US4855184A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Radiation-curable protective coating composition
Assignee: 3M Co
•
Filing: 1988-02-02
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Granted: 1989-08-08
•
Expires: 2008-02-02
Abstract
Abstract Normally solid, organic solvent-soluble, thermoplastic, polyethylenically-unsaturated, cellulosic polyurethane polymers are provided. These cellulosic polyurethane polymers comprise one or more cellulose ether or ester segments, one or more alkylene moieties having at least two carbon atoms and which can be substituted or interrupted by ether oxygen atoms, ester groups, or phenylene groups, two or more residues of diisocyanates, the segments, moieties, and residues being linked together by linking groups with the proviso that said alkylene moieties contain sufficient ethylenic unsaturation that said polymer can be crosslinked to a solvent-insoluble state. The cellulosic polyurethane polymers can be obtained by the polymerization of a reaction mixture comprising (a) aliphatic or cycloaliphatic diol comprising sufficient ethylenically-unsaturated diol to permit crosslinking of the polymerization product to a solvent-insoluble state; (b) organic solvent-soluble cellulose ether or ester having residual unreacted cellulosic hydroxyl groups; and (c) organic diisocyanate. The reaction product may optionally also contain primary or secondary aliphatic or aromatic diamines or dithiols. Also provided are coating compositions and shaped articles and methods for preparing same.
Inventors
- 👤 Thomas P. Klun
- 👤 David D. Lu
- 👤 Aida F. Robbins
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 12:26
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/40; C08G18/64; C08G18/6484; C08G18/67; C08G18/6705; C08G18/675; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31591; Y10T428/31971; Y10T428/31975; Y10T428/31978
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
56 words
Normally solid, organic solvent-soluble, thermoplastic, polyethylenically-unsaturated, cellulosic polyurethane polymers comprising the polymerization product of a reaction mixture of (a) aliphatic or cycloaliphatic diol comprising sufficient ethylenically-unsaturated organic diol to permit crosslinking of the polymerization product to a solvent-insoluble state; (b) organic solvent-soluble cellulosic ether or ester having residual unreacted cellulosic hydroxyl groups; and (c) organic diisocyanate.
Claim 2
Dependent Claim
56 words
Normally solid, organic solvent-soluble, thermoplastic, polyethylenically-unsaturated, cellulosic polyurethane polymers comprising the polymerization product of a reaction mixture of (a) aliphatic or cycloaliphatic diol comprising sufficient ethylenically-unsaturated organic diol to permit crosslinking of the polymerization product to a solvent-insoluble state; (b) organic solvent-soluble cellulosic ether or ester having residual unreacted cellulosic hydroxyl groups; and (c) organic diisocyanate.
Claim 3
Dependent Claim
24 words
The cellulosic polyurethane polymers of claim 1 wherein said ethylenically-unsaturated diol comprises at least about 5 weight percent of said aliphatic or cycloaliphatic diol.
Claim 4
Dependent Claim
18 words
The cellulosic polyurethane polymers of claim 1 wherein said ethylenically-unsaturated diol has two primary or secondary hydroxyl groups.
Claim 5
Dependent Claim
16 words
The cellulosic polyurethane polymers of claim 1 wherein said ethylenically-unsaturated diol is a polyethylenically unsaturated diol.
Claim 6
Dependent Claim
36 words
The cellulosic polyurethane polymers of claim 1 wherein said diol is a monomeric diol having 2 to about 30 carbon atoms and which may contain up to about 14 ether oxygen atoms and amide nitrogen atoms.
Claim 7
Dependent Claim
22 words
The cellulosic polyurethane polymers of claim 1 wherein said diol is a polymeric diol having a molecular weight of up to 100,000.
Claim 8
Dependent Claim
17 words
The cellulosic polyurethane polymers of claim 1 wherein said diols are poly(oxyalkylene)diols, polyester diols, poly(caprolactone)diols, and poly(carbonate)diols.
Claim 9
Dependent Claim
22 words
The cellulosic polyurethane polymers of claim 1 wherein said ethylenically-unsaturated diols have an ethylenic unsaturation equivalent weight of less than about 1000.
Claim 10
Dependent Claim
20 words
The cellulosic polyurethane polymers of claim 1 wherein said aliphatic or cycloaliphatic diol further comprises long-chain aliphatic group modified diol.
Claim 11
Dependent Claim
36 words
The cellulosic polyurethane polymers of claim 9 wherein said long-chain aliphatic group-modified diols are the addition reaction products of a long-chain aliphatic carboxylic acid or alcohol having about 4 to 30 carbon atoms and a diepoxide.
Claim 12
Dependent Claim
84 words
The cellulosic polyurethane polymers of claim 9 wherein said long-chain aliphatic group-modified diols are the reaction product of an ethylenically-unsaturated acid and a modified epoxy resin which resin is the reaction product of an hydroxyl group-containing glycidyl ether resin and a fatty acid ester oil, the fatty acid portion of said oil having 4 to 30 carbon atoms or the reaction product of an hydroxyl group-containing glycidyl ether resin and a lower alkyl ester of a fatty acid having 4 to 30 carbon atoms.
Claim 13
Dependent Claim
51 words
The cellulosic polyurethane polymers of claim 9 wherein said long-chain aliphatic group-modified diols are the reaction product of an ethylenically-unsaturated organic acid and a modified epoxy resin which resin is the reaction product of a hydroxyl group-containing glycidyl ether resin and a long-chain aliphatic isocyanate having 4 to 30 carbon atoms.
Claim 14
Dependent Claim
30 words
The cellulosic polyurethane polymers of claim 1 wherein said diol is pentaerythritol diacrylate or the reaction product of the diglycidyl ether of Bisphenol A and acrylic acid or propionic acid.
Claim 15
Dependent Claim
30 words
The cellulosic polyurethane polymers of claim 9 wherein said long-chain aliphatic group modified diol is the reaction product of the diglycidyl ether of Bisphenol A, acrylic acid, and stearic acid.
Claim 16
Dependent Claim
172 words
The polyurethane of claim 1 wherein said cellulose ether or ester can be represented by the formula ##STR29## wherein each R 2 is independently selected from --H, --R 3 , ##STR30## wherein R 3 is (1) a saturated aliphatic group which may be branched or cyclic having 1 to 20 carbon atoms and up to 3 non-adjacent oxygen atoms, (2) an ethylenically-unsaturated organic group which may be branched or cyclic having 2 to 20 carbon atoms and which may be substituted with acryloyloxy and acrylamido groups, or an aryl group having 6 to 10 carbon atoms; R 4 is hydrogen or a methyl group; and 0.01 to 30 weight percent of the --OR 2 groups are hydroxyl, R 5 is an alkylene group having 2 to 12 carbon atoms, and R i is a diisocyanate residue; and p is a number having a value from about 5 to 250; said cellulose ether or ester has a viscosity of about 0.01 to 60 and contains 0.01 to 30 weight percent unreacted hydroxyl units.
Claim 17
Dependent Claim
42 words
The cellulosic polyurethane polymers of claim 1 wherein said cellulose ester is the reaction product of a cellulose with at least one saturated or unsaturated organic acid halide, saturated or unsaturated organic acid anhydride, saturated or unsaturated organic isocyanate, or inorganic acid.
Claim 18
Dependent Claim
22 words
The cellulosic polyurethane polymers of claim 1 wherein said cellulose ester is the reaction product of cellulose and an ethylenically unsaturated azlactone.
Claim 19
Dependent Claim
31 words
The cellulosic polyurethane polymers of claim 1 wherein said cellulose ether is the reaction product of a cellulose with at least one haloalkane, haloalkylarene, haloalkoxyalkane, haloalkyl acylate, alkylene oxide, or N-methylolacrylamide.
Claim 20
Dependent Claim
23 words
The cellulosic polyurethane polymers of claim 1 wherein said cellulose ether is cellulose acetate propionate, cellulose acetate butyrate, or an ethyl ether-substituted cellulose.
Claim 21
Dependent Claim
23 words
The cellulosic polyurethane polymers of claim 1 wherein said organic diisocyanate is selected from linear, branched, and cyclic aliphatic, aromatic, and heterocyclic diisocyanates.
Claim 22
Dependent Claim
14 words
The cellulosic polyurethane polymers of claim 1 wherein said organic diisocyanate is isophorone diisocyanate.
Claim 23
Dependent Claim
25 words
The cellulosic polyurethane polymers of claim 1 wherein said reaction product further comprises primary or secondary aliphatic or aromatic diamine or aliphatic or cycloaliphatic dithiol.
Claim 24
Dependent Claim
81 words
The cellulosic polyurethane polymers of claim 1 wherein said aliphatic or cycloaliphatic diol is present in an amount of about 30 to 90 weight percent of which about 5 to 100 weight percent is ethylenically-unsaturated diol, said cellulose ether or ester is present in an amount of about 5 to 33 weight percent, and said organic diisocyanate is present in an amount that provides about 0.5 to 1.2 isocyanate equivalents per total equivalent weight of hydroxy groups present in said diol.
Claim 25
Dependent Claim
81 words
The cellulosic polyurethane polymers of claim 1 wherein said aliphatic or cycloaliphatic diol is present in an amount of about 30 to 60 weight percent of which about 5 to 100 weight percent is ethylenically-unsaturated diol, said cellulose ether or ester is present in an amount of about 9 to 30 weight percent, and said organic diisocyanate is present in an amount that provides about 0.8 to 1 isocyanate equivalents per total equivalent weight of hydroxy groups present in said diol.
Claim 26
Dependent Claim
85 words
The cellulosic polyurethane polymers of claim 9 wherein said ethylenically-unsaturated diol is present in an amount of about 30 to 50 weight percent, said long-chain aliphatic group-modified diol is present in an amount of about 9 to 30 weight percent, said cellulose ether or ester is present in an amount of about 8 to 25 weight percent, and said organic diisocyanate is present in an amount that provides about 0.8 to 1 isocyanate equivalents per total equivalent weight of hydroxy groups present in said diol.
Claim 27
Dependent Claim
60 words
The cellulosic polyurethane polymers of claim 25 wherein said ethylenically-unsaturated diol is the reaction product of the diglycidyl ether of Bisphenol A and acrylic acid, the long-chain aliphatic group-modified diol is the reaction product of the diglycidyl ether of Bisphenol A, acrylic acid and stearic acid, the cellulosic ester is cellulose acetate butyrate, and the organic diisocyanate is isophorone diisocyanate.
Claim 28
Dependent Claim
42 words
The cellulosic polyurethane polymers of claim 1 wherein said ethylenically-unsaturated diol is a mixture that is the reaction product of diglycidylether of Bisphenol A, acrylic acid, stearic acid; the cellulosic ester is cellulose acetate butyrate; and the organic diisocyanate is isophorone diisocyanate.
Claim 29
Dependent Claim
84 words
A normally solid, organic solvent-soluble, thermoplastic, polyethylenically-unsaturated, cellulosic polyurethane polymer comprising one or more cellulose ether or ester segments, R c , one or more alkylene moieties, R d , having at least two carbon atoms and which can be substituted, or interrupted by ether oxygen atoms, ester groups, and phenylene groups, and two or more residues of diisocyanates, R i , with the proviso that said alkylene moieties contain sufficient ethylenic unsaturation that said polymer can be crosslinked to a solvent insoluble state.
Claim 30
Dependent Claim
84 words
A normally solid, organic solvent-soluble, thermoplastic, polyethylenically-unsaturated, cellulosic polyurethane polymer comprising one or more cellulose ether or ester segments, R c , one or more alkylene moieties, R d , having at least two carbon atoms and which can be substituted, or interrupted by ether oxygen atoms, ester groups, and phenylene groups, and two or more residues of diisocyanates, R i , with the proviso that said alkylene moieties contain sufficient ethylenic unsaturation that said polymer can be crosslinked to a solvent insoluble state.
Claim 31
Dependent Claim
261 words
The cellulosic polyurethane polymers of claim 28, said polymers comprising one or a pluality of units represented by formula I: ##STR31## wherein each R c is independently a cellulose ether or ester residue of an organic solvent-soluble cellulose ether or ester, said residue containing an amount of unreacted hydroxyl groups equal to about 0.01 to 30 weight percent, minus an amount of hydroxyl groups equal to n; each R i is independently the residue of an organic diisocyanate devoid its two isocyanate groups; and n is a number having a value of at least 1; and one or a plurality of units represented by formula II: ##STR32## wherein R i is defined as above and each R d is independently the hydroxyl-free, amino-free, or thiol-free residue of an aliphatic or cycloaliphatic diol having a molecular weight of from 62 to 100,000 or more, aliphatic, cycloaliphatic, or aromatic diamine having a molecular weight of from 60 to 100,000 or more, or aliphatic or cycloaliphatic dithiol having a molecular weight of from 94 to 100,000, termed precursor diol, diamine, or dithiol, which residue is devoid two hydroxy groups, two amino groups, or two thiol groups, respectively, and which can be substituted, for example, with ethylenically-unsaturated groups, and/or hydrocarbyl groups having 4 to 30 carbon atoms, with the proviso that R d is derived from a sufficient amount of the ethylenically-unsaturated diol that the polymer can be crosslinked to an organic solvent-insoluble state; each X is independently --O--, --S--, or --NR-- wherein R is hydrogen or lower alkyl having 1 to 6 carbon atoms.
Claim 32
Dependent Claim
136 words
The cellulosic polyurethane polymers of claim 28 wherein said cellulose ether or ester segments contain units represented by the formula ##STR33## wherein each R 2 is independently selected from --H, --R 3 , ##STR34## --SO 2 R 4 , and --NO 2 , wherein R 3 is (1) a saturated aliphatic group which may be branched or cyclic having 1 to 20 carbon atoms and up to 3 non-adjacent oxygen atoms, (2) an ethylenically-unsaturated organic group which may be branched or cyclic having 2 to 20 carbon atoms and which may be substituted with acryloyloxy and acrylamido groups, or (3) an aryl group having 6 to 10 carbon atoms; R 4 is hydrogen or a methyl group; R 5 is an alkylene group having 2 to 12 carbon atoms, and R i is a diisocyanate residue.
Claim 33
Dependent Claim
12 words
The cellulosic polyurethane polymers of claim 28 wherein R i is ##STR35##
Claim 34
Dependent Claim
12 words
The cellulosic polyurethane polymers of claim 28 wherein R d is ##STR36##
Claim 35
Dependent Claim
17 words
A coating composition comprising an organic solvent solution of the thermoplastic, polyethylenically-unsaturated cellulosic polyurethane of claim 28.
Claim 36
Dependent Claim
9 words
The coating composition of claim 33 further comprising nitrocellulose.
Claim 37
Dependent Claim
20 words
A coated article comprising a substrate having a coating thereon, said coating comprising the cellulosic polyurethane polymer of claim 28.
Claim 38
Dependent Claim
11 words
The coated article of claim 35 wherein said coating is crosslinked.
Claim 39
Dependent Claim
11 words
The coated article of claim 35 wherein said substrate is wood.
Claim 40
Dependent Claim
33 words
A method for providing a substrate with a coating comprising applying to said substrate an organic solvent solution of the cellulosic polyurethane polymer of claim 28 and allowing said organic solvent to evaporate.
Claim 41
Dependent Claim
16 words
The method of claim 38 further comprising working said coating after evaporation of said organic solvent.
Claim 42
Dependent Claim
18 words
The method of claim 39 wherein said working comprises sanding, polishing, buffing, and solvent removal of said coating.
Claim 43
Dependent Claim
19 words
The method of claim 38 further comprising effecting crosslinking of said polyurethane polymer after evaporation of said organic solvent.
Claim 44
Dependent Claim
11 words
A shaped article comprising the cellulosic polyurethane polymer of claim 28.
Claim 45
Dependent Claim
18 words
A method for preparing a shaped article comprising molding or extruding the cellulosic polyurethane polymer of claim 28.
Claim 46
Dependent Claim
11 words
The method of claim 43 further comprising working said shaped article.
Claim 47
Dependent Claim
14 words
The method of claim 43 further comprising effecting crosslinking of said cellulosic polyurethane polymer.
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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) | 1992-08-07 | 1993-02-06 | 1993-08-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-08-07 | 1997-02-06 | 1997-08-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-08-07 | 2001-02-06 | 2001-08-08 | $7700.00 | Window Closed / Lapsed |