CA2096106A1 - Process for improving water-whitening resistance of pressure sensitive adhesives - Google Patents
Process for improving water-whitening resistance of pressure sensitive adhesivesInfo
- Publication number
- CA2096106A1 CA2096106A1 CA002096106A CA2096106A CA2096106A1 CA 2096106 A1 CA2096106 A1 CA 2096106A1 CA 002096106 A CA002096106 A CA 002096106A CA 2096106 A CA2096106 A CA 2096106A CA 2096106 A1 CA2096106 A1 CA 2096106A1
- Authority
- CA
- Canada
- Prior art keywords
- pressure sensitive
- water
- sensitive adhesive
- aqueous latex
- exchange resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
- C09J121/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
Abstract
ABSTRACT OF THE DISCLOSURE:
A process is disclosed for improving the water-whitening resistance of a pressure sensitive adhesive containing an aqueous latex emulsion and water-soluble ions by removing the water-soluble ions and adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø The preferred method of removing the water-soluble ions is to contact either the aqueous latex emulsion, the formulated pressure sensitive adhesive containing the aqueous latex emulsion, or both with ion exchange resin. The product produced by the process is also disclosed.
A process is disclosed for improving the water-whitening resistance of a pressure sensitive adhesive containing an aqueous latex emulsion and water-soluble ions by removing the water-soluble ions and adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø The preferred method of removing the water-soluble ions is to contact either the aqueous latex emulsion, the formulated pressure sensitive adhesive containing the aqueous latex emulsion, or both with ion exchange resin. The product produced by the process is also disclosed.
Description
2¢9~ .06 PROCESS FOR IMPROVING WATER-~HITENING RESISTANCE
OF PI~ESSURE SENSITIVE ADHESIVES
FIELD OF TEIE INVEN~lON:
This invention is directed to a process for improving aqueous latex emulsion coatings, and more particularly to a process for improving the water-whitening resistance of pressure sensitive adhesives.
BACKGROUND OF THE INVENTION: -Pressure sensitive adhesives may be used with transparent backings, such as for example polyvinyl chloride, polyethylene, polypropylene, polyester and the like, to forrn transparent labels and c~cals. I~ ~d decaLs are applied to the sides ~ ~c, store windows and the like. These surfaces are often squeegied clean prior to the application of the label or decal. This leaves a thin layer of water on the surface. The wet surface allows for the adjustment or positioning of the label or decal. In cases where the backings are transparent, this can result in the development of water-whitening or hazing in the pressure sensitive adhesive, which persists until the system is substantially dry. This drying period may be unacceptably long. For example, a large label, such as that applied to the side of a ~s~,~n6 truck, may take several hours to dry after application of the label.
Because the labels and decals are used in advertising and displays, this water-whitening, although only temporary and not detrimental to the pressure sensitive adhesive's ultimate performance, is not aesthetically acceptable.
Although not intending to be bound by theory, I believe that the water-whitening or hazing is caused by the diffusion of water across latex particle boundari~s into the interstitial areas in the dried coating forming pockets of water. This gives rise to an osmotic pressure which acts to push the latex particles apart. When the pockets of water become large enough, they scatter visible causing the water-whitening or hazing.
Normally when the aqueous latex emulsion dries, the latex particles coalesce to form a film and the other components of the adhesive formulation which may be ionically-charged and water-soluble become trapped in the interstitial areas of the film. These materials, such as for example, dispersants, surfactants, coalescents, wetting agents, rheology modifiers, thickeners, drying retarders, antifoaming agents, preservatives, heat stabilizers, ultraviolet light absorbers and the like, may attract water because they may be more 2~
hydrophilic than the emulsion particles and become the driving force for the migration of the water into the interstitial areas causing the water-whitening problem. Solvent-based adhesives do not experience this water-whitening problem, however they present safety, health and environmental concerns. By contacting the aqueous latex emulsion used in the adhesive formulation or the formulated adhesive with an ion exchange resin, I have found that water-soluble ions may be removed so that the water-whitening resistance or hazing of the pressure sensitive adhgsive is improved.
2S~
DESCRI~ION OF l~IE PRIOR ART:
U.S. Patent 3,033,811 concerns pigmented thermosetting coating compositions which can be applied from aqueous media to the surfaces to be coated. It teaches the removal of water-soluble ionizable compounds present in the dispersion by dialysis, deionization with ion exchange resins or precipitation to increase the water-resistance of the final baked coating.
U.S. Patent 3,494,878 teaches an ion exchange resin of anionic or cationic types or mixtures thereof which are incorporated in aqueous coating compositions the binder of which comprises a dispersed emulsion polymer. The clear or pigmented coating compositions resist staining when the coatings are applied over cedar, redwood, mahogany and rusty surfaces.
U.S. Patent 3,509,084 teaches a basic aqueous dispersion containing metallic ions which is contacted with a strongly acidic ion exchange resin charged with ammonium ions to produce an aqueous dispersion substantially free of metallic ions.
U.S. Patent 4,775,588 teaches a hydrophilic film-forming 2~s~,~n~
composition which comprises a resin paint comprising a resin binder and a paint vehicle with a solid ion exchange resin powder dispersed in the vehicle. The incorporation of the i~n exchange resin powder into an undercoat treatment provides improved corrosion resistance.
U.S. Patent 4,853,422 teaches a paint coating comprising a self-curing emulsion polymer having functional carboxyl groups or hydroxyl group as well as alkylol acrylamide where said self-curing emulsion polymer is ~n-exchanged to remove cations therefrom and the pH is less than 2.5.
U.S. Patent 4,900,592 teaches a paint coating containing a thermosetting polymeric binder based on an ion-exchange treated, thermosetting functional latex polymer. The functional latex polymer comprises emulsion polymerized ethylenic monomers including a ,B-hydroxy ester monomer, but specifically exclu~ing amine rnonomers,-to produce a functional latex. The functional latex is then treated in an ion-exchange process to produce a low pH functional latex adapted to self-crosslink by transesterification with respective ~-hydroxy ester groups in the latex.
It is an object of the invention to provide a process for improving the water-whitening resistance of pressure sensitive adhesives by removing the water-soluble ions from the latex polymer emulsion or pressure sensitive adhesive formulation containing latex polymer emulsion without adversely affecting the pressure sensitive adhesives performance properties.
It is a further object of the present invention to provide a pressure sensitive adhesive with improved water-whitening resistance. ~
Other objects and advantages will become apparent from the following description and claims.
SUMMARY OF THE INVENTION:
This invention is a process for improving the water-whitening resistance of a pressure sensitive adhesive containing an aqueous latex emulsion by removing the water-soluble ions either from the aqueous latex emulsion or the formulated pressure sensitive adhesive containing the aqueous latex emulsion and adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø It is preferred that the wa~er-soluble ions are removed by contacting the aqueous latex emulsion, the formulated pressure sensitive adhesive or both with ion exchange resins. The product of this process is a pressure sensitive adhesive with improved water-whitening resistance. The process is particularly useful for producing a pressure sensitive adhesive which is used to adhere clear labels and decals to surfaces, such as store windows and the sides of vehides. The process solves the water-whitening problem typically encountered by the use of water on the surface to aid in the positioning of the clear label or decal. The process improves the aesthetic characteristics of the pressure sensitive adhesive without having a detrimental effect on the functional characteristics.
ZC9~ )t;
DETAILED DESCRI~ION OF THE INVENTION:
The term "adhesive" as used herein refers to a coating containing an aqueous latex polymer which when applied to surfaces joins them together and resists separation.
The term "pressure sensitive" as used herein refers to adhesives which typically do not undergo hardening after they have been applied to surfaces and the joiTlt formed.
The term "latex" as used herein refers to a water-insoluble polymer which may be prepared by conventional polymerization techniques such as, for example, by emulsion polymerization.
The aqueous latex polymers used in the pressure sensitive adhesives of this invention are prepared by e~mulsion polyrnerization techniques well known in the art. The aqueous latex polyrner may be formed from any monomer or mixture of monomers which yields a water-insoluble latex, film-forming polymer. The aqueous latex polymers used in the pressure sensitive adhesives of this invention typically have a glass transition temperature as measured via differential scanning calorimetry of less than about -10C. The weight-~cs~,ln6 average molecular weight of the aqueous latex polymer may beadjusted through the addition of n-dodecyl mercaptan during emulsion polyrnerization to give a suitable balance of adhesive and cohesive strength.
A wide variety of monomers or mixture of monomers may be used to make the aqueous latex polymer used in the adhesives of this invention. For example, acrylic ester monomers, induding methyl acrylate, ethyl acrylate"propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, secondary butyl acrylate, t-butyl acrylate, pentyl acrylate, neopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, bornyl acrylate, isobornyl acrylate, myristyl acrylate, pentadecyl acrylate, stearyl acrylate and the like; methacrylic acid ester monomers, including methyl methacrylate, ethyl methacrylate, propyl methacrylate, isoprop~l methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, bornyl methacrylate, isobornyl methacrylate, myristyl methacrylate, pentadecyl methacrylate, stearyl methacrylate, phosphoethyl methacrylate and the like; acrylic acid, methacrylic acid, itaconic acid, maleic acid, furnaric acid, styrene, ~:C~ )6 substituted styrenes, butadiene, acrylonitrile, ethylene, vinyl acetate, vinyl chloride, sodium styrene sulfonates, sodium vinyl sulfonate, acrylamide, methacrylamide and the like may be used.
The removal of water-soluble ions from the aqueous latex polymer emulsion or pressure sensitive adhesive formulation is critical to the operation of this invention. The water-soluble ions may be removed by a number of techniques, including, but not limited to, centrifugation, dialysis, precipitation and deionization with ion exchange resins. The preferred method of removing the water-soluble ions is to contact the aqueous latex polymer emulsion or the formulated pressure sensitive adhesive containing the aqueous latex polymer emulsion with ion exchange resin. Contacting the final pressure sensitive adhesive formulation containing the aqueous latex polymer with the ion exchange resin is preferred.
The aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer may be treated with ion exchange resin either (1) by adding the ion exchange resin to the aqueous latex polymer emulsion or the pressure sensitive adhesive forrnulation containing the aqueous latex polymer; or r)~, (2~ by passing the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer over a column bed of ion exchange resin.
When adding the ion exchange resin to the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer, the ion exchange resin must be mixed thoroughly to permit_~ontact of the ion exchange resin surfaces with the water-soluble ions in the emulsion or adhesive. The contact can be effected by adding to the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer from about 1% by weight to about 100%, preferably greater than about 2%, by weight of the ion exchange resin to the weight of the emulsion or adhesive. The admixture may be agitated to facilitate contact between the ion exchange resin and~he water-soluble ions.
The ion exchange resin may be removed from the mixture by straining through a filter medium such as linen doth, nylon mesh filter and the like to remove all of the ion exchange resin. The procedure may be repeated several times, if necessary, to remove the water-insoluble ions from the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer.
2(~9~,:1{)6 The rate of from about 0.5 bed volume/hour to about 10 bed volumes/hour, of passing the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer over a column bed of ion exchange resin is effective to remove the water-soluble ions. A rate of from about 1 bed volume/hour to about 6 bed volumes/hour is preferred, with a rate of from about 1 bed volume/hour to about 3 bed volumes/hour most preferred.
The preferred method o~ using the ion exchange resins comprises making a mixture of a sulfonic acid type cation exchanger in the acid form (to remove anions) and a quaternary anion exchange resin in the free base form (to remove cations), and contacting the aqueous latex polymer emulsion or the pressure sensitive adhesive containing the aqueous latex polymer to be deionized with the mixture. Such mixtures of cation and anion exchange resins are well-known to those skilled in the art as "mixed beds." Cation and anion exchange resins may also be used in succession. Cation or anion exchange resins may also be used separately, however complete deionization may not be achieved.
OF PI~ESSURE SENSITIVE ADHESIVES
FIELD OF TEIE INVEN~lON:
This invention is directed to a process for improving aqueous latex emulsion coatings, and more particularly to a process for improving the water-whitening resistance of pressure sensitive adhesives.
BACKGROUND OF THE INVENTION: -Pressure sensitive adhesives may be used with transparent backings, such as for example polyvinyl chloride, polyethylene, polypropylene, polyester and the like, to forrn transparent labels and c~cals. I~ ~d decaLs are applied to the sides ~ ~c, store windows and the like. These surfaces are often squeegied clean prior to the application of the label or decal. This leaves a thin layer of water on the surface. The wet surface allows for the adjustment or positioning of the label or decal. In cases where the backings are transparent, this can result in the development of water-whitening or hazing in the pressure sensitive adhesive, which persists until the system is substantially dry. This drying period may be unacceptably long. For example, a large label, such as that applied to the side of a ~s~,~n6 truck, may take several hours to dry after application of the label.
Because the labels and decals are used in advertising and displays, this water-whitening, although only temporary and not detrimental to the pressure sensitive adhesive's ultimate performance, is not aesthetically acceptable.
Although not intending to be bound by theory, I believe that the water-whitening or hazing is caused by the diffusion of water across latex particle boundari~s into the interstitial areas in the dried coating forming pockets of water. This gives rise to an osmotic pressure which acts to push the latex particles apart. When the pockets of water become large enough, they scatter visible causing the water-whitening or hazing.
Normally when the aqueous latex emulsion dries, the latex particles coalesce to form a film and the other components of the adhesive formulation which may be ionically-charged and water-soluble become trapped in the interstitial areas of the film. These materials, such as for example, dispersants, surfactants, coalescents, wetting agents, rheology modifiers, thickeners, drying retarders, antifoaming agents, preservatives, heat stabilizers, ultraviolet light absorbers and the like, may attract water because they may be more 2~
hydrophilic than the emulsion particles and become the driving force for the migration of the water into the interstitial areas causing the water-whitening problem. Solvent-based adhesives do not experience this water-whitening problem, however they present safety, health and environmental concerns. By contacting the aqueous latex emulsion used in the adhesive formulation or the formulated adhesive with an ion exchange resin, I have found that water-soluble ions may be removed so that the water-whitening resistance or hazing of the pressure sensitive adhgsive is improved.
2S~
DESCRI~ION OF l~IE PRIOR ART:
U.S. Patent 3,033,811 concerns pigmented thermosetting coating compositions which can be applied from aqueous media to the surfaces to be coated. It teaches the removal of water-soluble ionizable compounds present in the dispersion by dialysis, deionization with ion exchange resins or precipitation to increase the water-resistance of the final baked coating.
U.S. Patent 3,494,878 teaches an ion exchange resin of anionic or cationic types or mixtures thereof which are incorporated in aqueous coating compositions the binder of which comprises a dispersed emulsion polymer. The clear or pigmented coating compositions resist staining when the coatings are applied over cedar, redwood, mahogany and rusty surfaces.
U.S. Patent 3,509,084 teaches a basic aqueous dispersion containing metallic ions which is contacted with a strongly acidic ion exchange resin charged with ammonium ions to produce an aqueous dispersion substantially free of metallic ions.
U.S. Patent 4,775,588 teaches a hydrophilic film-forming 2~s~,~n~
composition which comprises a resin paint comprising a resin binder and a paint vehicle with a solid ion exchange resin powder dispersed in the vehicle. The incorporation of the i~n exchange resin powder into an undercoat treatment provides improved corrosion resistance.
U.S. Patent 4,853,422 teaches a paint coating comprising a self-curing emulsion polymer having functional carboxyl groups or hydroxyl group as well as alkylol acrylamide where said self-curing emulsion polymer is ~n-exchanged to remove cations therefrom and the pH is less than 2.5.
U.S. Patent 4,900,592 teaches a paint coating containing a thermosetting polymeric binder based on an ion-exchange treated, thermosetting functional latex polymer. The functional latex polymer comprises emulsion polymerized ethylenic monomers including a ,B-hydroxy ester monomer, but specifically exclu~ing amine rnonomers,-to produce a functional latex. The functional latex is then treated in an ion-exchange process to produce a low pH functional latex adapted to self-crosslink by transesterification with respective ~-hydroxy ester groups in the latex.
It is an object of the invention to provide a process for improving the water-whitening resistance of pressure sensitive adhesives by removing the water-soluble ions from the latex polymer emulsion or pressure sensitive adhesive formulation containing latex polymer emulsion without adversely affecting the pressure sensitive adhesives performance properties.
It is a further object of the present invention to provide a pressure sensitive adhesive with improved water-whitening resistance. ~
Other objects and advantages will become apparent from the following description and claims.
SUMMARY OF THE INVENTION:
This invention is a process for improving the water-whitening resistance of a pressure sensitive adhesive containing an aqueous latex emulsion by removing the water-soluble ions either from the aqueous latex emulsion or the formulated pressure sensitive adhesive containing the aqueous latex emulsion and adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø It is preferred that the wa~er-soluble ions are removed by contacting the aqueous latex emulsion, the formulated pressure sensitive adhesive or both with ion exchange resins. The product of this process is a pressure sensitive adhesive with improved water-whitening resistance. The process is particularly useful for producing a pressure sensitive adhesive which is used to adhere clear labels and decals to surfaces, such as store windows and the sides of vehides. The process solves the water-whitening problem typically encountered by the use of water on the surface to aid in the positioning of the clear label or decal. The process improves the aesthetic characteristics of the pressure sensitive adhesive without having a detrimental effect on the functional characteristics.
ZC9~ )t;
DETAILED DESCRI~ION OF THE INVENTION:
The term "adhesive" as used herein refers to a coating containing an aqueous latex polymer which when applied to surfaces joins them together and resists separation.
The term "pressure sensitive" as used herein refers to adhesives which typically do not undergo hardening after they have been applied to surfaces and the joiTlt formed.
The term "latex" as used herein refers to a water-insoluble polymer which may be prepared by conventional polymerization techniques such as, for example, by emulsion polymerization.
The aqueous latex polymers used in the pressure sensitive adhesives of this invention are prepared by e~mulsion polyrnerization techniques well known in the art. The aqueous latex polyrner may be formed from any monomer or mixture of monomers which yields a water-insoluble latex, film-forming polymer. The aqueous latex polymers used in the pressure sensitive adhesives of this invention typically have a glass transition temperature as measured via differential scanning calorimetry of less than about -10C. The weight-~cs~,ln6 average molecular weight of the aqueous latex polymer may beadjusted through the addition of n-dodecyl mercaptan during emulsion polyrnerization to give a suitable balance of adhesive and cohesive strength.
A wide variety of monomers or mixture of monomers may be used to make the aqueous latex polymer used in the adhesives of this invention. For example, acrylic ester monomers, induding methyl acrylate, ethyl acrylate"propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, secondary butyl acrylate, t-butyl acrylate, pentyl acrylate, neopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, bornyl acrylate, isobornyl acrylate, myristyl acrylate, pentadecyl acrylate, stearyl acrylate and the like; methacrylic acid ester monomers, including methyl methacrylate, ethyl methacrylate, propyl methacrylate, isoprop~l methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, bornyl methacrylate, isobornyl methacrylate, myristyl methacrylate, pentadecyl methacrylate, stearyl methacrylate, phosphoethyl methacrylate and the like; acrylic acid, methacrylic acid, itaconic acid, maleic acid, furnaric acid, styrene, ~:C~ )6 substituted styrenes, butadiene, acrylonitrile, ethylene, vinyl acetate, vinyl chloride, sodium styrene sulfonates, sodium vinyl sulfonate, acrylamide, methacrylamide and the like may be used.
The removal of water-soluble ions from the aqueous latex polymer emulsion or pressure sensitive adhesive formulation is critical to the operation of this invention. The water-soluble ions may be removed by a number of techniques, including, but not limited to, centrifugation, dialysis, precipitation and deionization with ion exchange resins. The preferred method of removing the water-soluble ions is to contact the aqueous latex polymer emulsion or the formulated pressure sensitive adhesive containing the aqueous latex polymer emulsion with ion exchange resin. Contacting the final pressure sensitive adhesive formulation containing the aqueous latex polymer with the ion exchange resin is preferred.
The aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer may be treated with ion exchange resin either (1) by adding the ion exchange resin to the aqueous latex polymer emulsion or the pressure sensitive adhesive forrnulation containing the aqueous latex polymer; or r)~, (2~ by passing the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer over a column bed of ion exchange resin.
When adding the ion exchange resin to the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer, the ion exchange resin must be mixed thoroughly to permit_~ontact of the ion exchange resin surfaces with the water-soluble ions in the emulsion or adhesive. The contact can be effected by adding to the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer from about 1% by weight to about 100%, preferably greater than about 2%, by weight of the ion exchange resin to the weight of the emulsion or adhesive. The admixture may be agitated to facilitate contact between the ion exchange resin and~he water-soluble ions.
The ion exchange resin may be removed from the mixture by straining through a filter medium such as linen doth, nylon mesh filter and the like to remove all of the ion exchange resin. The procedure may be repeated several times, if necessary, to remove the water-insoluble ions from the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer.
2(~9~,:1{)6 The rate of from about 0.5 bed volume/hour to about 10 bed volumes/hour, of passing the aqueous latex polymer emulsion or the pressure sensitive adhesive formulation containing the aqueous latex polymer over a column bed of ion exchange resin is effective to remove the water-soluble ions. A rate of from about 1 bed volume/hour to about 6 bed volumes/hour is preferred, with a rate of from about 1 bed volume/hour to about 3 bed volumes/hour most preferred.
The preferred method o~ using the ion exchange resins comprises making a mixture of a sulfonic acid type cation exchanger in the acid form (to remove anions) and a quaternary anion exchange resin in the free base form (to remove cations), and contacting the aqueous latex polymer emulsion or the pressure sensitive adhesive containing the aqueous latex polymer to be deionized with the mixture. Such mixtures of cation and anion exchange resins are well-known to those skilled in the art as "mixed beds." Cation and anion exchange resins may also be used in succession. Cation or anion exchange resins may also be used separately, however complete deionization may not be achieved.
3~
Suitable anion exchange resins useful alone, in succession, or in mixed beds include copolymers of styrene and divinyl benzene containing amine or quaternized amine functional groups and the like. Preferred are those resins in spherical bead form, including gel and macroporous beads. Examples of anion exchange resins are disclosed in U.S. Patents 2,591,573; 2,591,574; 2~597r439; 2,597,440;
2,630,427; 2,630,428, 2,630,429; and 2,402,384 which are hereby incorporated herein by reference.
Suitable cation exchange resins useful alone, in succession, or in mixed beds include copolymers of styrene and divinyl benzene containing having strong acid functional groups such as sulfonic acid groups. Preferred are those resins in spherical bead form, including gel and macroporous beads. Examples of cation exchange resins are disclosed in U.S. Patents 4,224,415; 4,256,840; and 4,382,124 which are hereby incorporated herein by reference. ~
More preferred for mixed bed use are anion exchange resins and cation exchange resins having different hydraulic densities, such that the two types of resins in the mixed bed will separate during reversed liquid flow through the bed, to allow easy regeneration of the two reslns.
2c~ n~;
The pH of the pressure sensitive adhesive formulation containing the aqueous latex polymer emulsion after it has been deioni~ed affects the operation of this invention. The pressure sensitive adhesive formulation containing the aqueous latex polymer must have a pH of greater than about 6, with higher pH's preferred. In practice, the pH is limited only to an upper level which does not thicken the pressure sensitive adhesive formulation containing the aqueous latex polyme~,above a viscosity useful in conventional coating techniques. Films cast from deionized pressure sensitive adhesive formulations having pH's less than about 6 exhibit poor water-whitening resistance. To adjust the pH of the pressure sensitive adhesive formulation, non-permanent bases, such as for example ammonium hydroxide, and the like may be added. Permanent bases, such as for example sodium hydroxide, typically are not suitable to adjust the pH because they add permanent ions which are detrimental on water whitening resistance.
The aqueous latex polymer emulsion may have a level of solids from about 40% to about 70%.
The pressure sensitive adhesive may be applied to substrates via 2C~
conventional coating techniques including gravure, roller and slot-die coaters and the like.
The following examples are intended to illustrate the invention;
they are not intended to limit the invention as other applications of the invention will be obvious to ~ose of ordinary skill in the art.
ABB REVIATIONS:
g gra~ns BA butyl acrylate EA ethyl acrylate AA acrylic acid n~
EXAMPLE 1. Preparation of Pressure Sensitive Adhesive Formulations To a 1 pint can equipped with a laboratory stirrer, 100 g latex polymer emulsion was added:
.
Pressure Sensitive Adhesive Compositinn of Latex Polymer Fonnulation Comparative 1 49 BA/49 EA/2 AA
Comparative 2 59 BA~39 EA/2 AA
Comparative 3 75 BA/22 EA/3 AA
At mode~a~ ian, Q012 g Triton(D X-45 su~factan,t, ~0.3 g Emcol~9 4500 surfactant and 0.6 g Drew(E~ T-4201 defoamer were added and mixed. The pressure sensitive adhesive formulation was mixed for an additional 15 minutes. The pH of the final pressure sensitive adhesive formulation was adjusted to a range of 6.5 to 7.0 using 28% by weight solution of ammonium hydroxide.
~C~ )6 EXAMPLE 3. Deionization of Pressure Sensitive Adhesive Formulations Amberlite(3 IRN-150 ion exchange resin, a highly purified mixture of strongly acidic cation resin and strongly basic anion exchange resin with the mixture containing an equivalent of hydrogen ion for each equivalent of hydroxide ion, was added gradually to the pressure sensitive adhesive formulation and stirred to avoid the formation of large clumps. The mixture was stirred for about 2 hours and then filtered through a 325 mesh screen. The procedure was repeated, where necessary. The pressure sensitive adhesive formulations which were not deionized are designated as comparatives.
;~c~r~
EXAMPLE 4. Preparation of Test Specimens The pressure sensitive adhesive formulations were direct-coated onto Mylar~5D film using a Bird applicator and dried at 180F for 15 minutes to give a 1 mil dry film thickness. The test specimens were then nipped to untreated polypropylene. The test specimens were cut into the following sizes:
Test ~ Dimensinns 180 peel adhesion 1 inch wide strips Polyken tack 1 inch wide strips Shear resistance testing 1 inch wide strips Water-whitening resistance 1 inch by 5 inch strips - The test specimens were conditioned at 7~7F and 55% relative humidity overnight prior to all testing.
2~9~
EXAMPLE 5. Water-whitening Resistance Testing To evaluate water-whitening resistance, the test specimens prepared according to Example 4 were placed a 4 ounce glass jar filled with tap water equilibrated to room temperature. The degree of opacity was visually rated at 5 minute intervals for a total of 90 minutes, using the following rating system:
Rating ~ Description . . .
completely transparent 4 slight whitening 3 moderate whitening 2 severe whitening opaque The results are shown in Tables 5.1.
~s~i~n~i Table 5.1 _ . _ Waler whitening Resistance Pres~ure Sen,.itive Adhesive Formulation Time (minute~) Comp~rative 2- 2 16 _.
-~Note: Forml~lated ~ith 15 p~ p~r hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 01 part by weight Triton~ X~5 surfactant; 03 part by weight Emcol6~ 4500 surfactant; and 5 parts by weight Drew~ T~201dehamer EXAMPLE 6. Effect of Deionization Sequence The effect of deionization before and after formulation of the pressure sensitive adhesive was evaluated~ The results are shown in Table 6~1~ Deionization after formulation shows better water-whitening resistance than deionization before formulation~
Table 6.1 _ _ _ _ .
Water-whitening Resist~nce .
Pressure Sensitive Adhesive Fo~mubtion 2' Tirne (minute3) Deionization before formulation Deionization after formulation - 16 5 ~ 5 -~'Note: Formulated with 15 parts per hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 0.1 part by weight TritonE9 X-45 surfactant; 0.3 part by weight Emcol 19 4500 surfactant; and 5 parts by weight DrewX T-4201defoamer ~c~
EXAMPLE 7. Effect of Ion Exchange Resin Weight and Repeatæd Treatment The effect of ion exchange resin weight and repeated treatment were evaluated. The results are shown in Table 7.1. The results show that contacting from about 1% by weight to about 100%, preferably greater than about 2%, by weight of the ion exchange resin based on the weight of the pressure sensitive adhesive formulation is effective to improve the water-whitening resistance. When the procedure was repeated at the 2% by weight level an improvement in the water whitening resistance was also seen.
2~9~06 Table 7 1 Water-whitening Resisbnce P-es~lure Sensltive Adhe~ive Formubtion 2-Time Weight % lon Exchange 30 20 10 Z 2 0 ~minutes) Re~in How many times? 2 2 2 2 1 0 fi 5 5 5 5 5 5 .
'Note Formulated with 15 parts per hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 01 part by weight TritonlD X-45 surfactant; 0 3 part byweight Emcol !9 4500 surfactant; and 5 parts by weight DrewX T-4201defoamer E~XAMPLE 8. Effect of pH on Water Whitening Resistance The effect of pH of the final formulated pressure sensitive adhesive on the water-whitening resistance was evaluated. The results are shown in Table 8.1. The pressure sensitive adhesive formulation which had been deionized but which had not been readjusted to a pH
greater than about 6.0 did not demonstrate an improved resistance to water-whitening.
Table 8.1 Water-whitening Resistance Pres~ure Sensitive Adhesive Formulation Comparati~e 3 3 3 not deionized deionized deionized Time (minutes) pH = 6.7 pH = 1.75 pH = 6.5 , ~5 4 2 4 . _ . _ . .
XAMPLE 9. Pressure Sensitive Adhesive Proper,ty Performance Testing The following tests were performed to demonstrate that deionization does not adversely affect the pressure sensitive adhesive performance properties of formulations. The results for the pressure sensitive adhesive property testing are shown in Table 9.1.
180 Peel Adhesion Test The 180 peel adhesion test was performed according to Pressure Sensitive Tape Council Method Number 1 using dwell times of 20 minutes and 72 hours.
Poluken Tack Test The Polyken tack test was performed using a Polyken Tack Tester from Testing Machines, Inc. with a 1 second dwell tirne, 1 centimeter/second probe withdrawal speed and a 20 gram weight.
Sh~ar Resistance Test The shear resistance test was performed according to Pressure Sensitive Tape Council Method Number 7, using a 1 inch by 1 inch overlap area and 1 kilogram weight.
~c~
Table 9.1 .
180 Peel Adhe9ion ~ounce~/{nch) 20 minute dwell 72 hour dwell adhesive hilure mode adhesive failure mode - ComparaSive 1 58 71 adhesive failure mode adhesive failure mode Polyken Tack (grams) ComparaSive 1 655 Shear Resistance 86 li~ht cohesive failu~e mode Compara~ive 1 99 cohesive~failure mode )6 The results showed that deionization to improve water-whitening did not adversely affect the pressure sensitive adhesive formulations performance properties. In the 180 Peel Adhesion Test, the deionized formulation showed essentially the same peel strength values and the same type of failure mode as the comparative formulation which had not been deionized. In the Polyken Tack Test, the deionized formulation showed only a slight increase in the level of tack as compared to the comparative formulation which hall not been deionized. In the Shear Resistance Test, the deionized formulation showed essentially the same shear strength value and type of failure mode as the comparative formulation which had not been deionized.
Suitable anion exchange resins useful alone, in succession, or in mixed beds include copolymers of styrene and divinyl benzene containing amine or quaternized amine functional groups and the like. Preferred are those resins in spherical bead form, including gel and macroporous beads. Examples of anion exchange resins are disclosed in U.S. Patents 2,591,573; 2,591,574; 2~597r439; 2,597,440;
2,630,427; 2,630,428, 2,630,429; and 2,402,384 which are hereby incorporated herein by reference.
Suitable cation exchange resins useful alone, in succession, or in mixed beds include copolymers of styrene and divinyl benzene containing having strong acid functional groups such as sulfonic acid groups. Preferred are those resins in spherical bead form, including gel and macroporous beads. Examples of cation exchange resins are disclosed in U.S. Patents 4,224,415; 4,256,840; and 4,382,124 which are hereby incorporated herein by reference. ~
More preferred for mixed bed use are anion exchange resins and cation exchange resins having different hydraulic densities, such that the two types of resins in the mixed bed will separate during reversed liquid flow through the bed, to allow easy regeneration of the two reslns.
2c~ n~;
The pH of the pressure sensitive adhesive formulation containing the aqueous latex polymer emulsion after it has been deioni~ed affects the operation of this invention. The pressure sensitive adhesive formulation containing the aqueous latex polymer must have a pH of greater than about 6, with higher pH's preferred. In practice, the pH is limited only to an upper level which does not thicken the pressure sensitive adhesive formulation containing the aqueous latex polyme~,above a viscosity useful in conventional coating techniques. Films cast from deionized pressure sensitive adhesive formulations having pH's less than about 6 exhibit poor water-whitening resistance. To adjust the pH of the pressure sensitive adhesive formulation, non-permanent bases, such as for example ammonium hydroxide, and the like may be added. Permanent bases, such as for example sodium hydroxide, typically are not suitable to adjust the pH because they add permanent ions which are detrimental on water whitening resistance.
The aqueous latex polymer emulsion may have a level of solids from about 40% to about 70%.
The pressure sensitive adhesive may be applied to substrates via 2C~
conventional coating techniques including gravure, roller and slot-die coaters and the like.
The following examples are intended to illustrate the invention;
they are not intended to limit the invention as other applications of the invention will be obvious to ~ose of ordinary skill in the art.
ABB REVIATIONS:
g gra~ns BA butyl acrylate EA ethyl acrylate AA acrylic acid n~
EXAMPLE 1. Preparation of Pressure Sensitive Adhesive Formulations To a 1 pint can equipped with a laboratory stirrer, 100 g latex polymer emulsion was added:
.
Pressure Sensitive Adhesive Compositinn of Latex Polymer Fonnulation Comparative 1 49 BA/49 EA/2 AA
Comparative 2 59 BA~39 EA/2 AA
Comparative 3 75 BA/22 EA/3 AA
At mode~a~ ian, Q012 g Triton(D X-45 su~factan,t, ~0.3 g Emcol~9 4500 surfactant and 0.6 g Drew(E~ T-4201 defoamer were added and mixed. The pressure sensitive adhesive formulation was mixed for an additional 15 minutes. The pH of the final pressure sensitive adhesive formulation was adjusted to a range of 6.5 to 7.0 using 28% by weight solution of ammonium hydroxide.
~C~ )6 EXAMPLE 3. Deionization of Pressure Sensitive Adhesive Formulations Amberlite(3 IRN-150 ion exchange resin, a highly purified mixture of strongly acidic cation resin and strongly basic anion exchange resin with the mixture containing an equivalent of hydrogen ion for each equivalent of hydroxide ion, was added gradually to the pressure sensitive adhesive formulation and stirred to avoid the formation of large clumps. The mixture was stirred for about 2 hours and then filtered through a 325 mesh screen. The procedure was repeated, where necessary. The pressure sensitive adhesive formulations which were not deionized are designated as comparatives.
;~c~r~
EXAMPLE 4. Preparation of Test Specimens The pressure sensitive adhesive formulations were direct-coated onto Mylar~5D film using a Bird applicator and dried at 180F for 15 minutes to give a 1 mil dry film thickness. The test specimens were then nipped to untreated polypropylene. The test specimens were cut into the following sizes:
Test ~ Dimensinns 180 peel adhesion 1 inch wide strips Polyken tack 1 inch wide strips Shear resistance testing 1 inch wide strips Water-whitening resistance 1 inch by 5 inch strips - The test specimens were conditioned at 7~7F and 55% relative humidity overnight prior to all testing.
2~9~
EXAMPLE 5. Water-whitening Resistance Testing To evaluate water-whitening resistance, the test specimens prepared according to Example 4 were placed a 4 ounce glass jar filled with tap water equilibrated to room temperature. The degree of opacity was visually rated at 5 minute intervals for a total of 90 minutes, using the following rating system:
Rating ~ Description . . .
completely transparent 4 slight whitening 3 moderate whitening 2 severe whitening opaque The results are shown in Tables 5.1.
~s~i~n~i Table 5.1 _ . _ Waler whitening Resistance Pres~ure Sen,.itive Adhesive Formulation Time (minute~) Comp~rative 2- 2 16 _.
-~Note: Forml~lated ~ith 15 p~ p~r hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 01 part by weight Triton~ X~5 surfactant; 03 part by weight Emcol6~ 4500 surfactant; and 5 parts by weight Drew~ T~201dehamer EXAMPLE 6. Effect of Deionization Sequence The effect of deionization before and after formulation of the pressure sensitive adhesive was evaluated~ The results are shown in Table 6~1~ Deionization after formulation shows better water-whitening resistance than deionization before formulation~
Table 6.1 _ _ _ _ .
Water-whitening Resist~nce .
Pressure Sensitive Adhesive Fo~mubtion 2' Tirne (minute3) Deionization before formulation Deionization after formulation - 16 5 ~ 5 -~'Note: Formulated with 15 parts per hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 0.1 part by weight TritonE9 X-45 surfactant; 0.3 part by weight Emcol 19 4500 surfactant; and 5 parts by weight DrewX T-4201defoamer ~c~
EXAMPLE 7. Effect of Ion Exchange Resin Weight and Repeatæd Treatment The effect of ion exchange resin weight and repeated treatment were evaluated. The results are shown in Table 7.1. The results show that contacting from about 1% by weight to about 100%, preferably greater than about 2%, by weight of the ion exchange resin based on the weight of the pressure sensitive adhesive formulation is effective to improve the water-whitening resistance. When the procedure was repeated at the 2% by weight level an improvement in the water whitening resistance was also seen.
2~9~06 Table 7 1 Water-whitening Resisbnce P-es~lure Sensltive Adhe~ive Formubtion 2-Time Weight % lon Exchange 30 20 10 Z 2 0 ~minutes) Re~in How many times? 2 2 2 2 1 0 fi 5 5 5 5 5 5 .
'Note Formulated with 15 parts per hundred parts latex polymer of a mixture of 10 parts by weight of 59BA/39EA/2AA; 01 part by weight TritonlD X-45 surfactant; 0 3 part byweight Emcol !9 4500 surfactant; and 5 parts by weight DrewX T-4201defoamer E~XAMPLE 8. Effect of pH on Water Whitening Resistance The effect of pH of the final formulated pressure sensitive adhesive on the water-whitening resistance was evaluated. The results are shown in Table 8.1. The pressure sensitive adhesive formulation which had been deionized but which had not been readjusted to a pH
greater than about 6.0 did not demonstrate an improved resistance to water-whitening.
Table 8.1 Water-whitening Resistance Pres~ure Sensitive Adhesive Formulation Comparati~e 3 3 3 not deionized deionized deionized Time (minutes) pH = 6.7 pH = 1.75 pH = 6.5 , ~5 4 2 4 . _ . _ . .
XAMPLE 9. Pressure Sensitive Adhesive Proper,ty Performance Testing The following tests were performed to demonstrate that deionization does not adversely affect the pressure sensitive adhesive performance properties of formulations. The results for the pressure sensitive adhesive property testing are shown in Table 9.1.
180 Peel Adhesion Test The 180 peel adhesion test was performed according to Pressure Sensitive Tape Council Method Number 1 using dwell times of 20 minutes and 72 hours.
Poluken Tack Test The Polyken tack test was performed using a Polyken Tack Tester from Testing Machines, Inc. with a 1 second dwell tirne, 1 centimeter/second probe withdrawal speed and a 20 gram weight.
Sh~ar Resistance Test The shear resistance test was performed according to Pressure Sensitive Tape Council Method Number 7, using a 1 inch by 1 inch overlap area and 1 kilogram weight.
~c~
Table 9.1 .
180 Peel Adhe9ion ~ounce~/{nch) 20 minute dwell 72 hour dwell adhesive hilure mode adhesive failure mode - ComparaSive 1 58 71 adhesive failure mode adhesive failure mode Polyken Tack (grams) ComparaSive 1 655 Shear Resistance 86 li~ht cohesive failu~e mode Compara~ive 1 99 cohesive~failure mode )6 The results showed that deionization to improve water-whitening did not adversely affect the pressure sensitive adhesive formulations performance properties. In the 180 Peel Adhesion Test, the deionized formulation showed essentially the same peel strength values and the same type of failure mode as the comparative formulation which had not been deionized. In the Polyken Tack Test, the deionized formulation showed only a slight increase in the level of tack as compared to the comparative formulation which hall not been deionized. In the Shear Resistance Test, the deionized formulation showed essentially the same shear strength value and type of failure mode as the comparative formulation which had not been deionized.
Claims (5)
1. A process for improving the water-whitening resistance of a pressure sensitive adhesive containing an aqueous latex emulsion, where the pressure sensitive adhesive or the aqueous latex emulsion contain water-soluble ions, comprising:
(a) removing the water-soluble ions; and (b) adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø
(a) removing the water-soluble ions; and (b) adjusting the pH of the pressure sensitive adhesive formulation to at least about 6Ø
2. The process of claim 1 where the water-soluble ions are removed by contacting the aqueous latex emulsion or the pressure sensitive adhesive with ion exchange resin.
3. The process of claim 2 where the ion exchange resin is a mixture of a sulfonic acid type cation exchanger in the acid form and a quaternary anion exchange resin in the free base form.
4. The process of claim 2 where the pH is adjusted using a non-permanent base.
5. The product of the process of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/888,563 US5286843A (en) | 1992-05-22 | 1992-05-22 | Process for improving water-whitening resistance of pressure sensitive adhesives |
| US07/888,563 | 1992-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2096106A1 true CA2096106A1 (en) | 1993-11-23 |
Family
ID=25393418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002096106A Abandoned CA2096106A1 (en) | 1992-05-22 | 1993-05-12 | Process for improving water-whitening resistance of pressure sensitive adhesives |
Country Status (21)
| Country | Link |
|---|---|
| US (2) | US5286843A (en) |
| EP (1) | EP0571069B1 (en) |
| JP (1) | JPH0649431A (en) |
| KR (1) | KR930023434A (en) |
| CN (1) | CN1079241A (en) |
| AT (1) | ATE133697T1 (en) |
| AU (1) | AU665810B2 (en) |
| BR (1) | BR9301894A (en) |
| CA (1) | CA2096106A1 (en) |
| CZ (1) | CZ49593A3 (en) |
| DE (1) | DE69301425T2 (en) |
| ES (1) | ES2083823T3 (en) |
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| GR (1) | GR3018855T3 (en) |
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| HU (1) | HUT65764A (en) |
| IL (1) | IL105148A (en) |
| MX (1) | MX9302872A (en) |
| NO (1) | NO931097L (en) |
| SK (1) | SK23993A3 (en) |
| ZA (1) | ZA932161B (en) |
Families Citing this family (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997011996A1 (en) * | 1995-09-29 | 1997-04-03 | Avery Dennison Corporation | Process for preparing hot water whitening resistant emulsion pressure sensitive adhesives |
| AU2865797A (en) * | 1996-07-30 | 1998-02-05 | Rohm And Haas Company | The reduction of microfoam in spray applied thermoplastic coatings |
| AU714737B2 (en) * | 1996-10-15 | 2000-01-13 | Rohm And Haas Company | Coating compositions containing ion exchange resins |
| US7423167B2 (en) * | 1997-01-28 | 2008-09-09 | Stepan Company | Ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids |
| US20020161108A1 (en) * | 2000-03-09 | 2002-10-31 | Stepan Company, A Corporation Of The State Of Delaware | Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids |
| US6242526B1 (en) | 1997-01-28 | 2001-06-05 | Stepan Company | Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes |
| ATE258561T1 (en) * | 1997-01-28 | 2004-02-15 | Stepan Co | EMULSION POLYMERIZATION PROCESS USING ETHYLENEICALLY UNSATURATED AMINE SALTS OF SULFONIC ACID, PHOSPHORIC ACID AND CARBOXYLIC ACID |
| US6013722A (en) * | 1998-01-27 | 2000-01-11 | 3M Innovative Properties Company | Non-whitening emulsion pressure sensitive adhesives |
| DK1198502T3 (en) * | 1999-04-12 | 2004-11-22 | Ashland Inc | Pressure sensitive adhesives |
| IL136025A0 (en) * | 1999-05-14 | 2001-05-20 | Pfizer Prod Inc | Combination therapy for the treatment of migraine |
| US20040076785A1 (en) * | 2000-05-09 | 2004-04-22 | Richards Corlyss J. | Water-whitening resistant latex emulsion pressure sensitive adhesive and its production |
| US6964991B2 (en) | 2001-07-13 | 2005-11-15 | Surf Chip, Inc. | Process for improving water-whitening resistance of pressure sensitive adhesives |
| US7169846B2 (en) * | 2001-07-13 | 2007-01-30 | Cytec Surface Specialties, Inc. | Process for improving water-whitening resistance of pressure sensitive adhesives |
| US6995207B2 (en) * | 2003-03-31 | 2006-02-07 | Chen Augustin T | Removable pressure sensitive adhesives with plasticizer resistance properties |
| US20040260034A1 (en) * | 2003-06-19 | 2004-12-23 | Haile William Alston | Water-dispersible fibers and fibrous articles |
| US20110139386A1 (en) * | 2003-06-19 | 2011-06-16 | Eastman Chemical Company | Wet lap composition and related processes |
| US7892993B2 (en) * | 2003-06-19 | 2011-02-22 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
| US8513147B2 (en) | 2003-06-19 | 2013-08-20 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
| US7687143B2 (en) * | 2003-06-19 | 2010-03-30 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
| DE10353201A1 (en) * | 2003-11-13 | 2005-06-16 | Basf Ag | Polymer dispersions containing sulfosuccinic acid ester |
| US7304101B2 (en) * | 2004-07-19 | 2007-12-04 | 3M Innovative Properties Company | Method of purifying a dispersion of ionic fluoropolymer |
| US20060014887A1 (en) * | 2004-07-19 | 2006-01-19 | 3M Innovative Properties Company | Method of hydrolyzing a dispersion of ionic fluoropolymer |
| EP2789664B1 (en) * | 2005-05-20 | 2018-09-05 | Avery Dennison Corporation | Water whitening-resistant pressure sensitive adhesives |
| US7635745B2 (en) * | 2006-01-31 | 2009-12-22 | Eastman Chemical Company | Sulfopolyester recovery |
| US7645827B2 (en) * | 2006-03-08 | 2010-01-12 | 3M Innovative Properties Company | High shear pressure-sensitive adhesive |
| US7531595B2 (en) * | 2006-03-08 | 2009-05-12 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing silica nanoparticles |
| EP1862520A1 (en) * | 2006-06-01 | 2007-12-05 | Basf Aktiengesellschaft | film labels |
| US20080160859A1 (en) * | 2007-01-03 | 2008-07-03 | Rakesh Kumar Gupta | Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters |
| DE102008000270A1 (en) | 2007-02-14 | 2008-08-28 | Basf Se | Producing aqueous dispersions of polyadducts comprises reacting starting compounds in a high-boiling water-miscible solvent, dispersing the resulting solution in water and removing the solvent |
| US20080200587A1 (en) * | 2007-02-16 | 2008-08-21 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing acicular silica particles crosslinked with polyfunctional aziridines |
| US8512519B2 (en) | 2009-04-24 | 2013-08-20 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
| US20120183861A1 (en) | 2010-10-21 | 2012-07-19 | Eastman Chemical Company | Sulfopolyester binders |
| CN102746601B (en) | 2011-04-18 | 2014-11-26 | 罗门哈斯公司 | Water whitening resistance copolymer dispersion for coating material |
| US8882963B2 (en) | 2012-01-31 | 2014-11-11 | Eastman Chemical Company | Processes to produce short cut microfibers |
| US9617685B2 (en) | 2013-04-19 | 2017-04-11 | Eastman Chemical Company | Process for making paper and nonwoven articles comprising synthetic microfiber binders |
| US9598802B2 (en) | 2013-12-17 | 2017-03-21 | Eastman Chemical Company | Ultrafiltration process for producing a sulfopolyester concentrate |
| US9605126B2 (en) | 2013-12-17 | 2017-03-28 | Eastman Chemical Company | Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion |
| AR100280A1 (en) * | 2014-05-22 | 2016-09-21 | Rohm & Haas | POLYMER BINDERS FOR INK JET PRINTERS |
| BR112018071902A2 (en) | 2016-05-12 | 2019-02-05 | Basf Se | aqueous coating composition, polymer film, packaging, method of forming a polymeric film, and use of the composition. |
| CN106990024B (en) * | 2017-05-22 | 2019-10-11 | 武汉科技大学 | A kind of detection method of MgO-CaO material hydration resistance |
| WO2021023568A1 (en) | 2019-08-05 | 2021-02-11 | Basf Se | Method of improving shear stability of highly concentrated aqueous adhesive polymer compositions |
| WO2023208919A1 (en) | 2022-04-28 | 2023-11-02 | Röhm Gmbh | Poly(meth)acrylat impact modifier with reduced metal ion content and method for its production |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2402384A (en) * | 1941-04-09 | 1946-06-18 | Resinous Prod & Chemical Co | Ion exchange polyamine resins and method of preparing same |
| US2591573A (en) * | 1947-07-05 | 1952-04-01 | Rohm & Haas | Resinous insoluble reaction products of tertiary amines with haloalkylated vinyl aromatic hydrocarbon copolymers |
| NL73179C (en) * | 1947-07-05 | |||
| US2597439A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Weakly basic anion-exchange polymers |
| US2597440A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Strongly basic anion-exchange resins |
| US2630427A (en) * | 1951-10-05 | 1953-03-03 | Rohm & Haas | Preparation of strongly basic anion-exchange resins |
| US2630429A (en) * | 1951-10-05 | 1953-03-03 | Rohm & Haas | Preparation of weakly basic anion-exchange resins |
| US2630428A (en) * | 1951-10-05 | 1953-03-03 | Rohm & Haas | Preparation of insoluble quaternary ammonium alkoxides |
| NL241315A (en) * | 1958-07-18 | |||
| US4382124B1 (en) * | 1958-07-18 | 1994-10-04 | Rohm & Haas | Process for preparing macroreticular resins, copolymers and products of said process |
| BE587088A (en) * | 1959-01-29 | |||
| US3577375A (en) * | 1966-10-10 | 1971-05-04 | Gulf Research Development Co | Stable aqueous dispersion of ethylene polymers produced by contacting the dispersions with an acidic sulfonated cation exchange resin charged with ammonium ions |
| US3509084A (en) * | 1966-10-26 | 1970-04-28 | Gulf Research Development Co | Ion exchange process |
| US3494878A (en) * | 1967-11-02 | 1970-02-10 | Rohm & Haas | Stain resistant water-based coating compositions |
| JPS60102978A (en) * | 1983-11-11 | 1985-06-07 | Nippon Light Metal Co Ltd | Blank member having hydrophilic film |
| US4728680A (en) * | 1986-01-30 | 1988-03-01 | The Glidden Company | Pigmented low temperature cure emulsions |
| US4853422A (en) * | 1987-09-24 | 1989-08-01 | The Glidden Company | Thermosetting arcylic latexes |
| US5081166A (en) * | 1988-04-21 | 1992-01-14 | S. C. Johnson & Son, Inc. | Process for producing a stabilized latex emulsion adhesive |
| US5073457A (en) * | 1988-12-01 | 1991-12-17 | Minnesota Mining And Manufacturing Company | Repositionable adhesive |
| US4900592A (en) * | 1989-02-06 | 1990-02-13 | The Glidden Company | Ion-exchanged, crosslinking latex paints |
| US5424122A (en) * | 1991-12-09 | 1995-06-13 | Minnesota Mining And Manufacturing Company | Nonionic, Ph-neutral pressure sensitive adhesive |
-
1992
- 1992-05-22 US US07/888,563 patent/US5286843A/en not_active Expired - Fee Related
-
1993
- 1993-03-16 DE DE69301425T patent/DE69301425T2/en not_active Expired - Fee Related
- 1993-03-16 ES ES93301987T patent/ES2083823T3/en not_active Expired - Lifetime
- 1993-03-16 AT AT93301987T patent/ATE133697T1/en active
- 1993-03-16 EP EP93301987A patent/EP0571069B1/en not_active Expired - Lifetime
- 1993-03-23 FI FI931284A patent/FI931284A/en unknown
- 1993-03-23 AU AU35375/93A patent/AU665810B2/en not_active Ceased
- 1993-03-23 HU HU9300826A patent/HUT65764A/en unknown
- 1993-03-24 CZ CZ93495A patent/CZ49593A3/en unknown
- 1993-03-24 IL IL10514893A patent/IL105148A/en not_active IP Right Cessation
- 1993-03-25 NO NO931097A patent/NO931097L/en unknown
- 1993-03-25 SK SK239-93A patent/SK23993A3/en unknown
- 1993-03-26 ZA ZA932161A patent/ZA932161B/en unknown
- 1993-05-10 KR KR1019930007950A patent/KR930023434A/en not_active Application Discontinuation
- 1993-05-12 CA CA002096106A patent/CA2096106A1/en not_active Abandoned
- 1993-05-14 BR BR9301894A patent/BR9301894A/en not_active Application Discontinuation
- 1993-05-17 JP JP5115038A patent/JPH0649431A/en not_active Withdrawn
- 1993-05-18 MX MX9302872A patent/MX9302872A/en unknown
- 1993-05-21 CN CN93106250A patent/CN1079241A/en active Pending
- 1993-11-15 US US08/152,605 patent/US5536811A/en not_active Expired - Fee Related
-
1996
- 1996-02-01 GR GR960400071T patent/GR3018855T3/en unknown
- 1996-08-29 HK HK160796A patent/HK160796A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| US5536811A (en) | 1996-07-16 |
| EP0571069A3 (en) | 1993-12-08 |
| NO931097L (en) | 1993-11-23 |
| CZ49593A3 (en) | 1994-02-16 |
| FI931284A (en) | 1993-11-23 |
| HK160796A (en) | 1996-09-06 |
| JPH0649431A (en) | 1994-02-22 |
| ES2083823T3 (en) | 1996-04-16 |
| BR9301894A (en) | 1993-11-30 |
| HU9300826D0 (en) | 1993-07-28 |
| HUT65764A (en) | 1994-07-28 |
| CN1079241A (en) | 1993-12-08 |
| ZA932161B (en) | 1993-11-22 |
| SK23993A3 (en) | 1993-12-08 |
| FI931284A0 (en) | 1993-03-23 |
| ATE133697T1 (en) | 1996-02-15 |
| EP0571069B1 (en) | 1996-01-31 |
| AU665810B2 (en) | 1996-01-18 |
| MX9302872A (en) | 1993-11-01 |
| EP0571069A2 (en) | 1993-11-24 |
| GR3018855T3 (en) | 1996-05-31 |
| DE69301425T2 (en) | 1996-08-08 |
| KR930023434A (en) | 1993-12-18 |
| US5286843A (en) | 1994-02-15 |
| DE69301425D1 (en) | 1996-03-14 |
| IL105148A (en) | 1995-12-08 |
| IL105148A0 (en) | 1993-07-08 |
| AU3537593A (en) | 1993-11-25 |
| NO931097D0 (en) | 1993-03-25 |
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