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US4885320A Expired / Lapsed US ⏱️ 0.0 years remaining

Polymeric opaque particles and process for making same

Assignee: Rohm and Haas Co
•
Filing: 1988-11-30
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Granted: 1989-12-05
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Expires: 2008-11-30
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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 opaque 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 diametric 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 2026-10-27 13:53
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: 63
Claim 1
Independent Claim 64 words
Water-insoluble opacifying particles comprising polymerized core particles comprises of a polymer having pendant functional groups of the form: ##STR16## wherein A is an organic bridge at least 5 atoms long and R 3 is hydrogen or an organic radical, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 2
Dependent Claim 64 words
Water-insoluble opacifying particles comprising polymerized core particles comprises of a polymer having pendant functional groups of the form: ##STR16## wherein A is an organic bridge at least 5 atoms long and R 3 is hydrogen or an organic radical, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 3
Dependent Claim 36 words
The particles of claim 1 wherein said sheath polymer comprises 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 4
Dependent Claim 42 words
The particles of claim 1 wherein A comprises a carboxyl group, B and D, said pendant group having the form: ##STR17## wherein B is --O-- or --S--, and D is an organic radical at least 3 atoms long connecting the illustrated atoms.
Claim 5
Dependent Claim 73 words
The particles of claim 3 wherein D comprises a group of the form: ##STR18## wherein R 5 is hydrogen or an organic radical, 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: ##STR19## 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 6
Dependent Claim 29 words
The particles of claim 4 wherein Z is a covalent bond and Y is --(CH 2 ) x --, with X being an integer between 2 and about 10.
Claim 7
Dependent Claim 41 words
The particles of claim 5 wherein R 3 , R 5 and R 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.
Claim 8
Dependent Claim 75 words
Non-swellable, microvoid-free opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters, said core particles having a structure in which the polymer has pendant functional groups of the form: ##STR20## wherein A is an organic bridge at least 3 atoms long and R 3 is hydrogen or an organic radical, said core particles further being encapsulated with sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 9
Dependent Claim 75 words
Non-swellable, microvoid-free opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters, said core particles having a structure in which the polymer has pendant functional groups of the form: ##STR20## wherein A is an organic bridge at least 3 atoms long and R 3 is hydrogen or an organic radical, said core particles further being encapsulated with sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 10
Dependent Claim 101 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: ##STR21## 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 3 atoms long, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 11
Dependent Claim 101 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: ##STR21## 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 3 atoms long, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 12
Dependent Claim 42 words
The process of claim 8 wherein A comprises a carboxyl group, B, an inorganic bridge between the illustrated atoms and D, an organic radical, said monomer having the form: ##STR22## wherein B is --S-- or --O--, and D links B and C.
Claim 13
Dependent Claim 45 words
The process of claim 9 wherein D comprises a group of the general form: ##STR23## wherein R 5 is hydrogen or an organic radical, R 7 is as defined for R 1 and Y and Z are independently selected from organic radicals and covalent bonds.
Claim 14
Dependent Claim 32 words
The process of claim 10 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 15
Dependent Claim 25 words
The process of claim 10 where said organic radicals are free of olefinic and alkynyl linkages and contain no more than about 20 carbon atoms.
Claim 16
Dependent Claim 45 words
The process of claim 11 wherein R 1 , R 2 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 17
Dependent Claim 26 words
The process of claim 12 wherein said organic radicals further comprise one or more hetero atoms selected from the class consisting sulfur, oxygen, nitrogen and phosphorus.
Claim 18
Dependent Claim 27 words
The process of claim 12 wherein said radicals further comprise one or more substituents selected from the class consisting of thiol, hydroxy, nitro, amino, nitrile or halogen.
Claim 19
Dependent Claim 47 words
The process of claim 12 wherein said organic radicals are cyclic radicals selected from the class consisting of substituted and unsubstituted aryl, alkylaryl, arylalkyl, cycloalkyl, alkyl substituted cycloalkyl and cycloalkyl substituted alkyl groups, said radicals having no more than about 10 carbon atoms and only 1 ring.
Claim 20
Dependent Claim 28 words
The process of claim 12 wherein said organic radicals are substituted or unsubstituted, saturated, straight or branched chained aliphatic radicals having no more than about 10 carbon atoms.
Claim 21
Dependent Claim 9 words
Opaque particles made by the process of claim 8.
Claim 22
Dependent Claim 49 words
A paint composition comprising a mixture of between about 5% and about 50%, by weight, of the opacifying particles of claim 18 and a film forming latex comprising one or more pigments, binders and extenders to form a coating composition having a significant level of opacity to incident light.
Claim 23
Dependent Claim 183 words
Water insoluble opacifying particles made by the process of claim 8 wherein said monomer charge comprises between 15 and 40 percent, by weight, of a monomer having the form: ##STR24## wherein R 1 , R 2 , R 3 , R 4 and A are as defined therein, the remainder comprising 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 24
Dependent Claim 33 words
A paint composition comprising between about 5 and about 50 weight percent of the opacifying particles of claim 20 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 25
Dependent Claim 100 words
The opacifying particles of claim 20 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 26
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 22 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 27
Dependent Claim 16 words
The process of claim 8 wherein said monomer is emulsion polymerized to form said core particles.
Claim 28
Dependent Claim 50 words
The opacifying particles of claim 20 wherein R 3 , when an organic radical, is free of olefinic and alkynyl linkages and contains no more than about 20 carbon atoms, and A is of the following form: ##STR25## wherein B is --S-- or --O--, and D is an organic radical.
Claim 29
Dependent Claim 68 words
The opaque particles of claim 25 wherein R 3 is hydrogen or a substituted or unsubstituted, straight or branched chain alkyl radical having no more than about 10 carbon atoms, and D comprises a group of the form: ##STR26## 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 30
Dependent Claim 29 words
The opaque particles of claim 26 wherein Z is a covalent bond and Y is --(CH 2 ) x -- with X being an integer from 0 to 4.
Claim 31
Dependent Claim 37 words
The opaque particles of claim 27 wherein R 7 is 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 32
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 33
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 20 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 34
Dependent Claim 123 words
A process for making water insoluble opacifying particles comprising polymerizing a monomer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR27## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl and halogen groups, and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 3 atoms long, to form core particles, said polymerization resulting in a polymer having pendant functional groups of the formula: ##STR28## wherein A and R 3 are as described above, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 35
Dependent Claim 123 words
A process for making water insoluble opacifying particles comprising polymerizing a monomer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR27## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl and halogen groups, and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 3 atoms long, to form core particles, said polymerization resulting in a polymer having pendant functional groups of the formula: ##STR28## wherein A and R 3 are as described above, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 36
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 31 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 37
Dependent Claim 89 words
Opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR29## 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 3 atoms long, said core particles further being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 38
Dependent Claim 89 words
Opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR29## 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 3 atoms long, said core particles further being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 39
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 33 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 40
Dependent Claim 99 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: ##STR30## 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, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 41
Dependent Claim 99 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: ##STR30## 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, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 42
Dependent Claim 33 words
A paint composition comprising between about 5 and about 50 weight percent of the opacifying particles of claim 35 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 43
Dependent Claim 64 words
The process of claim 35 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 44
Dependent Claim 33 words
A paint composition comprising between about 5 and about 50 weight percent of the opacifying particles of claim 37 and a latex film-forming composition comprised of one or more pigments, binders and extenders.
Claim 45
Dependent Claim 112 words
Water insoluble opacifying particles comprising core particles comprised of one or more polymerized ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR31## 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 comprising a bridge at least 5 atoms long, and the polymer has pendant functional groups of the form: ##STR32## wherein A and R 3 are as defined above, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 46
Dependent Claim 112 words
Water insoluble opacifying particles comprising core particles comprised of one or more polymerized ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR31## 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 comprising a bridge at least 5 atoms long, and the polymer has pendant functional groups of the form: ##STR32## wherein A and R 3 are as defined above, said core particles being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers, said particles being substantially free of microvoids.
Claim 47
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 39 and a film-forming composition comprised of one or more pigments, binders and extenders.
Claim 48
Dependent Claim 64 words
The particles of claim 39 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 49
Dependent Claim 32 words
The particles of claim 39 wherein said core particles are copolymerized at a temperature of from about 60° C. to about 90° C. in an aqueous medium containing a free radical initiator.
Claim 50
Dependent Claim 87 words
A process for making non-swellable, microvoid-free 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: ##STR33## wherein R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen and organic radicals, and A is an organic radical bridge at least 3 atoms long, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 51
Dependent Claim 87 words
A process for making non-swellable, microvoid-free 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: ##STR33## wherein R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen and organic radicals, and A is an organic radical bridge at least 3 atoms long, to form core particles, and then encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 52
Dependent Claim 64 words
The process of claim 43 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 53
Dependent Claim 32 words
The process of claim 43 wherein said core particles are copolymerized at a temperature of from about 60° C. to about 90° C. in an aqueous medium containing a free radical initiator.
Claim 54
Dependent Claim 42 words
The process of claim 43 wherein A comprises a carboxyl group, B, an inorganic bridge between the illustrated atoms and D, an organic radical, said monomer having the form: ##STR34## wherein B is --S-- or --O--, and D links B and C.
Claim 55
Dependent Claim 45 words
The process of claim 46 wherein D comprises a group of the general form: ##STR35## wherein R 5 is hydrogen or an organic radical, R 7 is as defined for R 1 and Y and Z are independently selected from organic radicals and covalent bonds.
Claim 56
Dependent Claim 32 words
The process of claim 47 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 57
Dependent Claim 48 words
The process of claim 48 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 58
Dependent Claim 25 words
The process of claim 43 where said organic radicals are free of olefinic and alkynyl linkages and contain no more than about 20 carbon atoms.
Claim 59
Dependent Claim 28 words
The process of claim 50 wherein said organic radicals are substituted or unsubstituted, saturated, straight or branched chained aliphatic radicals having no more than about 10 carbon atoms.
Claim 60
Dependent Claim 118 words
A process for making non-swellable, microvoid-free water insoluble opacifying particles comprising polymerizing a monomer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR36## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl and halogen groups, and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 3 atoms long, to form core particles, said polymerization resulting in a polymer having pendant functional groups of the formula: ##STR37## wherein A and R 3 are as described above, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 61
Dependent Claim 118 words
A process for making non-swellable, microvoid-free water insoluble opacifying particles comprising polymerizing a monomer comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR36## wherein R 1 , R 2 and R 4 are independently selected from hydrogen, nitro, nitrile, hydroxyl and halogen groups, and organic radicals, R 3 is hydrogen or an organic radical, and A is an organic radical bridge at least 3 atoms long, to form core particles, said polymerization resulting in a polymer having pendant functional groups of the formula: ##STR37## wherein A and R 3 are as described above, and encapsulating said core particles with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 62
Dependent Claim 75 words
Non-swellable, microvoid-free opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR38## wherein R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen and organic radicals, and A is an organic radical bridge at least 3 atoms long, said core particles further being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.
Claim 63
Dependent Claim 75 words
Non-swellable, microvoid-free opaque particles comprising polymerized core particles comprised of one or more ethylenically unsaturated carboxylic acids or esters thereof of the form: ##STR38## wherein R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen and organic radicals, and A is an organic radical bridge at least 3 atoms long, said core particles further being encapsulated with a sheath polymer comprised of one or more ethylenically unsaturated nonionic monomers.

References Cited (Backward Citations)

US4427836A Cited
US4829102A Cited

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