Patent Grant
10590315
The invention relates to acrylic emulsion pressure sensitive adhesives, and more particularly, to acrylic adhesives for use in removable polymeric film labels.
It is common practice to apply labels to containers or bottles formed from polymers or glass. Such containers and bottles are available in a wide variety of shapes and sizes for holding many different types of materials such as detergents, chemicals, motor oil, beverages, including juices, soft drinks, alcoholic beverages, etc. The labels provide information such as the supplier of the container or the contents of the container.
Polymeric film materials and film facestocks have been described for use as labels in various fields. Polymeric labels are increasingly desired for many applications, particularly clear polymeric labels since they provide a no-label look to decorated glass and plastic containers. Paper labels block the visibility of the container and/or the contents in the container. Clear polymeric labels enhance the visual aesthetics of the container, and therefore the product, and are growing much faster than paper labels in the package decoration market as consumer product companies are continuously trying to upgrade the appearance of their products. Polymeric film labels also have superior mechanical properties, such as tensile strength and abrasion resistance.
In the bottled beverage industry, particularly the bottled beer industry, the standards to which the labels are held can be quite stringent. For example, the labeled bottles must withstand the pasteurization process. The labels must be abrasion resistant because of the demands of the bottling, packing, shipping and storage processes. The labels must also survive being immersed in ice water for extended periods of time.
In addition, the bottles used in the beverage industry are generally reused many times. The bottles must be cleaned and the labels removed prior to refilling and relabeling the bottles. Paper labels, while being generally less aesthetically desirable, are easily removed during the washing process in which the bottles are subjected to hot washing liquid such as dilute caustic soda that has been heated to 50-90° C. Because polymeric labels do not possess the water permeability of the paper labels, the polymeric labels have been found to be more difficult to completely remove with the existing washing process.
Accordingly, it would be desirable to produce polymeric film labels that can be completely removed from the bottles during the washing process, yet maintain their superior aesthetic and mechanical properties. It would also be desirable to produce a polymeric label having a pressure sensitive adhesive that is capable of being coated onto the polymeric film at high speeds and that can be quickly and cleanly removed from the bottle or substrate.
The present invention provides an acrylic emulsion pressure sensitive adhesive (PSA) that removes quickly and cleanly from glass and polymer-coated glass bottles in water at elevated temperatures and dilute caustic solution.
An emulsion based pressure sensitive adhesive composition is provided that comprises a pressure sensitive adhesive copolymer of a plurality of copolymerizable monomers comprising at least one polymerizable acid, wherein the composition is neutralized to a pH of greater than 4.5 with at least one hydroxy functional amine, and wherein the composition is removable upon exposure to an aqueous caustic solution at a temperature of at least 50° C.
In one embodiment, the adhesive composition includes a pressure sensitive adhesive copolymer comprising a copolymer of (a) about 75% to about 90% by weight of one or more alkyl acrylates having from about 4 to about 12 carbon atoms in the alkyl group; (b) about 0.25% to about 5% by weight of one or more acid monomers; (c) about 10% to about 20% by weight of at least one hard monomer; (d) 0 to about 1% by weight of at least one multifunctional crosslinking monomers.
The pressure sensitive adhesive is particularly useful for a removable label for reusable containers. In one embodiment, there is provided a removable label comprising: (a) a first polymeric layer having a first coefficient of thermal expansion; (b) a second polymeric layer having a second coefficient of linear thermal expansion underlying the first polymeric layer, wherein the first coefficient of linear thermal expansion is less than the second coefficient of linear thermal expansion; and (c) an adhesive layer underlying the second polymeric layer, the adhesive layer comprising an emulsion based pressure sensitive adhesive composition comprising a pressure sensitive adhesive copolymer of a plurality of copolymerizable monomers comprising at least one polymerizable acid; wherein the composition is neutralized to a pH of greater than 4.5 with at least one hydroxy functional amine; and wherein the label is reversibly curled toward the first polymeric layer at a temperature at or above 50° C. and the adhesive is removable upon exposure to an aqueous caustic solution at a temperature of at least 50° C.
In another embodiment, there is provided a removable label comprising: (a) a polymeric layer comprising at least one shrinkable film wherein the film is stretched in at least one direction; (b) an adhesive layer underlying the polymeric layer, the adhesive layer comprising an emulsion based pressure sensitive adhesive composition comprising a pressure sensitive adhesive copolymer of a plurality of copolymerizable monomers comprising at least one polymerizable acid; wherein the composition is neutralized to a pH of greater than 4.5 with at least one hydroxy functional amine; and wherein the polymeric layer irreversibly shrinks at a temperature at or above 50° C. and the adhesive is removable upon exposure to an aqueous caustic solution at a temperature of at least 50° C.
In one embodiment of the present invention, the acrylic emulsion pressure sensitive adhesive contains a pressure sensitive adhesive copolymer of a plurality of copolymerizable monomers. The copolymerizable monomers include (a) one or more alkyl acrylates having from about 4 to about 12 carbon atoms in the alkyl group; (b) one or more acid monomers; (c) at least one hard monomer; and (d) optionally, at least one multifunctional crosslinking monomers.
The acrylic emulsion pressure sensitive adhesive copolymer, in one embodiment, comprises a plurality of copolymerizable monomers, the major portion of which is one or more alkyl acrylates having about 4 to about 12 carbon atoms in the alkyl group. Non-limiting examples of alkyl acrylates having about 4 to about 12 carbon atoms in the alkyl group include butyl acrylate, hexyl acrylate, heptyl acrylate, n-octyl acrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate and nonyl acrylate. In one embodiment, the copolymer comprises about 75% to about 90% by weight of the alkyl acrylate having from about 4 to about 12 carbon atoms in the alkyl group. In another embodiment, the copolymer comprises about 77% to about 85% by weight of the alkyl acrylate.
The copolymer comprises about 0.25% up to about 5% by weight, or from about 0.5% to about 3% by weight of at least one unsaturated carboxylic acid containing from 3 to about 8 carbon atoms. Non-limiting examples of ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, itaconic acid and beta-carboxyethyl acrylate.
As used herein, the term “multifunctional crosslinking monomer” means a monomer means a monomer that is copolymerizable with acrylic monomers and that has at least one carbon-carbon double bond and at least one other functional group capable of entering into a polymerization or crosslinking reaction. In one embodiment, the copolymer comprises up to about 1% by weight of at least one multifunctional crosslinking monomer. In another embodiment, the copolymer comprises up to about 0.5%, or from about 0.01% to about 0.5% by weight of at least one multifunctional crosslinking monomer. Non-limiting examples of such monomers include multifunctional (meth)acrylates, e.g., diacrylates, triacrylates, dimethacrylates, and trimethylacrylates; multifunctional allylic compounds, e.g., diallyl maleate and allyl methacrylate; multifunctional crosslinking monomers having a vinyl group; and multifunctional crosslinking monomers having a reactive heteroatom-containing functional group such as the imidazolidone group. A non-limiting list includes the following:
As used herein, the term “hard monomer” refers to a monomer the homopolymer of which is not inherently tacky at ambient temperatures and which has a Tg greater than about −25° C. Non-limiting examples include methyl and ethyl acrylate, methyl and ethyl methacrylate, vinyl acetate, styrene, and acrylonitrile. In one embodiment, the copolymer comprises about 10% to about 20% by weight of hard monomer, or about 15% to about 20% by weight of hard monomer.
The monomers may be polymerized in the presence of a surfactant or a mixture of surfactants. The total amount of surfactant used can be in the range of about 0 to about 7%, or about 1.3% to about 5% based on the weight of the polymer. Anionic surfactants, nonionic surfactants, and combinations thereof may be used. Suitable anionic surfactants include, for example, alkyl sulfates, alkyl phenol ethoxysulfates, alkyl sulfonates, alkaryl sulfonates and alkyl sulfosuccinates, such as for example, sodium lauryl sulfate, nonyl phenol ethoxy(4)sulfate, sodium dodecyl benzene sulfonate, disodium dioctyl sulfosuccinates, as well as mixtures thereof. Suitable nonionic surfactants include, for example, ethoxylated alkyl phenols, poly(ethylene oxide/propylene oxide) block copolymers, such as, for example, ethoxylated (10-60 moles ethylene oxide) nonyl phenol, as well as mixtures thereof.
In one embodiment, a combination of surfactants is used in the course of polymerizing the monomers, with anionic surfactants being particularly useful. In particular, a mixture of two different surfactants may be used. In one embodiment, the first type of surfactant is a sulfate of an ethoxylated alcohol, e.g., a sodium lauryl ether sulfate. Non-limiting examples include Disponil FES 77 and Disponil FES 993 from Cognis Corp. and Polystep B-19 from Stepan Company. The second type of surfactant is, in one embodiment, a sulfosuccinate or derivative, e.g., a dioctyl ester of sodium sulfosuccinic acid. Non-limiting examples include Aerosol OT-75 from Cytec Industries, Inc. and Disponil SUS IC 875 from Cognis Corp. In another embodiment, the second type of surfactant is a modified fatty alcohol polyglycolether. Non-limiting examples include Disponil AFX 1080 and Disponil AFX 2075 from Cognis Corp.
In addition to the monomers and surfactants described above, additional ingredients, reagents, processing aids, and other components are used in preparing preferred embodiments of the invention. A non-limiting list includes polymerization catalysts (initiators), chain transfer agents, neutralizers, accelerators, tackifiers, defoaming agents, thickeners or rheology modifiers, buffers, antioxidants and biocides.
Suitable thermal polymerization initiators include, but are not limited to, sodium persulfate, potassium persulfate, ammonium persulfate, sodium perborated, and ammonium or alkali metal peroxy disulfate salts. The initiator may be used alone or in combination with a minor amount of one or more reducing components or activators, such as, for example sodium sulfoxylate formaldehyde, alkali metal and ammonium salts of sulfur-containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formadinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite, amines such as ethanolamine, glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glyceric acid, malic acid, 2-hydroxy-2-sulfinatoacetic acid, tartaric acid and salts of the preceding acids.
A chain transfer agent may be employed in the preparation of the adhesive. The weight average molecular weight (Mw) of the emulsion polymer may be adjusted through the addition of a chain transfer agent, such as n-dodecyl mercaptan, during emulsion polymerization to give a suitable balance of adhesive and cohesive strength. Suitable chain transfer agents include, but are not limited to, isopropanol, halogenated compounds, n-butyl mercaptan, n-amyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, alkyl thioglycolate, mercaptopropionic acid, and alkyl mercaptoalkanoate. According to one embodiment of the invention, chain transfer agent is not required but in some embodiments it is used in an amount of from 0.001 to 0.5, including from 0.0025 to 0.1, moles per kg dry polymer weight. Linear or branched C4-C22 alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan are particularly useful.
In the preparation of the acrylic emulsion polymer, a neutralizer is included. By “neutralizer”, what is meant is a basic material that is capable of entering into an acid-base reaction with the acid monomer. Suitable neutralizers include poly-hydroxy functional amines, such as for example, triethanolamine, 2-[bis-(2-hydroxyethyl)-amino]-2-hydroxymethyl propane-1,3-diol (bis tris methane), 2-amino-2-(hydroxymethyl)-1,3-propanediol (trizma base), N-methyl-D-glucamine, N,N,N′N′-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N′N′-tetrakis-(2-hydroxypropyl)-ethylenediamine.
An organic salt, for example, sodium citrate, sodium gluconate or sodium acetate may be used in combination with the neutralizer to enhance the removability of the adhesive. An inorganic acid salt may also be used. Alternatively, an organic acid neutralized by a hydroxy amine can be used. Non-limiting examples of organic acids include acetic acid, p-toluene sulfonic acid, citric acid, gluconic acid, maleic acid and dodecylbenzene sulfonic acid. The organic acids can be either added to the water phase during the polymerization or added post polymerization.
Chemical crosslinkers may or may not be present in the composition. If present, the external crosslinkers are provided in an amount up to about 5 by weight, based on the weight of dry adhesive, to further increase the cohesive strength. Non-limiting examples of external crosslinkers include chromium acetate, zirconium ammonium carbonate, aluminum acetate, polyaziridines, carbodiimides and the like. For polyaziridines, the amount of crosslinker used is typically less than about 1% by weight, or about 0.6% or less by weight, based on the weight of dry adhesive.
The adhesive composition may contain, in addition to the emulsion acrylic copolymer, an emulsifiable wax and a plasticizer. Non-limiting examples of emulsifiable waxes include emulsified petroleum resins, paraffin waxes, oxidized paraffin waxes, microcrystalline waxes, carnauba waxes, montan waxes, polyethylene waxes, and the like. Non-limiting examples of plasticizers include phthalates, such as butyl benzyl phthalate, and dioctyl phthalate; adipates; benzoates; citrates, such as triethyl citrate and acyl tributyl citrate; maleates; oleates; phosphates; sebacates; stearates; epoxidized vegetable oils; rosin derivatives, and polymeric plasticizers, such as low molecular weight acrylic polymers that lower the Tg and storage modulus of the PSA.
The pressure sensitive adhesives can be applied to a release liner or facestock using conventional methods. For example, the PSA can be applied to a release liner using slide coating, multilayer die coating, die/slide combination coating and the like, and then laminated to a facestock.
While adhesive coat weights can vary considerably, depending upon the facestock and intended application, in general, the adhesive is applied to a dry coat weight of from about 12 to about 25 grams per square meter (g/m2), or from 13 to about 21 g/m2.
A wide variety of facestocks or backings, including paper and polymeric film facestocks, are contemplated for use with the adhesive composition. The facestock may be primed or unprimed. The facestock may be surface treated by, for example, corona discharge, flame, plasma, etc, to provide the surfaces with desirable properties such as improved adhesion to subsequently applied layers. Procedures for corona treating and flame treating of polymeric films are a well known to those skilled in the art.
The term “overlies” and cognate terms such a overlying and the like, when referring to the relationship of one or a first layer relative to another or a second layer, refer to the fact that the first layer partially or completely overlies the second layer. The first layer overlying the second layer may or may not be in contact with the second layer. For example, one or more additional layers may be positioned between the first and the second layer. The term “underlies” and cognate terms such as “underlying” and the like have similar meanings except that the first layer partially or completely lies under, rather than over the second layer.
The term “transparent” when referring to one or more layers of the label means any material beneath such layers can be seen through such layers. In reference to the use of the “transparent” or “clear” labels applied to clear containers, such as beer bottles, the bottle and the beer within the bottle are visible through the label.
The term “clear” when referring to one or more layers of the label or to the label itself means the opacity of the layers or label is less than about 5%, and the layers or the label has a haze of less than about 10%. Opacity is measured in accordance with TAPPI Test T425 os, and haze is measured in accordance with ASTM Test Method D-1003.
The polymeric facestock may be a monolayer film or a multilayer film. The multilayer film may comprise from two to ten or more layers. The polymer facestock may be oriented or not oriented. The polymer facestock may be transparent or opaque. Opaque facestocks generally comprise a polymer as described below and one or more pigments to provide the facestock, or one layer of a multilayer facestock with the desired color. Pigments useful for this purpose are well known in the art. For example, white films can be prepared by introducing titanium dioxide and other white pigments into the polymer. Carbon black may be introduced to provide a black or grey facestock or film.
A wide variety of polymer film materials are useful in preparing the polymeric layers useful in the present invention. For example, the polymeric film material may include polymers and copolymers such as at least one polyolefin, polyacrylate, polystyrene, polyamide, polyvinyl alcohol, poly(alkylene acrylate), poly(ethylene vinyl alcohol), poly(alkylene vinyl acetate), polyurethane, polyacrylonitrile, polyester, polyester copolymer, fluoropolymer, polysulfone, polycarbonate, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, ionomers based on sodium or zinc salts of ethylene methacrylic acid, cellulosics, polyacrylonitrile, alkylene-vinyl acetate copolymer, or mixtures of two or more thereof.
In one embodiment, the adhesive is applied to a reversibly curlable facestock film. Such films are described in International Publication WO2006/076327, the disclosure of which is hereby incorporated by reference. Reversibly curable films contain at least two polymeric layers having different coefficients of linear thermal expansion, such that, upon exposure to elevated temperatures, the film is reversibly curled. These films are particularly useful for removable labels for reusable containers. The labels for reusable beverage bottles, including beer bottles, are subjected to hot, caustic washing liquid to remove the label. The temperature of the washing liquid may be greater than or equal to about 50° C., about 60° C., about 70° C., about 80° C. or higher. As the label curls or distorts, the adhesive is exposed to the washing liquid and the label is quickly and cleanly removed from the bottle.
As illustrated in
The coefficient of thermal expansion is determined by the equation:
Coefficient of Linear Thermal Expansion (%)=[(B−A)/A]×100 (1)
where A and B represent the measured length (cm) of a specimen of a resin after standing at 0° C. and 50° C., respectively, for 2 minutes, the specimen being 1 cm in width, 4.5 cm in length, and not more than 0.5 cm in thickness as prepared at room temperature.
When subjected to the higher temperature, such as that of the wash liquid, the label will curl and be removed from the underlying substrate to which it is adhered provided the curl force of the label (FLabel) is greater than the peel adhesion of the label to the underlying substrate (FPA):
FLabel>FPA
The curl force of the label, FLabel, can be determined using the following equation:
FLabel=(α2−α1)(T−T0)(⅛t)(E1E2/(E1+E2)) (2)
wherein α2 is the coefficient of linear thermal expansion of the bottom layer (polymeric layer 12); α1 is the coefficient of linear thermal expansion of the top layer (polymeric layer 11); T is the temperature of the washing liquid. T0 is the temperature at which the label is made, typically, room temperature (23° C.); t is the total thickness of the label; E1 is the modulus of elasticity of the top layer (polymeric layer 11) and E2 is the modulus of elasticity of the bottom layer (polymeric layer 12).
In one embodiment, the difference between the coefficient of linear thermal expansion of the bottom layer and that of the top layer, (α2−α1) is greater than or equal to about 3×10−5 (1/° C.). In one embodiment, α2−α1 is about 7×10−5 (1/° C.).
The polymeric layers useful in the present invention do not exhibit heat shrinkage beyond the typically accepted limits of heat stable pressure sensitive adhesive films. e.g., <1% at 70° C. and <2% at 100° C. In one embodiment, the polymeric layer 11 has a heat shrinkage of less than 4% at 80° C.
The polymeric layers 11 and 12 may comprise any of the polymeric film materials described above. Each of the polymeric layers 11 and 12 may be a monolayer film or a multilayer film. In one embodiment, polymeric layers 11 and 12 are coextruded. For example polymeric layers 11 and 12 may comprise a polypropylene/ethylene vinyl acetate coextrudate; a polyacrylate/polyethylene coextrudate; or a polyacrylate/ethylene vinyl alcohol coextrudate. Many other coextruded combinations are possible, including coextrudates comprising more than two layers.
In one embodiment, polymeric layer 11 and polymeric layer 12 are laminated together. Polymeric layer 12 may comprise a coextruded film or may comprise a monolayer film. Polymeric layer 11 may comprise a coextruded film or may comprise a monolayer film. Polymeric layers 11 and 12 typically have a different coefficient of linear thermal expansion in the machine direction (MD) and have a very low coefficient of linear thermal expansion in the cross direction (CD) when the curt is in the machine direction of the label. Alternatively, when the curt is in the cross direction of the label, the polymeric layers 11 and 12 have different coefficient of linear thermal expansion in the CD and have a very low coefficient of linear thermal expansion in the MD. The difference in the coefficient of thermal expansion can be obtained by using different polymeric materials, for example polyethylene for polymeric layer 12 and polyethylene terephthalate for polymeric layer 11. Alternatively, the difference in coefficient of thermal expansion can be obtained by differences in molecular orientation. For example, a cross direction (trans direction) oriented film for polymer layer 11 and a machine direction oriented film for polymer layer 12.
Polymeric layers 11 and 12 may be coextruded films. Alternatively, as shown in
The adhesive labels of the invention may, and generally do contain other layers. For example, as shown in
In one embodiment, one of polymeric layers of the label comprises a polymeric ink layer. For example, the first polymeric layer 11 may comprise a crosslinked ink that has been screen printed onto the second polymeric layer 12. Alternatively, the second polymeric layer 12 may comprise an ink layer that has been printed onto the first polymeric layer 11.
The labels of the invention may also contain adhesion promoting layers between one or more of the layers shown. For example, an adhesion promoting layer can be inserted between the second polymeric layer 12 and the adhesive layer 16; between the first polymeric layer 11 and the metal layer 13 or the print layer 14; etc.
The label may also contain a metal layer. As illustrated in
In another embodiment, illustrated in
In one embodiment, the adhesive is applied to a shrink film facestock. Such films are stretched in at least one direction and, upon exposure to heat, shrink back. The shrinking of the film is irreversible. That is, upon cooling, the film does not expand back to its pre-heated dimensions. A PSA coated shrink label may be removed from the container or substrate to which it is applied by exposing the label to heat, for example the high temperature washing fluid, so that the label shrinks and overcomes the retention force of the adhesive label. The degree of shrinkage of the facestock film at temperatures greater than 50° C., or 60° C. or 70° C. is greater than about 5% in one embodiment, or greater than about 10%, or about 15 to 20% or more.
In one embodiment, the PSA label is attached to the circumferential surface of a cylindrical container, wherein the shrinkage label film is stretched in at least the circumferential direction. Examples of shrinkage films include, but are not limited to, monoaxially or biaxially stretched shrinkable polyvinyl chloride, polyester, polyethylene terephthalate, polyolefin, polyethylene, polypropylene, acetate, cocyloolefin copolymer films and combinations of two or more of these.
The following examples illustrate several non-limiting embodiments of the invention, its preparation, and performance.
Base polymers are prepared by free-radical emulsion polymerization according to the following procedure, using the components identified in Table 2.
A reactor equipped with a stirrer, heat source and nitrogen inlet is purged with nitrogen and charged with water, then heated to 78° C. Potassium persulfate or ammonium persulfate is added to the reactor, and the reactor contents are mixed for five minutes. Thereafter, the pre-emulsion mixture is fed into the reactor over a 230 minute period. The temperature of the reactor batch is allowed to rise to 79-81° C. and then maintained at that temperature throughout the polymerization reaction. An initiator solution feed is commenced after the pre-emulsion feed begins. Twenty-five minutes after the pre-emulsion feed is complete, the initiator feed is complete and the reactor contents are held at 79-81° C. for 60 minutes. The reactor contents are then allowed to cool, and when the temperature reaches 38° C., a biocide is added. The rinse water is used throughout the process to wash out the various feed vessels and lines, and to rinse the reactor at the end of the polymerization. Base Polymer A has a solids content of about 66% and a pH of 1.8.
Using the Base Polymers described above, a series of pressure sensitive adhesive compositions are prepared by compounding the base polymer and neutralizing it with a hydroxy functional amine or blend thereof. In several examples, a salt from an organic acid is used.
Table 3 identifies the neutralizing agent, and the salt, if any, used to produce the adhesive compositions of Examples 1-8 and Comparative Example A. Examples 1-7 are prepared using Base Polymer A. Example 8 is prepared using Base Polymer B. Comparative Example A is Base Polymer A neutralized with ammonia. The amount of neutralizing agent and salt listed is in parts by weight per 100 parts dry polymer.
The abbreviations used below are as follows:
Each of the adhesives of Examples 1-8 and Comparative Example A is coated onto a siliconized polyester liner at a coat weight of 20 grams per square meter (g/m2), and then transferred onto a curling film of the type shown in
The wash-off test consists of immersing the labeled glass bottle in a 2% sodium hydroxide solution at 80° C. The label was examined after 1, 3 and 5 minute intervals. If the label is not washed off, the amount of lift in mm (total of both sides of the label) is measured. A value of 50 mm would mean that the label has been washed off. Each adhesive formulation was tested twice. The labels employing the adhesives having hydroxy functional amine neutralized copolymers have improved removability in hot caustic water, yet the adhesive strength of the adhesive, i.e., the peel strength, is not adversely affected.
Using Base Polymer A, pressure sensitive adhesive compositions are prepared substantially in accordance with the procedure of Example 1 with the exception that varying amounts of a carbodiimide crosslinker (Carbodilite E-02 from Nisshinbo Industries) is used.
Each of the adhesives of Examples 1 and 9-12 is coated onto a siliconized polyester liner at a coat weight of 15 grams per square meter (g/m2), and then transferred onto a curling film of the type shown in
The wash-off test consists of immersing the labeled glass bottle in a 2% sodium hydroxide solution at 80° C. The time in seconds for the label to completely wash off of the bottle is measured. Each adhesive formulation was tested twice. The addition of an external crosslinker improves wash-off, particularly on aged samples (1 day at 50° C.).
Example 13 is prepared substantially in accordance with the procedure of Example 1, with the exception that Base Polymer C is used. Examples 14 and 15 are prepared substantially in accordance with the procedure of Example 1, with the exception that Base Polymer D is used. Base Polymers C and D both include an organic acid in the polymerization pre-emulsion.
Each of the adhesives of Examples 13-15 is coated onto a siliconized polyester liner at a coat weight of 20 grams per square meter (g/m2), and then transferred onto a curling film of the type shown in
The wash-off test consists of immersing the labeled glass bottle in a 2% sodium hydroxide solution at 80° C. The time in seconds for the label to completely wash off of the bottle is measured. Each adhesive formulation was tested twice. The wash off times for the labels remains low after ageing and the peel strength is more stable after ageing than adhesives wherein no organic acid is added to the pre-emulsion and no external crosslinker is used.
While the invention has been explained in relation to embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the inventions disclosed herein is intended to cover such modifications as fall within the scope of the appended claims, and to cover insubstantial variations thereof.
This application claims is a division of U.S. patent application Ser. No. 12/447,478 filed Jul. 30, 2009, which claims the benefit of International Application No. PCT/US2007/083312, which was published in English on May 15, 2008. International Application No. PCT/US2007/083312 claims priority from U.S. Application No. 60/864,028 filed Nov. 2, 2006. All of the noted applications are incorporated herein by reference in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3312563 | Rusch | Apr 1967 | A |
| 4501845 | Baus et al. | Feb 1985 | A |
| 4536060 | Takamatsu et al. | Aug 1985 | A |
| 4562684 | Dreher | Jan 1986 | A |
| 4608284 | Roales | Aug 1986 | A |
| 4662965 | DiFrank et al. | May 1987 | A |
| 4725454 | Galli et al. | Feb 1988 | A |
| 4744918 | Heppke et al. | May 1988 | A |
| 4879177 | Boice | Nov 1989 | A |
| 5100963 | Lin | Mar 1992 | A |
| 5156911 | Stewart | Oct 1992 | A |
| 5190609 | Lin et al. | Mar 1993 | A |
| 5229447 | Miyajima et al. | Jul 1993 | A |
| 5251048 | Doane et al. | Oct 1993 | A |
| 5292566 | Shacklett, III | Mar 1994 | A |
| 5330961 | Takeyama et al. | Jul 1994 | A |
| 5384067 | Doane et al. | Jan 1995 | A |
| 5387450 | Stewart | Feb 1995 | A |
| 5437811 | Doane et al. | Aug 1995 | A |
| 5466496 | Jin | Nov 1995 | A |
| 5626955 | Goetz et al. | May 1997 | A |
| 5665443 | Hata et al. | Sep 1997 | A |
| 5668614 | Chien et al. | Sep 1997 | A |
| 5668651 | Yamada et al. | Sep 1997 | A |
| 5691795 | Doane et al. | Nov 1997 | A |
| 5695682 | Doane et al. | Dec 1997 | A |
| 5709391 | Arakawa et al. | Jan 1998 | A |
| 5709937 | Adams et al. | Jan 1998 | A |
| 5712031 | Kelch et al. | Jan 1998 | A |
| 5725966 | Abe et al. | Mar 1998 | A |
| 5748277 | Huang et al. | May 1998 | A |
| 5766508 | Kawasumi et al. | Jun 1998 | A |
| 5766694 | West et al. | Jun 1998 | A |
| 5928803 | Yasuda | Jul 1999 | A |
| 5929960 | West et al. | Jul 1999 | A |
| 5940150 | Faris et al. | Aug 1999 | A |
| 5964975 | Hinton | Oct 1999 | A |
| 6042930 | Kelch et al. | Mar 2000 | A |
| 6049366 | Hakemi et al. | Apr 2000 | A |
| 6072549 | Faris et al. | Jun 2000 | A |
| 6106982 | Mientus et al. | Aug 2000 | A |
| 6108062 | Takeuchi et al. | Aug 2000 | A |
| 6136903 | Su et al. | Oct 2000 | A |
| 6153288 | Shih et al. | Nov 2000 | A |
| 6249332 | Bryan-Brown et al. | Jun 2001 | B1 |
| 6319428 | Michot et al. | Nov 2001 | B1 |
| 6416857 | Wright | Jul 2002 | B1 |
| 6429961 | Harary et al. | Aug 2002 | B1 |
| 6489387 | Mallya | Dec 2002 | B2 |
| 6508560 | Epstein et al. | Jan 2003 | B2 |
| 6621539 | Nakamura | Sep 2003 | B2 |
| 6674504 | Li et al. | Jan 2004 | B1 |
| 6680097 | Amberger et al. | Jan 2004 | B1 |
| 6680758 | Faris | Jan 2004 | B1 |
| 6726969 | Balaji et al. | Apr 2004 | B1 |
| 6761969 | Li et al. | Jul 2004 | B2 |
| 6821592 | Rodick | Nov 2004 | B2 |
| 6927267 | Varela de la Rosa et al. | Aug 2005 | B1 |
| 7144542 | Holzer et al. | Dec 2006 | B2 |
| 7217463 | Henderson | May 2007 | B2 |
| 7294380 | Squier et al. | Nov 2007 | B2 |
| 7514131 | Funato et al. | Apr 2009 | B2 |
| 7700189 | Amon et al. | Apr 2010 | B2 |
| 8535464 | Lorence et al. | Sep 2013 | B2 |
| 9387652 | Doornheim et al. | Jul 2016 | B2 |
| 20010003765 | Mallya | Jun 2001 | A1 |
| 20010018125 | Shibuya et al. | Aug 2001 | A1 |
| 20020084565 | Dautartas et al. | Jul 2002 | A1 |
| 20020119292 | Venkatasanthanam et al. | Aug 2002 | A1 |
| 20030083523 | Ando et al. | May 2003 | A1 |
| 20030150148 | Spear et al. | Aug 2003 | A1 |
| 20030193709 | Mallya et al. | Oct 2003 | A1 |
| 20030207065 | Sher et al. | Nov 2003 | A1 |
| 20040033349 | Henderson | Feb 2004 | A1 |
| 20040038026 | Li et al. | Feb 2004 | A1 |
| 20040219321 | Squier et al. | Nov 2004 | A1 |
| 20050083564 | Mallya et al. | Apr 2005 | A1 |
| 20050090619 | Yoshimura | Apr 2005 | A1 |
| 20060036556 | Knispel | Feb 2006 | A1 |
| 20060228504 | Song | Nov 2006 | A1 |
| 20060251891 | Aarnio | Nov 2006 | A1 |
| 20060263600 | Bartholomew et al. | Nov 2006 | A1 |
| 20060269755 | Song | Nov 2006 | A1 |
| 20060275602 | Nakada et al. | Dec 2006 | A1 |
| 20070154668 | Rhee et al. | Jul 2007 | A1 |
| 20070213449 | Lewandowski | Sep 2007 | A1 |
| 20080118740 | Kuwahara et al. | May 2008 | A1 |
| 20080191880 | Tuffe et al. | Aug 2008 | A1 |
| 20080197540 | McAllister et al. | Aug 2008 | A1 |
| 20090218307 | Davies et al. | Sep 2009 | A1 |
| 20090233067 | Doornheim | Sep 2009 | A1 |
| 20100285249 | Mitchell et al. | Nov 2010 | A1 |
| 20120018098 | Henderson | Jan 2012 | A1 |
| 20120034402 | Henderson | Feb 2012 | A1 |
| 20130008613 | Henderson | Jan 2013 | A1 |
| 20130146230 | Davies et al. | Jun 2013 | A1 |
| 20150255008 | Henderson | Sep 2015 | A1 |
| 20150279247 | Henderson | Oct 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| PI9709104 | Aug 1999 | BR |
| 1201475 | Dec 1998 | CN |
| 1608083 | Apr 2005 | CN |
| 1692386 | Nov 2005 | CN |
| 1791651 | Jun 2006 | CN |
| 101246653 | Aug 2008 | CN |
| 101258213 | Sep 2008 | CN |
| 101102889 | Sep 2011 | CN |
| 3909089 | Sep 1990 | DE |
| 19716875 | Nov 1997 | DE |
| 0317180 | May 1989 | EP |
| 0471767 | Feb 1992 | EP |
| 0498249 | Aug 1998 | EP |
| 0924678 | Jun 1999 | EP |
| 0951004 | Oct 1999 | EP |
| 1055715 | Nov 2000 | EP |
| 1116745 | Jul 2001 | EP |
| 1375621 | Jan 2004 | EP |
| 1688445 | Aug 2006 | EP |
| 1743006 | Jan 2007 | EP |
| 1866895 | Dec 2007 | EP |
| 2328694 | Jun 2011 | EP |
| 2259291 | Mar 1993 | GB |
| 2411877 | Sep 2005 | GB |
| 2411881 | Sep 2005 | GB |
| 2424865 | Oct 2006 | GB |
| 2425107 | Oct 2006 | GB |
| 5-173487 | Jul 1993 | JP |
| 6-158006 | Jun 1994 | JP |
| 6-266288 | Sep 1994 | JP |
| 9-251272 | Sep 1997 | JP |
| 11-057558 | Mar 1999 | JP |
| 11-246395 | Sep 1999 | JP |
| 11-273636 | Oct 1999 | JP |
| 2000-144086 | May 2000 | JP |
| 2000-271204 | Oct 2000 | JP |
| 2002-071204 | Mar 2002 | JP |
| 2002-322448 | Nov 2002 | JP |
| 10-0369453 | Jan 2003 | KR |
| 2007008258 | Aug 2007 | MX |
| 2160932 | Dec 2000 | RU |
| 26272 | Nov 2002 | RU |
| 9213901 | Aug 1992 | WO |
| 9323496 | Nov 1993 | WO |
| 9534263 | Dec 1995 | WO |
| 9711996 | Apr 1997 | WO |
| 9838547 | Sep 1998 | WO |
| 9919415 | Apr 1999 | WO |
| 99058421 | Nov 1999 | WO |
| 9963400 | Dec 1999 | WO |
| 0013887 | Mar 2000 | WO |
| 0013888 | Mar 2000 | WO |
| 0060407 | Oct 2000 | WO |
| 0140853 | Jun 2001 | WO |
| 0142325 | Jun 2001 | WO |
| 0159024 | Aug 2001 | WO |
| 0242832 | May 2002 | WO |
| 02074874 | Sep 2002 | WO |
| 03087251 | Oct 2003 | WO |
| 03099953 | Dec 2003 | WO |
| 2004061037 | Jul 2004 | WO |
| 2004092295 | Oct 2004 | WO |
| 2005085381 | Sep 2005 | WO |
| 2006033925 | Mar 2006 | WO |
| 2006076327 | Jul 2006 | WO |
| 2006078038 | Jul 2006 | WO |
| 2006106309 | Oct 2006 | WO |
| 2007030583 | Mar 2007 | WO |
| 2008093333 | Aug 2008 | WO |
| 2008124581 | Oct 2008 | WO |
| 2009043975 | Apr 2009 | WO |
| 2010027507 | Mar 2010 | WO |
| 2010117767 | Oct 2010 | WO |
| 2010117771 | Oct 2010 | WO |
| 2010117774 | Oct 2010 | WO |
| 03029002 | Apr 2013 | WO |
| Entry |
|---|
| Overview of materials for Ethylene Vinyl Alcohol (EVOH), available at http://www.matweb.com/search/datasheet.aspx?matguid=744899e4ab06482da9cf86d8f450bd0d&ckck=1 , hereafter referred to as “Matweb”. |
| International Preliminary Report on Patentability issued in corresponding IA No. PCT/US2007/083312 dated Oct. 16, 2008. |
| TOPAS 8007S datasheet, available at http://www.topas.com/sites/default/files/TDS_8007S_04_e_1.pdf (2014). |
| TOPAS 9506F-500 datasheet, available at http://www.topas.com/sites/default/files/TDS_9506F-500_e_0.pdf (2014). |
| Wypych, George (2012), Handbook of Polymers . . . ChemTec Publishing, Online version available at: http://www.knovel.com.web.portal/browse/display?_EXT_KNOVEL_DISPLAY_bookid=5141&verticalID=0. |
| Polylactic Acid Technology; http://www.jimluntllc.com/pdfs/polylactic_acid_technology.pdf. |
| The Engineering Toolbox; http://engineeringtoolbox.com/linear-expansion-coefficients-d_95.html. |
| Wood et al., “5.1: Large Area, High Resolution Portable ZBD Display”, SID 02 Digest, ISSN/002-0866X/02/3301-0022-$1.00 © 2002 SID, pp. 22-25. |
| Pentermann et al., Letters to Nature, “Single-substrate liquid-crystal displays by photo-enforced stratification”, Nature/vol. 417/May 2, 2002/www.nature.com, © 2002 Maxmillan Magazines Ltd., pp. 55-58. |
| International Search Report and Written Opinion issued in corresponding IA No. PCT/US2007/083312 dated May 16, 2008. |
| Number | Date | Country | |
|---|---|---|---|
| 20160355708 A1 | Dec 2016 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60864028 | Nov 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12447478 | US | |
| Child | 15242855 | US |
