue of one or more of the drying oil acids selected from tung oil acids, linseed oil acids, dehydrated castor oil acids, safflower and conjugated safflower oil acids, soybean oil acids, and oiticica oil acids, the Mv is between about 20,000 and 80,000 and the thickness of the cured coating being between about 0.1 and 10 mils.
Claim 6
Dependent Claim
73 words
The method of claim 4 in which a blend of said drying oil acids is utilized which contains 50-90% by weight of dehydrated castor, safflower, conjugated safflower, or soybean oil acids, or a mixture thereof, with 10-50% by weight of tung oil acids, the T g of a cured film of the polymer being less than about 60° C., and the calculated T g of the backbone polymer being below about 50° C.
Claim 7
Dependent Claim
92 words
The method of claim 1 in which the polymer contains units consisting essentially of: (ab) 45-90 parts by weight of butyl methacrylate (c) 5-20 parts of an ethylenically unsaturated carboxylic acid, the quantity of ethylenically unsaturated acid being between about 0.6 and 4.5 meq/g. of polymer, optionally with up to 20 parts of a different ethylenically unsaturated monomer which confers hydrophilicity to the polymer and enhances its solubility in aqueous liquids, and (d) 10-50 parts by weight of units of Formula V, and the total of (ab), (c), and (d) being 100.
Claim 8
Dependent Claim
33 words
The method of claim 6 in which (c) is selected from one or more of acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and the Mv is between about 10,000 and 200,000.
Claim 9
Dependent Claim
94 words
The method of claim 7 in which the units of Formula V are such that n is 2, R 3 is --H, --CH 2 CH 3 , or --CH 3 , and R 4 is the residue of one or more of the drying oil acids selected from tung oil acids, linseed oil acids, dehydrated castor oil acids, safflower and conjugated safflower oil acids, soybean oil acids, and oiticica oil acids, the Mv is between about 20,000 and about 80,000 and the thickness of the cured coating is between about 0.1 and 10 mils.
Claim 10
Dependent Claim
43 words
The method of claim 8 in which a blend of said drying oil acids is utilized which contains 50-90% by weight of dehydrated castor oil acids, safflower or conjugated safflower acids, or a mixture thereof, with 10-50% by weight of tung oil acids.
Claim 11
Dependent Claim
48 words
An article of manufacture prepared by the method of claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, in which the cured coating is from 0.1 mil to 10 mils in thickness, the Tukon hardness of the cured film being between about 0.2 and about 15.
Claim 12
Dependent Claim
35 words
The method of claim 1 in which the soluble polymer is blended with an insoluble latex polymer, the proportions being 1-70% of the soluble polymer to 30-99% of the latex polymer on a solids basis.
Claim 13
Dependent Claim
23 words
The method of claim 11 in which 1-25% of the soluble polymer acid 75-99% of the latex polymer is present in the blend.
Claim 14
Dependent Claim
23 words
The method of claim 11 in which 1-15% of the soluble polymer and 85-99% of the latex polymer is present in the blend.
Claim 15
Dependent Claim
11 words
An article of manufacture prepared by the method of claim 11.
Claim 16
Dependent Claim
293 words
A polymer composition consisting essentially of the following mer units in the amount of (a) 0-50 parts by weight of one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate, and isopropyl acrylate, (b) 20-70 parts by weight of one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, isopropyl methacrylate, acrylonitrile, isobutyl methacrylate, styrene, and vinyl toluene, (c) 5-20 parts by weight of one or more of acrylic acid, methacrylic acid, maleic acid, and itaconic acid, with 0-20 parts by weight of one or more of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, (d) 10-50 parts by weight of units of the formula: ##STR14## wherein R 1 is H, a lower alkyl radical having one to five carbon atoms, halogen, --CN, or --CH 2 COOR, --COOR, or --CH 2 COOH, R being a lower alkyl radical having from one to eight carbon atoms; R 3 is H, or a lower alkyl radical having from one to eight carbon atoms; R 4 is an unsaturated, air curable alkyl radical; the total of (a), (b), (c), and (d) being 100, the quantity of (c) being 0.5 to 6 meq/g. of polymer and being sufficient, when in the form of salt groups with a volatile amine or ammonia, to confer water solubility upon the polymer, the Mv of the polymer being between about 5,000 and 200,000, the polymer being oxidatively curable by air, the residue ##STR15## being a drying oil acid residue derived from one or more of tung oil acids, linseed oil acids, dehydrated castor oil acids, safflower oil acids, conjugated safflower oil acids, soybean oil acids, and oiticica oil acids, the T g of a cured film of the polymer being between about 10° and 65° C.
Claim 17
Dependent Claim
293 words
A polymer composition consisting essentially of the following mer units in the amount of (a) 0-50 parts by weight of one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate, and isopropyl acrylate, (b) 20-70 parts by weight of one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, isopropyl methacrylate, acrylonitrile, isobutyl methacrylate, styrene, and vinyl toluene, (c) 5-20 parts by weight of one or more of acrylic acid, methacrylic acid, maleic acid, and itaconic acid, with 0-20 parts by weight of one or more of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, (d) 10-50 parts by weight of units of the formula: ##STR14## wherein R 1 is H, a lower alkyl radical having one to five carbon atoms, halogen, --CN, or --CH 2 COOR, --COOR, or --CH 2 COOH, R being a lower alkyl radical having from one to eight carbon atoms; R 3 is H, or a lower alkyl radical having from one to eight carbon atoms; R 4 is an unsaturated, air curable alkyl radical; the total of (a), (b), (c), and (d) being 100, the quantity of (c) being 0.5 to 6 meq/g. of polymer and being sufficient, when in the form of salt groups with a volatile amine or ammonia, to confer water solubility upon the polymer, the Mv of the polymer being between about 5,000 and 200,000, the polymer being oxidatively curable by air, the residue ##STR15## being a drying oil acid residue derived from one or more of tung oil acids, linseed oil acids, dehydrated castor oil acids, safflower oil acids, conjugated safflower oil acids, soybean oil acids, and oiticica oil acids, the T g of a cured film of the polymer being between about 10° and 65° C.
Claim 18
Dependent Claim
46 words
The polymer of claim 15 in which said residue ##STR16## is derived from a blend of 50-90% by weight of one or more of dehydrated castor oil acids, safflower oil acids, conjugated safflower oil, or soybean oil acids, with 10-50% by weight of tung oil acids.
Claim 19
Dependent Claim
43 words
The polymer composition of claim 15 in alkaline aqueous solution blended with a polymer latex which is insoluble in said aqueous solution, the proportions of soluble polymer to latex being 1-70% of soluble polymer to 30-99% of latex polymer on a solids basis.
Claim 20
Dependent Claim
23 words
The composition of claim 17 in which 1-25% of the soluble polymer acid 75-99% of the latex polymer is present in the blend.
Claim 21
Dependent Claim
23 words
The composition of claim 17 in which 1-15% of the soluble polymer and 85-99% of the latex polymer is present in the blend.
Claim 22
Dependent Claim
20 words
A method of coating a substrate comprising applying the composition of claim 17 to a substrate and curing the same.
Claim 23
Dependent Claim
9 words
An article prepared by the method of claim 20.
Claim 24
Dependent Claim
49 words
The polymer of claim 16 in the form of an alkaline aqueous solution combined with a latex the polymer of which is insoluble in said solution, the proportions of soluble polymer to latex polymer on a solids basis being from 1-70% of soluble polymer to 30-99% of latex polymer.
Claim 25
Dependent Claim
23 words
The blend of claim 22 in which 1-25% of the soluble polymer and 75-99% of the latex polymer is present in the blend.
Claim 26
Dependent Claim
23 words
The blend of claim 22 in which 1-15% of the soluble polymer and 85-99% of the latex polymer is present in the blend.
Claim 27
Dependent Claim
20 words
A method of coating a substrate comprising applying the composition of claim 22 to a substrate and curing the same.
Claim 28
Dependent Claim
9 words
An article prepared by the method of claim 25.
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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) | 1983-11-11 | 1984-05-12 | 1984-11-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-11-11 | 1988-05-12 | 1988-11-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-11-11 | 1992-05-12 | 1992-11-11 | $7700.00 | Window Closed / Lapsed |