US4464524A
Expired / Lapsed
US
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Polymeric thickeners and coatings containing same
Assignee: Sherwin Williams Co
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Filing: 1983-07-26
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Granted: 1984-08-07
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Expires: 2003-07-26
Abstract
Abstract This invention relates to a latex thickener which consists essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR1## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR2## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms. The novel thickeners of this invention are especially useful in increasing the high shear viscosity of latex coating compositions, and especially coating compositions which contain polymeric vesiculated beads as part of the pigmentation.
Inventors
- 👤 Michael Karickhoff
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 04:36
CPC Classifications
C; C09; C09D; C09D11/00; C09D11/02; C09D11/03; C08; C08F; C08F220/00; C08F220/02; C08F220/04; C09D7/00; C09D7/40; C09D7/43; C08L; C08L25/00; C08L25/02; C08L25/04; C08L25/08; C08L33/00; C08L33/02; C08L33/04; C08L33/06; C08L33/10
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
150 words
A thickener consisting essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR10## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR11## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 2
Dependent Claim
150 words
A thickener consisting essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR10## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR11## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 3
Dependent Claim
14 words
The thickener of claim 1 further characterized in that the acid is methacrylic acid.
Claim 4
Dependent Claim
14 words
The thickener of claim 1 further characterized in that the anhydride is maleic anhydride.
Claim 5
Dependent Claim
16 words
The thickener of claim 1 further characterized in that the ethoxylated alcohol as the formula: ##STR12##
Claim 6
Dependent Claim
35 words
The thickener of claim 1 further characterized in that the mixture of esters is the condensation reaction product obtained by admixing at reaction temperatures about 1.0 mole of anhydride for each chemical equivalent of hydroxyl.
Claim 7
Dependent Claim
21 words
The thickener of claim 1 further characterized in that the mole ratio of ethoxylated alcohol to diol is at least 1.1/l.
Claim 8
Dependent Claim
22 words
The thickener of claim 1 further characterized in that the mole ratio of ethoxylated alcohol to diol is between 2/1 and 15/1.
Claim 9
Dependent Claim
41 words
The thickener of claim 1 further characterized in that the mixture of esters consists essentially of the condensation reaction product of maleic anhydride, an ethoxylated alcohol having the formula: ##STR13## and 1,6 hexane diol in a mole ratio of approximately 10/8/1.
Claim 10
Dependent Claim
194 words
A process for thickening an aqueous system comprising water and a natural or synthetic polymer, which process comprises adding a thickening amount of an in situ thickener to said aqueous system, and adjusting the system to a pH of at least about 6.0, wherein said thickener consists essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR14## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR15## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 11
Dependent Claim
194 words
A process for thickening an aqueous system comprising water and a natural or synthetic polymer, which process comprises adding a thickening amount of an in situ thickener to said aqueous system, and adjusting the system to a pH of at least about 6.0, wherein said thickener consists essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR14## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR15## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 12
Dependent Claim
14 words
The process of claim 9 further characterized in that the acid is methacrylic acid.
Claim 13
Dependent Claim
14 words
The process of claim 9 further characterized in that the anhydride is maleic anhydride.
Claim 14
Dependent Claim
16 words
The process of claim 9 further characterized in that the ethoxylated alcohol has the formula: ##STR16##
Claim 15
Dependent Claim
35 words
The process of claim 9 further characterized in that the mixture of esters in the condensation reaction product obtained by admixing at reaction temperatures about 1.0 mole of anhydride for each chemical equivalent of hydroxyl.
Claim 16
Dependent Claim
21 words
The process of claim 9 further characterized in that the mole ratio of ethoxylated alcohol to diol is at least 1.1/l.
Claim 17
Dependent Claim
22 words
The process of claim 9 further characterized in that the mole ratio of ethoxylated alcohol to diol is between 5/1 and 10/1.
Claim 18
Dependent Claim
41 words
The process of claim 9 further characterized in that the mixture of esters consists essentially of the condensation reaction product of maleic anhydride, an ethoxylated alcohol having the formula: ##STR17## and 1,6 hexane diol in a mole ratio of approximately 10/8/1.
Claim 19
Dependent Claim
20 words
The process of claim 9 wherein the pH is adjusted to a level of from about 6.0 to about 10.0.
Claim 20
Dependent Claim
166 words
A coating composition which comprises a natural or synthetic latex vehicle; and a thickening amount of a thickener consisting essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR18## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR19## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 21
Dependent Claim
166 words
A coating composition which comprises a natural or synthetic latex vehicle; and a thickening amount of a thickener consisting essentially of the free radical addition product obtained by the emulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR18## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing from 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR19## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 22
Dependent Claim
14 words
The coating of claim 18 further characterized in that the acid is methacrylic acid.
Claim 23
Dependent Claim
27 words
The coating of claim 18 further characterized in that the natural or synthetic vehicle is selected from the group consisting of acrylic latices and vinyl acrylic latices.
Claim 24
Dependent Claim
14 words
The coating of claim 18 further characterized in that the anhyride is maleic anhydride.
Claim 25
Dependent Claim
16 words
The coating of claim 18 further characterized in that the ethoxylated alcohol has the formula: ##STR20##
Claim 26
Dependent Claim
35 words
The coating of claim 18 further characterized in that the mixture of esters in the condensation reaction product obtained by admixing at reaction temperatures about 1.0 mole of anhydride for each chemical equivalent of hydroxyl.
Claim 27
Dependent Claim
21 words
The coating of claim 18 further characterized in that the mole ratio of ethoxylated alcohol to diol is at least 1.1/l.
Claim 28
Dependent Claim
22 words
The coating of claim 18 further characterized in that the mole ration of ethoxylated alcohol to diol is between 2/1 and 15/1.
Claim 29
Dependent Claim
41 words
The coating of claim 18 further characterized in that the mixture of esters consists essentially of the condensation reaction product of maleic anhydride, an ethoxylated alcohol having the formula: ##STR21## and 1,6 hexane diol in a mole ratio of approximately 10/8/1.
Claim 30
Dependent Claim
168 words
A coating composition which comprises a natural or synthetic latex vehicle; polymeric vesiculated beads; and a thickening amount of a thickener consisting essentially of the free radical addition product obtained by the amulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR22## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR23## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 31
Dependent Claim
168 words
A coating composition which comprises a natural or synthetic latex vehicle; polymeric vesiculated beads; and a thickening amount of a thickener consisting essentially of the free radical addition product obtained by the amulsion polymerization of: (a) 3-15 parts styrene; (b) 15-45 parts ethyl acrylate; (c) 30-60 parts of at least one acid having the formula: ##STR22## wherein R 1 and R 2 can be the same or different and are hydrogen or lower alkyl of 1 to about 3 carbons; and (d) 10-25 parts of a mixture of esters; wherein the mixture of esters is the condensation reaction product of reactive amounts of (i) an ethylenically unsaturated cyclic carboxylic acid anhydride containing 4 to about 8 carbon atoms; and (ii) an ethoxylated alcohol having the general formula: ##STR23## wherein R is from one to three aliphatic radicals of 1 to about 30 carbon atoms each and n is an integer from about 6 to 150; and (iii) a diol containing from about 2 to about 10 carbon atoms.
Claim 32
Dependent Claim
14 words
The coating of claim 27 further characterized in that the acid is methacrylic acid.
Claim 33
Dependent Claim
27 words
The coating of claim 27 further characterized in that the natural or synthetic vehicle is selected from the group consisting of acrylic latices and vinyl acrylic latices.
Claim 34
Dependent Claim
14 words
The coating of claim 27 further characterized in that the anhydride is maleic anhydride.
Claim 35
Dependent Claim
16 words
The coating of claim 27 further characterized in that the ethoxylated alcohol has the formula: ##STR24##
Claim 36
Dependent Claim
35 words
The coating of claim 27 further characterized in that the mixture of esters is the condensation reaction product obtained by admixing at reaction temperatures about 1.0 mole of anhydride for each chemical equivalent of hydroxyl.
Claim 37
Dependent Claim
21 words
The coating of claim 27 further characterized in that the mole ratio of ethoxylated alcohol to diol is at least 1.1/l.
Claim 38
Dependent Claim
22 words
The coating of claim 27 further characterized in that the mole ratio of ethoxylated alcohol to diol is between 5/1 and 10/1.
Claim 39
Dependent Claim
41 words
The coating of claim 27 further characterized in that the mixture of esters consists essentially of the condensation reaction product of maleic anhydride, an ethoxylated alcohol having the formula: ##STR25## and 1,6 hexane diol in a mole ratio of approximately 10/8/1.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-08-07 | 1988-02-06 | 1988-08-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-08-07 | 1992-02-06 | 1992-08-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-08-07 | 1996-02-06 | 1996-08-07 | $7700.00 | Window Closed / Lapsed |