US4829102A
Expired / Lapsed
US
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Polymeric opaque particles and process for making same
Assignee: Rohm and Haas Co
•
Filing: 1987-11-05
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Granted: 1989-05-09
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Expires: 2007-11-05
Abstract
Abstract Polymer opaque particles and a process for making same are disclosed. These particles comprise an emulsion polymerized core copolymer having, as one constituent thereof, between about 15% and about 40% by weight of a monomer having the general formula: ##STR1## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, amino nitrile, hydroxyl and halogen groups, and organic radicals such as substituted or unsubstituted alkyl, cycloalkyl or aryl groups, R 3 is selected from hydrogen or substituted or unsubstituted organic radicals such as alkyl, cycloalkyl or aryl groups and A is an organic or inorganic bridge connecting the illustrated atoms, the remainder being a mixture of selected olefinically unsaturated acid and ester monomers, said core particles, in turn being encapsulated with an emulsion polymerized sheath copolymer comprised of one or more nonionic olefinically unsaturated monomers to produce said opague particles. In the present invention, the core polymer resulting from the polymerization of the above-described monomer has a structure in which ##STR2## is a pendant functional group. The finished particles have an average diameter particle size ranging from about 70 to about 4500 nm. and are free of internal microvoids. The present invention further comprises compositions such as paints and paper coatings containing said particles.
Inventors
- 👤 John Biale
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 00:24
CPC Classifications
C; C08; C08F; C08F265/00; C08F265/10; C09; C09D; C09D151/00; C09D151/003; Y; Y10; Y10S; Y10S525/00; Y10S525/902
Claims Analysis
Total Claims: 159
Claim 1
Independent Claim
127 words
A process for making water-insoluble opacifying particles which are substantially free of microvoids, said process comprising sequentially polymerizing a monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR16## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 5 atoms long, and further includes as part of the bridge, a moiety of the form --NR 6 --, wherein R 6 is hydrogen or an organic radical, thus forming core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 2
Dependent Claim
127 words
A process for making water-insoluble opacifying particles which are substantially free of microvoids, said process comprising sequentially polymerizing a monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR16## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 5 atoms long, and further includes as part of the bridge, a moiety of the form --NR 6 --, wherein R 6 is hydrogen or an organic radical, thus forming core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 3
Dependent Claim
10 words
Opaque particles as made by the process of claim 1.
Claim 4
Dependent Claim
14 words
The process of claim 1 wherein said core particles are formed by emulsion polymerization.
Claim 5
Dependent Claim
10 words
Opaque particles as made by the process of claim 3.
Claim 6
Dependent Claim
128 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially copolymerizing a first monomer of the form: ##STR17## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, R 3 , R 5 and R 6 are independently selected from hydrogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, and X is an integer in the range of from 0 to about 10, with one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 7
Dependent Claim
128 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially copolymerizing a first monomer of the form: ##STR17## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, R 3 , R 5 and R 6 are independently selected from hydrogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, and X is an integer in the range of from 0 to about 10, with one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 8
Dependent Claim
46 words
The process of claim 5 wherein said core particles are emulsion copolymerized onto a multiplicity of seed particles having an average diametric particle size distribution in the range of from about 30 to about 100 nm to form a latex having an essentially unimodal particle distribution.
Claim 9
Dependent Claim
40 words
The process of claim 5 wherein R 1-7 , when organic radicals, have from 1 to about 10 carbon atoms, are free of olefinic and alkynyl linkages and, when they are cycloalkyl or aryl containing groups, have only 1 ring.
Claim 10
Dependent Claim
51 words
The process of claim 5 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 is hydrogen or an alkyl group having up to about 7 carbon atoms, R 4 and R 5 are hydrogen or methyl, and X ranges from 0 to about 4.
Claim 11
Dependent Claim
45 words
The process of claim 5 wherein said first monomer is selected from the class consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-propionic acid, acryloamido-2-hydroxybutanoic acid, methacrylamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the methyl esters of said acids and mixtures thereof, and methyl acryloamidoglycolate-methyl ether.
Claim 12
Dependent Claim
12 words
The process of claim 5 wherein said first monomer is acryloamidoglycolic acid.
Claim 13
Dependent Claim
13 words
The process of claim 5 wherein said first monomer is methyl acryloamidoglycolate-methyl ether.
Claim 14
Dependent Claim
28 words
The process of claim 5 wherein said first monomer is present in a concentration of between about 15% and about 40%, by weight, of said core monomer mixture.
Claim 15
Dependent Claim
107 words
The process of claim 5 wherein said other ethylenically unsaturated monomer is selected from the class consisting of (1) acids selected from acrylic acid, methacrylic acid, ethylacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloracrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) of nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 16
Dependent Claim
99 words
The process of claim 13 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid with the alkyl component of said ester having from 1 to about 20 carbon atoms, and mixtures thereof.
Claim 17
Dependent Claim
36 words
The process of claim 5 wherein said sheath polymer comprises a mixture of methyl methacrylate with up to about 10% of an alkyl acrylate with the alkyl portion thereof having up to about 8 carbon atoms.
Claim 18
Dependent Claim
22 words
The process of claim 15 wherein said alkyl acrylate is butyl acrylate in an amount ranging from about 4 to about 7%.
Claim 19
Dependent Claim
161 words
The process of claim 5 wherein said copolymerization is an emulsion copolymerization performed at a temperature of from between about 10° C. to about 100° C. in an aqueous medium, with a mixture comprising between about 15% and about 40% of one or more of said first monomers, with R 6 and R 7 both being hydrogen, the remainder comprising one or more of said other ethylenically unsaturated acidic or nonionic monomers, said mixture being copolymerized in the presence of a sufficient amount of seed particles having an average diametric particle size distribution in the range of about 30 to about 100 nm to form core copolymer particles having a molecular weight distribution of from about 20,000 to about 4 million and an essentially unimodal particle size distribution in the range of about 50 to about 1000 nm, and with the final core/sheath combination having an average diametric particle size distribution in the range of about 70 to about 4500 nm.
Claim 20
Dependent Claim
163 words
The process of claim 17 wherein said copolymerization temperature ranges from about 60° C. to about 90° C., said aqueous medium contains a free radical initiator, said monomeric mixture has between about 20% and about 30%, by weight of said first monomer with R 1 , R 2 , and R 3 being independently selected from hydrogen and substituted or unsubstituted alkyl or cycloalkyl containing radicals, with R 4 and R 5 being hydrogen or a methyl group, and X is an integer in the range of from 0 to 4, with said seed particles having an average diametric particle size distribution in the range of about 40 to about 70 nm, said molecular weight distribution being from about 500,000 to about 2 million, said unimodal particle size distribution being in the range of about 100 to about 500 nm, and with the final core/sheath combination having an average diametric particle size distribution in the range of about 150 to about 3500 nm.
Claim 21
Dependent Claim
36 words
The process of claim 18 wherein said sheath polymer comprises a mixture of methyl methacrylate with up to about 10% of an alkyl acrylate with the alkyl portion thereof having up to about 8 carbon atoms.
Claim 22
Dependent Claim
22 words
The process of claim 19 wherein said alkyl acrylate is butyl acrylate in an amount ranging from about 4 to about 7%.
Claim 23
Dependent Claim
10 words
Non-swellable opaque particles made by the process of claim 5.
Claim 24
Dependent Claim
29 words
The non-swellable opaque particles of claim 21 wherein said core particles are emulsion copolymerized and comprised of between about 15% and about 40% by weight, of said first monomer.
Claim 25
Dependent Claim
50 words
The opaque particles of claim 22 wherein said other ethylenically unsaturated acidic or non-acidic monomers have but one olefinic group, are free of alkynyl or --C═N-- linkages and no more than one other functionality selected from the group consisting of a carboxylate, sulfonate, phosphonate, amino, nitrile, epoxide or ketonic group.
Claim 26
Dependent Claim
34 words
The opaque particles of claim 23 wherein said other monomers either have no functional group or but one carboxylate group of the form: ##STR18## wherein R 8 is as defined for R 3 .
Claim 27
Dependent Claim
24 words
The opaque particles of claim 24 wherein R 8 is hydrogen or an unsubstituted alkyl group having no more than about 20 carbon atoms.
Claim 28
Dependent Claim
110 words
The opaque particles of claim 22 wherein said other ethylenically unsaturated acidic or nonionic monomer is selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 29
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 26 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 30
Dependent Claim
128 words
The non-swellable, water insoluble opacifying particles of claim 26 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid with the alkyl component of said esters having from 1 to about 20 carbon atoms, and mixtures thereof, in an amount sufficient to form composite core/sheath particles having an average diametric particle size in the range between about 200 to about 2000 nm.
Claim 31
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 28 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 32
Dependent Claim
22 words
The opaque particles of claim 21 wherein said first monomer is emulsion copolymerized with said other monomers to form said core particles.
Claim 33
Dependent Claim
41 words
The opaque particles of claim 30 wherein R 1-7 , when organic radicals, have from 1 to about 10 carbon atoms, are free of olefinic and alkynyl linkages and, when they are cycloalkyl or aryl containing groups, have only 1 ring.
Claim 34
Dependent Claim
65 words
The opaque particles of claim 31 wherein said core particles are copolymerized onto a multiplicity of seed particles having an average diametric particle size in the range between about 30 to about 100 nm to form core particles having an average molecular weight distribution between about 20,000 and about 4 million and an essentially unimodal particle size distribution between about 50 and about 1000 nm.
Claim 35
Dependent Claim
28 words
The opaque particles of claim 31 wherein said first monomer is present in a concentration between about 15% and about 40%, by weight of the core monomer mixture.
Claim 36
Dependent Claim
52 words
The opaque particles of claim 30 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 is hydrogen or an alkyl group having up to about 7 carbon atoms, R 4 and R 5 are hydrogen or methyl and X ranges from 0 to about 4.
Claim 37
Dependent Claim
46 words
The opaque particles of claim 30 wherein said first monomer is selected from the group consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-hydroxypropionic acid, acryloamido-2-hydroxybutanoic acid, methacryloamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the ethyl esters of said acids and mixtures thereof, and methyl acryloamidoglycolate-methyl ether.
Claim 38
Dependent Claim
110 words
The opaque particles of claim 35 wherein said other ethylenically unsaturated acidic or nonionic monomer is selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 39
Dependent Claim
100 words
The opaque particles of claim 36 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid with the alkyl component of said esters having from 1 to about 20 carbon atoms, and mixtures thereof.
Claim 40
Dependent Claim
40 words
The opaque particles of claim 37 wherein said other monomer comprises a mixture having between about 3 and about 5 parts, by weight, of methyl methacrylate and between about 10 parts and about 6 parts, by weight, of butyl acrylate.
Claim 41
Dependent Claim
37 words
The opaque particles of claim 38 wherein said sheath polymer comprises a mixture of methyl methacrylate with up to about 10% of an alkyl acrylate, with the alkyl portion thereof having up to about 8 carbon atoms.
Claim 42
Dependent Claim
26 words
The opaque particles of claim 39 wherein said alkyl acrylate is butyl acrylate in an an amount between about 4 and about 7 percent, by weight.
Claim 43
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 39 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 44
Dependent Claim
13 words
The paint composition of claim 41 wherein said first monomer is acryloamidoglycolic acid.
Claim 45
Dependent Claim
14 words
The paint composition of claim 41 wherein said first monomer is methyl acryloamidoglycolate-methyl ether.
Claim 46
Dependent Claim
50 words
The opaque particles of claim 21 wherein said other ethylenically unsaturated acidic or nonionic monomers have but one olefinic group, are free of alkynyl or --C═N-- linkages and no more than one other functionality selected from the group consisting of a carboxylate, sulfonate, phosphonate, amino, nitrile, epoxide or ketonic group.
Claim 47
Dependent Claim
33 words
The particles of claim 44 wherein said other monomers either have no functional group or but one carboxylate group of the form: ##STR19## wherein R 8 is as defined for R 3 .
Claim 48
Dependent Claim
23 words
The particles of claim 45 wherein R 8 is hydrogen or an unsubstituted alkyl group having no more than about 20 carbon atoms.
Claim 49
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 46 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 50
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 21 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 51
Dependent Claim
21 words
The process of claim 5 wherein said first monomer is emulsion copolymerized with said other monomers to form said core particles.
Claim 52
Dependent Claim
46 words
The process of claim 49 wherein said other ethylenically unsaturated monomers have but one olefinic group, are free of alkynyl or --C═N-- linkages and no more than one other functionality selected from the group consisting of a carboxylate, sulfonate, phosphonate, amino, nitrile, epoxide or ketonic group.
Claim 53
Dependent Claim
33 words
The process of claim 50 wherein said other monomers either have no functional group or but one carboxylate group of the form: ##STR20## wherein R 8 is as defined for R 3 .
Claim 54
Dependent Claim
23 words
The process of claim 51 wherein R 8 is hydrogen or an unsubstituted alkyl group having no more than about 20 carbon atoms.
Claim 55
Dependent Claim
237 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially emulsion copolymerizing, at a temperature of from about 60° C. to about 90° C., in the presence of between about 0.01% to about 2% of a water soluble, free radical initiator and between about 0.1 and about 0.5% of an emulsifier, a monomer composition having between 20 and 30% of acryloamidoglycolic acid, the remainder being a mixture comprised of methyl methacrylate and butyl acrylate which are present in a ratio of between 3 parts methyl methacrylate to 10 parts butyl acrylate and 5 parts methyl methacrylate to 6 parts butyl acrylate, the total core monomer mixture further comprising about 0.3% of a cross linkable polyethylenically unsaturated monomer, said copolymerization occurring in the presence of an amount of a seed polymer having an average diametric particle size distribution in the range of about 30 to about 50 nm to form core particles having a molecular weight distribution of between about 500,000 and 2 million and an essentially unimodal particle size distribution in the range of about 150 to about 400 nm, and encapsulating said core particles with an emulsion copolymerized mixture comprising between about 93% and 96% methyl methacrylate and about 7% to about 4% butyl acrylate in an amount sufficient to form composite core/sheath particles having an average diametric particle size distribution in the range of between about 200 to about 2000 nm.
Claim 56
Dependent Claim
237 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially emulsion copolymerizing, at a temperature of from about 60° C. to about 90° C., in the presence of between about 0.01% to about 2% of a water soluble, free radical initiator and between about 0.1 and about 0.5% of an emulsifier, a monomer composition having between 20 and 30% of acryloamidoglycolic acid, the remainder being a mixture comprised of methyl methacrylate and butyl acrylate which are present in a ratio of between 3 parts methyl methacrylate to 10 parts butyl acrylate and 5 parts methyl methacrylate to 6 parts butyl acrylate, the total core monomer mixture further comprising about 0.3% of a cross linkable polyethylenically unsaturated monomer, said copolymerization occurring in the presence of an amount of a seed polymer having an average diametric particle size distribution in the range of about 30 to about 50 nm to form core particles having a molecular weight distribution of between about 500,000 and 2 million and an essentially unimodal particle size distribution in the range of about 150 to about 400 nm, and encapsulating said core particles with an emulsion copolymerized mixture comprising between about 93% and 96% methyl methacrylate and about 7% to about 4% butyl acrylate in an amount sufficient to form composite core/sheath particles having an average diametric particle size distribution in the range of between about 200 to about 2000 nm.
Claim 57
Dependent Claim
10 words
Non-swellable opaque particles made by the process of claim 53.
Claim 58
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 54 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 59
Dependent Claim
144 words
A process for making non-swellable water insoluble opacifying particles comprising providing seed particles having an average diametric particle size in the range of about 30 to about 100 nm, copolymerizing onto said seed particles a core composition comprised of a mixture of an alpha-beta ethylenically unsaturated amide of the form: ##STR21## and a keto carboxylic acid or ester of the form: ##STR22## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are independently selected from hydrogen and organic radicals and Z is an organic radical or a covalent bond, with one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 60
Dependent Claim
144 words
A process for making non-swellable water insoluble opacifying particles comprising providing seed particles having an average diametric particle size in the range of about 30 to about 100 nm, copolymerizing onto said seed particles a core composition comprised of a mixture of an alpha-beta ethylenically unsaturated amide of the form: ##STR21## and a keto carboxylic acid or ester of the form: ##STR22## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are independently selected from hydrogen and organic radicals and Z is an organic radical or a covalent bond, with one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 61
Dependent Claim
10 words
Non-swellable opaque particles made by the process of claim 56.
Claim 62
Dependent Claim
47 words
The non-swellable opaque particles of claim 57 wherein said core composition is comprised of between about 15% and about 40% of a stoichiometric amount of said alpha-beta ethylenically unsaturated amide and said keto carboxylic acid or ester, the balance comprising one or more ethylenically unsaturated nonionic monomers.
Claim 63
Dependent Claim
36 words
A coating composition comprising a mixture of between about 5% and about 50%, by weight, of the opaque particles of claim 58 and a latex film forming composition comprising one or more pigments, binders and extenders.
Claim 64
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 57 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 65
Dependent Claim
27 words
The particles of claim 57 wherein each of said organic radicals is free of olefinic and alkynyl linkages and contains no more than about 20 carbon atoms.
Claim 66
Dependent Claim
33 words
The particles of claim 61 wherein said organic radicals are substituted or unsubstituted, straight or branched chained alkyl radicals having no more than about 10 carbon atoms, and Z is a covalent bond.
Claim 67
Dependent Claim
34 words
The particles of claim 57 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 and R 4 are hydrogen or methyl, and Z is a covalent bond.
Claim 68
Dependent Claim
132 words
The particles of claim 57 wherein said core composition comprises between about 20 and about 30 percent, by weight, of a stoichiometric mixture of acrylamide and glyoxylic acid, the remainder comprising one or more of said other monomers selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 69
Dependent Claim
98 words
The particles of claim 64 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride acrylonitrile, and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid with the alkyl component of said esters having from 1 to about 20 carbon atoms, and mixtures thereof.
Claim 70
Dependent Claim
53 words
The process of claim 56 wherein each of R 1-4 , R 6 and R 7 is hydrogen or is an organic radical free of olefinic and alkynyl linkages, each of said radicals containing no more than about 20 carbon atoms, and Z is an alkyl or cycloalkyl radical or a covalent bond.
Claim 71
Dependent Claim
27 words
The process of claim 66 wherein said organic radicals are substituted or unsubstituted, straight or branched chained alkyl radicals having no more than about 10 carbon atoms.
Claim 72
Dependent Claim
34 words
The process of claim 56 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 and R 4 are hydrogen or methyl, and Z is a covalent bond.
Claim 73
Dependent Claim
129 words
The process of claim 56 wherein said core composition comprises between about 20 and about 30 percent, by weight, of a stoichiometric mixture of acrylamide and glyoxylic acid, the remainder comprising one or more monomers selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 74
Dependent Claim
98 words
The process of claim 69 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, with the alkyl component of said esters having from 1 to about 20 carbon atoms, and mixtures thereof.
Claim 75
Dependent Claim
193 words
A process for making a water dispersion of insoluble opacifying particles substantially free of microvoids comprising providing a seed particle containing latex wherein said seed particles have an average diametric particle size distribution in the range of from about 30 to about 100 nm, emulsion copolymerizing onto said seed particles a core composition comprised of one or more first monomers of the form: ##STR23## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, R 3 , R 5 and R 6 are independently selected from hydrogen and substituted and unsubstituted alkyl, cycloalkyl and aryl containing radicals, and Y and Z are saturated or aryl containing radicals or covalent bonds, and one or more ethylenically unsaturated acidic or nonionic monomers to form core particles, and encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers to form said dispersion, with said encapsulated particles having an average diametric particle size distribution in the range of between about 70 and about 4500 nm.
Claim 76
Dependent Claim
193 words
A process for making a water dispersion of insoluble opacifying particles substantially free of microvoids comprising providing a seed particle containing latex wherein said seed particles have an average diametric particle size distribution in the range of from about 30 to about 100 nm, emulsion copolymerizing onto said seed particles a core composition comprised of one or more first monomers of the form: ##STR23## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and substituted or unsubstituted alkyl, cycloalkyl and aryl containing radicals, R 3 , R 5 and R 6 are independently selected from hydrogen and substituted and unsubstituted alkyl, cycloalkyl and aryl containing radicals, and Y and Z are saturated or aryl containing radicals or covalent bonds, and one or more ethylenically unsaturated acidic or nonionic monomers to form core particles, and encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers to form said dispersion, with said encapsulated particles having an average diametric particle size distribution in the range of between about 70 and about 4500 nm.
Claim 77
Dependent Claim
11 words
Non-swellable opaque particles as made by the process of claim 71.
Claim 78
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 72 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 79
Dependent Claim
199 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially copolymerizing a monomeric mixture comprising between about 15% and about 40%, by weight of a first ethylenically unsaturated monomer selected from the class consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-propionic acid, acryloamido-2-hydroxybutanoic acid, methacrylamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the methyl esters of said acids and mixtures thereof, and methylacryloamidoglycolate-methyl ether, the remaider comprising one or more other ethylenically unsaturated monomers selected from the class consisting of (1) acids selected from acrylic acid, methacrylic acid, ethylacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloracrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyll-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof to form core particles and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more of said ethylenically unsaturated nonionic polymerizable monomers.
Claim 80
Dependent Claim
199 words
A process for making water insoluble opacifying particles substantially free of microvoids comprising sequentially copolymerizing a monomeric mixture comprising between about 15% and about 40%, by weight of a first ethylenically unsaturated monomer selected from the class consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-propionic acid, acryloamido-2-hydroxybutanoic acid, methacrylamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the methyl esters of said acids and mixtures thereof, and methylacryloamidoglycolate-methyl ether, the remaider comprising one or more other ethylenically unsaturated monomers selected from the class consisting of (1) acids selected from acrylic acid, methacrylic acid, ethylacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloracrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyll-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof to form core particles and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more of said ethylenically unsaturated nonionic polymerizable monomers.
Claim 81
Dependent Claim
9 words
Opaque particles made by the process of claim 74.
Claim 82
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5% and about 50%, by weight, of the opacifying particles of claim 75 and a film forming latex comprised of one or more pigments, binders and extenders.
Claim 83
Dependent Claim
99 words
Opaque particles which are substantially free of microvoids, said particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR24## wherein R 3 is hydrogen or an organic radical, provided that when R 3 is an organic radical, it is free of olefinic and alkynyl linkages and contains no more than about 20 carbon atoms, R 6 is hydrogen or an organic radical, and D is an organic radical connecting the illustrated atoms, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 84
Dependent Claim
99 words
Opaque particles which are substantially free of microvoids, said particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR24## wherein R 3 is hydrogen or an organic radical, provided that when R 3 is an organic radical, it is free of olefinic and alkynyl linkages and contains no more than about 20 carbon atoms, R 6 is hydrogen or an organic radical, and D is an organic radical connecting the illustrated atoms, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 85
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 77 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 86
Dependent Claim
33 words
The opaque particles of claim 77 wherein R 3 and R 6 are independently hydrogen or substituted or unsubstituted, straight or branched chain alkyl radicals having no more than about 10 carbon atoms.
Claim 87
Dependent Claim
44 words
The opaque particles of claim 79 wherein D comprises a group of the form: ##STR25## wherein R 5 and R 7 are hydrogen or organic radicals as defined for R 3 and Y and Z are independently selected from organic radicals and covalent bonds.
Claim 88
Dependent Claim
29 words
The opaque particles of claim 80 wherein Z is a covalent bond and Y is --(CH 2 ) x -- with X being an integer from 0 to 4.
Claim 89
Dependent Claim
40 words
The opaque particles of claim 81 wherein R 6 and R 7 are hydrogen, R 3 is an unsubstituted cycloalkyl or alkyl group having up to about 7 carbon atoms, R 5 is hydrogen or methyl and X is 0.
Claim 90
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 82 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 91
Dependent Claim
189 words
Opaque particles comprising copolymerized core particles substantially free of microvoids composed of a monomeric mixture having between about 15% and about 40%, by weight, of a first monomer selected from the class consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-propionic acid, acryloamido-2-hydroxybutanoic acid, methacrylamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the methyl esters of said acids and mixtures thereof, and methyl acryloamidoglycolate-methyl ether, the remainder comprising one or more other ethylenically unsatuated monomers selected from the class consisting of (1) acids selected from acrylic acid, methacrylic acid, ethylacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloracrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof, said core particles being encapsulated with an emulsion polymerized sheath comprised of one or more of said ethylenically unsaturated nonionic polymerizable monomers.
Claim 92
Dependent Claim
189 words
Opaque particles comprising copolymerized core particles substantially free of microvoids composed of a monomeric mixture having between about 15% and about 40%, by weight, of a first monomer selected from the class consisting of acryloamidoglycolic acid, methacryloamidoglycolic acid, acryloamido-2-hydroxypropionic acid, methacryloamido-2-propionic acid, acryloamido-2-hydroxybutanoic acid, methacrylamido-2-hydroxybutanoic acid, acryloamido-2-hydroxypentanoic acid, methacryloamido-2-hydroxypentanoic acid, the methyl esters of said acids and mixtures thereof, and methyl acryloamidoglycolate-methyl ether, the remainder comprising one or more other ethylenically unsatuated monomers selected from the class consisting of (1) acids selected from acrylic acid, methacrylic acid, ethylacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloracrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof, said core particles being encapsulated with an emulsion polymerized sheath comprised of one or more of said ethylenically unsaturated nonionic polymerizable monomers.
Claim 93
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 84 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 94
Dependent Claim
98 words
A process for making water insoluble opacifying particles comprising sequentially polymerizing a monomer charge comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR26## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are hydrogen or an organic radical, and D is an organic radical bridge linking the illustrated atoms, to form core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenicaly unsaturated nonionic monomers.
Claim 95
Dependent Claim
98 words
A process for making water insoluble opacifying particles comprising sequentially polymerizing a monomer charge comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR26## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are hydrogen or an organic radical, and D is an organic radical bridge linking the illustrated atoms, to form core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenicaly unsaturated nonionic monomers.
Claim 96
Dependent Claim
27 words
The process of claim 86 wherein each of said organic radicals is free of olefinic and alkynyl linkages and contains no more than about 20 carbon atoms.
Claim 97
Dependent Claim
28 words
The process of claim 87 wherein said organic radicals are substituted or unsubstituted, saturated, straight or branched chained aliphatic radicals having no more than about 10 carbon atoms.
Claim 98
Dependent Claim
55 words
The process of claim 86 wherein D comprises a carbon-oxygen group of the general form: ##STR27## wherein R 5 is hydrogen or an organic radical, R 7 is as defined for R 1 and the resultant monomers further have the form: ##STR28## wherein Y and Z are independently selected from organic radicals and covalent bonds.
Claim 99
Dependent Claim
32 words
The process of claim 89 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer in the range of from 0 to 4.
Claim 100
Dependent Claim
48 words
The process of claim 90 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 is an unsubstituted cycloalkyl or alkyl group having up to about 7 carbon atoms, R 4 and R 5 are hydrogen or methyl and X is 0.
Claim 101
Dependent Claim
157 words
Water insoluble opacifying particles made by the process of claim 43 wherein said monomer charge further comprises between 85 and 60 percent, by weight, of: one or more ethylenically unsaturated monomers selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl 2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof and, when said core particles are encapsulated with said sheath polymer, the composite core/sheath particles have an average diametric particle size in the range between about 200 to about 2000 nm.
Claim 102
Dependent Claim
33 words
A paint composition comprising between about 5 and about 50 weight percent of the opacifying particles of claim 92 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 103
Dependent Claim
100 words
The opacifying particles of claim 92 wherein said sheath polymer comprises one or more monomers selected from the group consisting of styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl-2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, with the alkyl component of said ester having from 1 to about 20 carbon atoms, and mixtures thereof.
Claim 104
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 94 weight percent of the opacifying particles of claim 48 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 105
Dependent Claim
17 words
The process of claim 86 wherein said monomer charge is emulsion polymerized to form said core particles.
Claim 106
Dependent Claim
42 words
A water base latex paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles made by the process of claim 96 and a film-forming composition comprised of one or more pigments, binders and extenders.
Claim 107
Dependent Claim
110 words
Water-insoluble opacifying particles which are substantially free of microvoids, said particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR29## wherein A is an organic bridge at least 5 atoms long, said bridge comprising an organic radical which includes, as a part thereof, a moiety of the form --NR 6 --, and R 3 and R 6 are independently hydrogen or an organic radical, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of a copolymerized monomer mixture comprising between about 93 and about 97 weight percent methyl methacrylate and between about 3 and about 7 weight percent n-butyl acrylate.
Claim 108
Dependent Claim
110 words
Water-insoluble opacifying particles which are substantially free of microvoids, said particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR29## wherein A is an organic bridge at least 5 atoms long, said bridge comprising an organic radical which includes, as a part thereof, a moiety of the form --NR 6 --, and R 3 and R 6 are independently hydrogen or an organic radical, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of a copolymerized monomer mixture comprising between about 93 and about 97 weight percent methyl methacrylate and between about 3 and about 7 weight percent n-butyl acrylate.
Claim 109
Dependent Claim
36 words
The particles of claim 98 wherein A further comprises a carboxyl group and D, said pendant group having the form: ##STR30## wherein D is an organic radical at least 3 atoms long connecting the illustrated atoms.
Claim 110
Dependent Claim
74 words
The particles of claim 99 wherein D comprises a group of the form: ##STR31## wherein R 5 is as defined for R 6 , and R 7 is selected from hydrogen, nitro, nitrile, hydroxy, halogen and organic radicals with the resultant core polymer having pendant groups of the form: ##STR32## wherein Y and Z are independently selected from organic radicals and covalent bonds, provided that Y and Z combined have at least 2 atoms.
Claim 111
Dependent Claim
29 words
The particles of claim 100 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer between 2 and about 10.
Claim 112
Dependent Claim
42 words
The particles of claim 101 wherein R 3 and R 5-7 are each independently hydrogen or organic radicals free of olefinic and alkynyl linkages, with each of said organic radicals contains no more than about 20 carbon atoms, said particles being non-swellable.
Claim 113
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 98 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 114
Dependent Claim
112 words
A process for making water insoluble opacifying particles comprising sequentially polymerizing a monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR33## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A comprises a bridge at least 3 atoms long, said bridge comprising an --NR 6 -- moiety therein, with R 6 being as defined for R 3 , to form core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 115
Dependent Claim
112 words
A process for making water insoluble opacifying particles comprising sequentially polymerizing a monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR33## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A comprises a bridge at least 3 atoms long, said bridge comprising an --NR 6 -- moiety therein, with R 6 being as defined for R 3 , to form core particles, and then encapsulating said core particles with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 116
Dependent Claim
138 words
The process of claim 104 wherein the monomer charge for said core particles comprises between about 15 and about 40 percent, by weight, of one or more of said acids or esters, the balance comprising one or more ethylenically unsaturated monomers selected from the group consisting of (1) acids selected acrylic acid, methacrylic acid, ethacrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl 2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid and mixtures thereof, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 117
Dependent Claim
51 words
The process of claim 105 wherein the sheath polymer comprises a mixture of between about 93 and about 97 methyl methacrylate and between about 7 and about 3 percent, by weight n-butyl acrylate and the composite average diametric size of the finished particles is between about 150 and about 3500 nm.
Claim 118
Dependent Claim
64 words
The process of claim 104 wherein the core particles are emulsion polymerized onto a multiplicity of seed particles having an average diametric particle size distribution in the range of between about 30 and about 70 nm to form core particles having a molecular weight distribution from about 20,000 to about 4,000,000 and an essentially unimodal distribution in the range of 50 to 1000 nm.
Claim 119
Dependent Claim
50 words
The process of claim 107 wherein said sequential polymerization process comprises copolymerizing, at a temperature of from about 60° C. to about 90° C. in an aqueous medium containing a free radical initiator, said monomer charge to form said core particles, said copolymerization then being followed by said sheath encapsulation.
Claim 120
Dependent Claim
10 words
Opaque particles as made by the process of claim 108.
Claim 121
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 109 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 122
Dependent Claim
19 words
Opaque particles as defined in claim 109 wherein said core particles are formed by emulsion copolymerizing said monomer charge.
Claim 123
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 111 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 124
Dependent Claim
10 words
Opaque particles as made by the process of claim 104.
Claim 125
Dependent Claim
17 words
The process of claim 104 wherein said core particles are formed by emulsion polymerizing said monomer charge.
Claim 126
Dependent Claim
10 words
Opaque particles as made by the process of claim 114.
Claim 127
Dependent Claim
134 words
Water insoluble opacifying particles comprising a core comprised of a polymerized monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR34## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A comprises a bridge at least 3 atoms long, said bridge comprising an --NR 6 -- moiety therein, with R 6 being as defined for R 3 , and an emulsion polymerized sheath polymerized over said core so as to encapsulate it, said sheath comprising one or more ethylenically unsaturated nonionic monomers in an amount sufficient to form composite particles having an average diametric particle size in the range between about 70 and about 4500 nm.
Claim 128
Dependent Claim
134 words
Water insoluble opacifying particles comprising a core comprised of a polymerized monomer charge containing one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR34## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, and A comprises a bridge at least 3 atoms long, said bridge comprising an --NR 6 -- moiety therein, with R 6 being as defined for R 3 , and an emulsion polymerized sheath polymerized over said core so as to encapsulate it, said sheath comprising one or more ethylenically unsaturated nonionic monomers in an amount sufficient to form composite particles having an average diametric particle size in the range between about 70 and about 4500 nm.
Claim 129
Dependent Claim
66 words
The particles of claim 116 wherein said core particles are emulsion polymerized onto a multiplicity of seed particles having an average diametric particle size distribution in the range of between about 30 and about 70 nm, the final core particles having a molecular weight distribution from about 20,000 to about 4,000,000 and an essentially unimodal distribution in the range of about 100 to about 1000 nm.
Claim 130
Dependent Claim
137 words
The particles of claim 117 wherein said monomer charge for said core particles comprises between about 15 and about 40 percent, by weight, of one or more of said acids and esters, the balance comprising one or more ethylenically unsaturated monomers selected from the group consisting of (1) acids selected from acrylic acid, methacrylic acid, ethyl acrylic acid, 2-propyl propenoic acid, 2-butyl propenoic acid, 2-pentyl propenoic acid, 2-hexyl propenoic acid, cyclohexylacrylic acid, chloroacrylic acid, phenylacrylic acid, furylacrylic acid, 2-butenoic acid, 2-ethylhexyl 2-butenoic acid, 2-pentenoic acid, 3-methyl-3-pentenoic acid, acryloxypropionic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, and (2) nonionic monomers selected from alkyl esters of said acids, with the alkyl component thereof having from 1 to about 20 carbon atoms, styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and acrylonitrile, and mixtures thereof.
Claim 131
Dependent Claim
48 words
The particles of claim 118 wherein the sheath polymer comprises a mixture of between about 93 and about 97 methyl methacrylate and between about 7 and about 3 percent, by weight n-butyl acrylate and the composite average diametric particle size is between about 150 and about 3500 nm.
Claim 132
Dependent Claim
36 words
A paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 116 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 133
Dependent Claim
122 words
Water insoluble opacifying particles comprising core particles comprised of one or more polymerized ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR35## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, with A being an organic bridge at least 3 carbon atoms long, said bridge comprising an NR 6 moiety, wherein R 6 is as defined for R 3 , and the polymer has pendant functional groups of the form: ##STR36## wherein A and R 3 are as defined above, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 134
Dependent Claim
122 words
Water insoluble opacifying particles comprising core particles comprised of one or more polymerized ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR35## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 is hydrogen or an organic radical, with A being an organic bridge at least 3 carbon atoms long, said bridge comprising an NR 6 moiety, wherein R 6 is as defined for R 3 , and the polymer has pendant functional groups of the form: ##STR36## wherein A and R 3 are as defined above, said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 135
Dependent Claim
31 words
The particles of claim 121 wherein A comprises a carboxyl group and D, and said pendant groups have the form: ##STR37## wherein D is an organic radical connecting the illustrated atoms.
Claim 136
Dependent Claim
72 words
The particles of claim 122 wherein D comprises a group of the form: ##STR38## wherein R 5 is as defined for R 6 , and R 7 is selected from hydrogen, nitro, nitrile, hydroxy, halogen and organic radicals, and the pendant groups have the form: ##STR39## wherein Y and Z are independently selected from organic radicals and covalent bonds, provided that at least one of Y and Z is an organic radical.
Claim 137
Dependent Claim
40 words
The particles of claim 173 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer between 1 and about 10, and each of R 1-7 are independently hydrogen or organic radicals.
Claim 138
Dependent Claim
38 words
The particles of claim 124 wherein each of said organic radicals is free of olefinic and alkynyl linkages and each of said radicals contains no more than about 20 carbon atoms, said particles being substantially free of microvoids.
Claim 139
Dependent Claim
36 words
The particles of claim 121 wherein said sheath polymer comprises a copolymerized monomer mixture of between about 93 and about 97 weight percent methyl methacrylate and between about 3 and about 7 weight percent n-butyl acrylate.
Claim 140
Dependent Claim
38 words
A water base latex paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 121 and a film-forming composition comprised of one or more pigments, binders and extenders.
Claim 141
Dependent Claim
78 words
Water insoluble opacifying particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR40## wherein R 3 is hydrogen or an organic radical and A comprises an organic bridge at least 3 carbon atoms long, said bridge comprising an NR 6 moiety, wherein R 6 is as defined for R 3 , said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 142
Dependent Claim
78 words
Water insoluble opacifying particles comprising polymerized core particles comprised of a polymer having pendant functional groups of the form: ##STR40## wherein R 3 is hydrogen or an organic radical and A comprises an organic bridge at least 3 carbon atoms long, said bridge comprising an NR 6 moiety, wherein R 6 is as defined for R 3 , said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 143
Dependent Claim
30 words
The particles of claim 128 wherein A comprises a carboxyl group and D, said pendant groups having the form: ##STR41## wherein D is an organic radical connecting the illustrated atoms.
Claim 144
Dependent Claim
60 words
The particles of claim 129 wherein D comprises a group of the form: ##STR42## and the pendant groups have the form: ##STR43## wherein Y and Z are independently selected from organic radicals and covalent bonds, provided that at least one of Y and Z is an organic radical, and R 3 and R 5-7 are independently hydrogen or organic radicals.
Claim 145
Dependent Claim
38 words
A water base latex paint composition comprising a mixture of between about 5 and about 50 weight percent of the opacifying particles of claim 130 and a film-forming composition comprised of one or more pigments, binders and extenders.
Claim 146
Dependent Claim
29 words
the particles of claim 130 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer between 1 and about 10.
Claim 147
Dependent Claim
38 words
The particles of claim 132 wherein each of said organic radicals is free of olefinic and alkynyl linkages and each of said radicals contains no more than about 20 carbon atoms, said particles being substantially free of microvoids.
Claim 148
Dependent Claim
36 words
The particles of claim 133 wherein said sheath polymer comprises a copolymerized monomer mixture of between about 93 and about 97 weight percent methyl methacrylate and between about 3 and about 7 weight percent n-butyl acrylate.
Claim 149
Dependent Claim
140 words
Water insoluble opacifying particles comprised of seed particles having an average diametric particle size in the range of about 30 to about 100 nm, said seed particles having polymerized thereonto a core composition comprised of a mixture of an alpha-beta ethylenically unsaturated amide of the form: ##STR44## and a keto carboxylic acid or ester of the form: ##STR45## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are independently selected from hydrogen and organic radicals and Z is an organic radical or a covalent bond, and one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 150
Dependent Claim
140 words
Water insoluble opacifying particles comprised of seed particles having an average diametric particle size in the range of about 30 to about 100 nm, said seed particles having polymerized thereonto a core composition comprised of a mixture of an alpha-beta ethylenically unsaturated amide of the form: ##STR44## and a keto carboxylic acid or ester of the form: ##STR45## wherein R 1 , R 2 , R 4 and R 7 are independently selected from hydrogen, nitro, amino, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are independently selected from hydrogen and organic radicals and Z is an organic radical or a covalent bond, and one or more other ethylenically unsaturated acidic or nonionic monomers to form core particles, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 151
Dependent Claim
32 words
The particles of claim 135 wherein said mixture comprises between about 15 and about 40 weight percent of a stoichiometric mixture of said unsaturated amide and said keto carboxylic acid or ester.
Claim 152
Dependent Claim
88 words
Water insoluble opacifying particles comprising a core polymer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR46## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are hydrogen or an organic radical, and D is an organic radical bridge linking the illustrated atoms, with said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 153
Dependent Claim
88 words
Water insoluble opacifying particles comprising a core polymer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR46## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl, halogen and organic radicals, R 3 and R 6 are hydrogen or an organic radical, and D is an organic radical bridge linking the illustrated atoms, with said core particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 154
Dependent Claim
58 words
The particles of claim 137 wherein D comprises a group of form: ##STR47## wherein R 5 is as defined for R 6 , and R 7 is selected from hydrogen, nitro, nitrile, hydroxy, halogen and organic radicals, and the core polymer has the form: ##STR48## wherein Y and Z are independently selected from organic radicals and covalent bonds.
Claim 155
Dependent Claim
38 words
The particles of claim 138 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer between 0 and about 10 and R 1-7 are independly hydrogen or organic radicals.
Claim 156
Dependent Claim
81 words
Water insoluble opacifying particles which are substantially free of microvoids, said particles comprising a first monomer of the form: ##STR49## wherein R 1-7 are independently selected from hydrogen and saturated aliphatic radicals having no more than about 7 carbon atoms and X is an integer from 0 to about 10, and one or more other ethylenically unsaturated acidic or nonionic monomers, said particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 157
Dependent Claim
81 words
Water insoluble opacifying particles which are substantially free of microvoids, said particles comprising a first monomer of the form: ##STR49## wherein R 1-7 are independently selected from hydrogen and saturated aliphatic radicals having no more than about 7 carbon atoms and X is an integer from 0 to about 10, and one or more other ethylenically unsaturated acidic or nonionic monomers, said particles being encapsulated with an emulsion polymerized sheath polymer comprised of one or more ethylenically unsaturated nonionic polymerizable monomers.
Claim 158
Dependent Claim
50 words
The particles of claim 140 wherein R 1 , R 2 , R 6 and R 7 are hydrogen, R 3 is hydrogen or an alkyl group having up to about 5 carbon atoms, R 4 and R 5 are hydrogen or methyl and X ranges from 0 to 2.
Claim 159
Dependent Claim
13 words
The particles of claim 140 wherein X ranges from 3 to about 10.
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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) | 1992-05-08 | 1992-11-07 | 1993-05-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-08 | 1996-11-07 | 1997-05-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-08 | 2000-11-07 | 2001-05-09 | $7700.00 | Window Closed / Lapsed |