# US 2016/0355708 A1 · Emulsion Adhesive for Washable Film > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2016/0355708 A1 - Document ID: US20160355708A1 - Status: Published application - Kind: A1 - Application number: 15/242,855 - Filed: 2016-08-22 - Published: 2016-12-08 - Earliest claimed: 2006-11-02 - Assignees: Avery Dennison Corporation - Applicants: Avery Dennison Corporation - Inventors: Alfredo MUELLER; Jos VAN NOORT; Graham YEADON - Web page: https://patentgrep.com/patent/US20160355708A1 ## CPC - C09J 133/08: Homopolymers or copolymers of acrylic acid esters - B32B 7/12: using interposed adhesives or interposed materials with bonding properties - B32B 27/06: as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08)} - B32B 38/10: Removing layers, or parts of layers, mechanically or chemically - B32B 43/006: {Delaminating} - C09J 7/22: Plastics; Metallised plastics - C09J 7/29: Laminated material (metallised plastics C09J7/22) - B32B 2519/00: Labels, badges - C09J 2203/334: as a label - C09J 2301/122: the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape - C09J 2301/162: the carrier being a laminate constituted by plastic layers only - C09J 2301/302: the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C - C09J 2301/312: parameters being the characterizing feature - C09J 2433/00: Presence of (meth)acrylic polymer - Y10T 156/1111: Using solvent during delaminating [e.g., water dissolving adhesive at bonding face during delamination, etc.] - Y10T 156/1142: Changing dimension during delaminating [e.g., crushing, expanding, warping, etc.] - Y10T 156/1153: Temperature change for delamination [e.g., heating during delaminating, etc.] - Y10T 428/24942: including components having same physical characteristic in differing degree - Y10T 428/2891: including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract This invention relates to removable pressure sensitive adhesive compositions and constructions that contain an emulsion acrylic pressure sensitive adhesive copolymer of a plurality of acrylic monomers and at least one polymerizable acid. The invention further relates to labels, particularly removable polymeric labels for use on reusable containers. ## Claims ### Claim at position 1 -28. (canceled) ### Claim 29 A facestock material comprising; a coating of a copolymer of copolymerizable monomers including (a) at least one alkyl acrylate having from about 4 to about 12 carbon atoms in the alkyl group; (b) at least one acid monomer; (c) at least one hard monomer, wherein a homopolymer of the hard monomer is not inherently tacky at ambient temperatures and has a Tg greater than −25° C.; and (d) optionally, at least one multifunctional crosslinking monomer; wherein the copolymer is neutralized to a pH of greater than 4.5 with a neutralizer, the neutralizer including at least one of 2-[bis-(2-hydroxyethyl)-amino]-2-hydroxymethyl propane-1,3-diol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, N-methyl-D-glucamine, N,N,N′,N′-tetrakis-(2-hydroxyethyl)-ethylenediamine, and N,N,N′,N′-tetrakis-(2-hydroxypropyl); and wherein the composition is washed off upon exposure to an aqueous caustic solution at a temperature of at least 50° C.; wherein the at least one alkyl acrylate is selected from butyl acrylate, hexyl acrylate, heptyl acrylate, n-octyl acrylate, iso-octyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and nonyl acrylate, and combinations of two or more thereof; wherein the at least one acid monomer is selected from acrylic acid, methacrylic acid, itaconic acid, beta-carboxyethyl-acrylate, and combinations of two or more thereof; wherein the at least one hard monomer is selected from methyl and ethyl acrylate, methyl and ethyl methacrylate, vinyl acetate, styrene, and combinations of two or more thereof; and wherein the multifunctional crosslinking monomer is selected from diallyl maleate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, allyl methacrylate, divinyl benzene, N,N′-methylene-bis-acrylamide, triallyl cyanurate, and combinations of two or more thereof. ### Claim 30 (depends on 29) The facestock material of claim 29 wherein the facestock comprises (a) a first polymeric layer having a first coefficient of thermal expansion; and (b) a second polymeric layer having a second coefficient of thermal expansion underlying the first polymeric layer, wherein the first coefficient of thermal expansion is less than the second coefficient of thermal expansion. ### Claim 31 A wash-off label comprising: a first polymeric layer having a first coefficient of thermal expansion; 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 an adhesive layer underlying the second polymeric layer, the adhesive layer comprising an emulsion based pressure sensitive adhesive composition comprising an acrylic pressure sensitive adhesive copolymer of copolymerizable monomers comprising at least one ethylenically unsaturated carboxylic acid; wherein the composition is neutralized to a pH of greater than 4.5 with at least one of 2-[bis-(2-hydroxyethyl)-amino]-2-hydroxymethyl propane-1,3-diol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, N-methyl-D-glucamine, N,N,N′,N′-tetrakis-(2-hydroxyethyl)-ethylenediamine, and N,N,N′,N′-tetrakis-(2-hydroxypropyl)-ethylenediamine; and wherein the label is reversibly curled toward the first polymeric layer at a temperature at or above 50° C. and the adhesive is washed off upon exposure to an aqueous caustic solution at a temperature of at least 50° C. ### Claim 32 (depends on 31) The label of claim 31 wherein the label is bondable to a cylindrically curved surface of an article and the main expansion direction of the label extends in the circumferential direction of the article. ### Claim 33 (depends on 31) The label of claim 31 wherein the first polymeric layer and the second polymeric layer are coextruded. ### Claim 34 (depends on 31) The label of claim 31 wherein the first polymeric layer and the second polymeric layer are bonded to each other by a lamination adhesive. ### Claim 35 (depends on 31) The label of claim 31 further comprising a metal layer. ### Claim 36 (depends on 35) The label of claim 35 wherein the metal layer overlies the first polymeric layer. ### Claim 37 (depends on 31) The label of claim 31 further comprising a print layer. ### Claim 38 (depends on 37) The label of claim 37 wherein the print layer overlies the first polymeric layer. ### Claim 39 (depends on 31) The label of claim 31 wherein the pressure sensitive adhesive copolymer comprises a copolymer of (a) about 75% to about 90% by weight of at least one 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 at least one acid monomer; (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 monomer, wherein the weight is based on the total weight of the monomers. ### Claim 40 (depends on 37) The label of claim 37 wherein the print layer underlies the first polymeric layer. ### Claim 41 A wash-off label comprising: a polymeric layer comprising at least one shrinkable film wherein the film is stretched in at least one direction; an adhesive layer underlying the polymeric layer, the adhesive layer comprising an emulsion based pressure sensitive adhesive composition comprising an acrylic pressure sensitive adhesive copolymer of copolymerizable monomers comprising at least one ethylenically unsaturated carboxylic acid; wherein the composition is neutralized to a pH of greater than 4.5 with at least one of 2-[bis-(2-hydroxyethyl)-amino]-2-hydroxymethyl propane-1,3-diol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, N-methyl-D-glucamine, N,N,N′,N′-tetrakis-(2-hydroxyethyl)-ethylenediamine, and N,N,N′,N′-tetrakis-(2-hydroxypropyl)-ethylenediamine; and wherein the polymeric layer irreversibly shrinks at a temperature at or above 50° C. and the adhesive is washed off upon exposure to an aqueous caustic solution at a temperature of at least 50° C. ### Claim 42 A method of detaching a label from an article, wherein the label comprises: a first polymeric layer having a first coefficient of linear thermal expansion; 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 an adhesive layer underlying the second polymeric layer, the adhesive comprising an emulsion based pressure sensitive adhesive composition comprising an acrylic pressure sensitive adhesive copolymer of copolymerizable monomers comprising at least one ethylenically unsaturated carboxylic acid; wherein the composition is neutralized to a pH of greater than 4.5 with at least one of 2-[bis-(2-hydroxyethyl)-amino]-2-hydroxymethyl propane-1,3-diol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, N-methyl-D-glucamine, N,N,N′,N′-tetrakis-(2-hydroxyethyl)-ethylenediamine, and N,N,N′,N′-tetrakis-(2-hydroxypropyl)-ethylenediamine; the method comprising heating a washing liquid to form a hot washing liquid; and gradually detaching the label from the article, wherein the step of gradually detaching the label from the article comprises the step of exposing the label to the hot washing liquid for at least a predetermined amount of time so that the label is reversibly curled toward the first polymeric layer thereby overcoming the adhesive force of the adhesive layer. ### Claim 43 (depends on 42) The method of claim 42 wherein the liquid comprises caustic soda. ### Claim 44 (depends on 42) The method of claim 42 wherein the hot washing liquid has a temperature in the range of about 50° C. to about 90° C. ### Claim 45 (depends on 42) The method of claim 42 wherein the pressure sensitive adhesive copolymer comprises a copolymer of (a) about 75% to about 90% by weight of at least one 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 at least one acid monomer; (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 monomer, wherein the weight is based on the total weight of the monomers.