# US 8,785,540 B2 · Vinyl ester copolymer dispersions, their preparation and use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,785,540 B2 - Document ID: US8785540B2 - Status: Granted - Kind: B2 - Application number: 11/835,102 - Filed: 2007-08-07 - Published: 2008-02-14 - Granted: 2014-07-22 - Earliest claimed: 2006-08-08 - Assignees: Celanese Emulsions GmbH - Applicants: Harmin Müller; Hans Uwe Faust; Martin Schäfer - Inventors: Harmin Müller; Hans Uwe Faust; Martin Schäfer - Web page: https://patentgrep.com/patent/US8785540B2 ## CPC - C08F 218/08: Vinyl acetate - C08L 29/06: Copolymers of allyl alcohol - C09J 131/04: Homopolymers or copolymers of vinyl acetate - C08L 31/04: Homopolymers or copolymers of vinyl acetate - C08L 2205/02: containing two or more polymers of the same C08L -group - C08L 2666/04: Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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) ## Abstract A description is given of an aqueous vinyl ester copolymer dispersion stabilized with a combination of at least one protective colloid and of at least one emulsifier, said dispersion having a viscosity of less than 8000 mPa*s, a weight average dw of the particle sizes of 0.5 to 10 μm, and a ratio of weight average to number average of the particle sizes, dw/dn, of at least 2.5, and the polymer possessing a glass transition temperature of between −30 and +15° C. The dispersion can be used as an adhesive for nozzle application processes. ## Claims ### Claim 1 An aqueous vinyl ester copolymer dispersion stabilized with at least two polyvinyl alcohols having different molecular weights combined with from 0.05% to 5% by weight, based on the total amount of monomers employed, of at least one emulsifier, said dispersion having a viscosity of less than 8000 mPa*s, a weight average dw of the particle sizes of 0.5 to 10 and a ratio of weight average to number average of the particle sizes, dw/dn, in the range of from 2.5 to 20.0, wherein said copolymer possesses a glass transition temperature of from −20 to +5° C., wherein said at least one emulsifier is selected from the group consisting of ethoxylated, non-ionic emulsifiers, ethoxylated, anionic emulsifiers, or combinations thereof and wherein an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 18 to 60 mPa*s and an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 2 to 18 mPa*s. ### Claim 2 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said viscosity is from 100 to 8000 mPa*s. ### Claim 3 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said weight average of the particle sizes, dw, is 0.5 to 6.0 μm. ### Claim 4 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1 derived from at least one vinyl ester copolymer obtained by emulsion polymerization of A1) vinyl esters of aliphatic, saturated carboxylic acids having a chain length of C1-C4; A2) alpha-olefins having 2 to 8 carbon atoms; and/or A3) vinyl esters of aliphatic, saturated carboxylic acids having a chain length of C5-C18; wherein the sum of A1), A2), and/or A3) is 100% by weight. ### Claim 5 (depends on 4) The aqueous vinyl ester copolymer dispersion of claim 4, wherein said at least one vinyl ester copolymer is obtained by emulsion polymerization of A1), A2) and/or A3) with A4) esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids with monohydric saturated alcohols; and/or A5) further comonomers which are not A1), A2), A3), or A4); wherein the sum of A1), A2), and/or A3), and/or A4), and/or A5) making 100% by weight. ### Claim 6 (depends on 4) The aqueous vinyl ester copolymer dispersion of claim 4, comprising polyvinyl acetate-ethylene copolymers or polyvinyl acetate ethylene copolymers which further contain, in copolymerized form, 0.5 to 40 parts by weight of esters of acrylic acid and/or of esters of methacrylic acid and/or of diesters of maleic acid with monohydric saturated alcohols. ### Claim 7 (depends on 6) The aqueous vinyl ester copolymer dispersion of claim 6, comprising polyvinyl acetate-ethylene copolymers. ### Claim 8 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said at least one emulsifier is at least one nonionic emulsifier. ### Claim 9 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein the amount of said at least one protective colloid is 3% to 10% by weight and the amount of said at least one emulsifier is 0.05% to 1.5% by weight, based in each case on the total amount of monomers employed. ### Claim 10 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said dispersion has a yield point of 0.2 to 1.0 Pa. ### Claim 11 (depends on 10) The aqueous vinyl ester copolymer dispersion of claim 10, wherein said yield point is 0.3 to 0.6 Pa. ### Claim 12 (depends on 1) A process for preparing the aqueous vinyl ester copolymer dispersion of claim 1 by emulsion polymerization of at least one vinyl ester of an aliphatic carboxylic acid comprising a) initially introducing 2% to 10% by weight, based on the total weight of all the monomers used to prepare said aqueous vinyl ester copolymer dispersion, of at least two polyvinyl alcohols having different molecular weights, wherein at least one of said at least two polyvinyl alcohols has a viscosity of the 4% strength aqueous solution, measured by the method of Höppler at 20° C., of at least 18 mPa*s and at least one of said at least two polyvinyl alcohols has a viscosity of the 4% strength aqueous solution, measured by the method of Höppler at 20° C., of from 2 to 18 mPa*s; b) adding 0.05% to 5% by weight, based on the total weight of all the monomers used to prepare said aqueous vinyl ester copolymer dispersion, at least one nonionic emulsifier and/or ionic emulsifier to the said at least two polyvinyl alcohols to form a mixture; c) adding 0% to 60% by weight, based on the total weight of all the monomers used to prepare said aqueous vinyl ester copolymer dispersion, of monomer or monomers to the mixture of b) to form a mixture; d) adding at least one vinyl ester of a carboxylic acid and at least one initiator of free-radical emulsion polymerization to the mixture of c); and e) forming an aqueous vinyl ester copolymer dispersion having a glass transition temperature of between −30 and 15° C. ### Claim 13 (depends on 12) The process of claim 12, wherein one polyvinyl alcohol of said at least two polyvinyl alcohols has a degree of hydrolysis of from 70 to 100 mol % and its 4% strength aqueous solution has a viscosity at 20° C. of 18 to 60 mPa*s and wherein a second polyvinyl alcohol has a degree of hydrolysis of from 70 to 100 mol % and its 4% strength aqueous solution has a viscosity at 20° C. of 2 to 18 mPa*s. ### Claim 14 (depends on 1) An adhesive for nozzle application to a substrate, wherein said adhesive comprises the aqueous vinyl ester copolymer dispersion of claim 1. ### Claim 15 (depends on 14) The adhesive of claim 14, wherein the substrates are hydrophobic substrates. ### Claim 16 (depends on 14) The adhesive of claim 14, wherein said nozzle application is dotwise or linear. ### Claim 17 (depends on 14) The adhesive of claim 14, wherein said substrate is bonding paper used in the production-line fabrication of folding boxes, envelopes, brochures, or cigarettes. ### Claim 18 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said at least two polyvinyl alcohols each have a degree of hydrolysis of from 80 to 99 mol % and/or wherein an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 18 to 50 mPa*s and an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 3 to 18 mPa*s. ### Claim 19 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein said at least two polyvinyl alcohols each have a degree of hydrolysis of from 87 to 99 mol % and/or wherein an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 18 to 40 mPa*s and an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 4 to 18 mPa*s. ### Claim 20 (depends on 1) The aqueous vinyl ester copolymer dispersion of claim 1, wherein the amount of said at least one emulsifier is from 0.05% to 1.5% by weight, based on the total amount of monomers employed. ### Claim 21 An aqueous vinyl ester copolymer dispersion stabilized with at least one protective colloid combined with at least one emulsifier, said protective colloid is a mixture two polyvinyl alcohols having different molecular weights, and said dispersion having a viscosity of less than 8000 mPa*s, a weight average dw of the particle sizes of 0.5 to 10 μm, and a ratio of weight average to number average of the particle sizes, dw/dn, in the range of from 4.5 to 20.0, wherein said copolymer possesses a glass transition temperature of between −30 and 15° C., wherein said at least one emulsifier is selected from the group consisting of ethoxylated, non-ionic emulsifiers, ethoxylated, anionic emulsifiers, or combinations thereof and wherein an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 18 to 60 mPa*s and an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 2 to 18 mPa*s. ### Claim 22 A process comprising the step of applying an adhesive through a nozzle to a substrate, wherein said adhesive comprises an aqueous vinyl ester copolymer dispersion stabilized with at least two polyvinyl alcohols having different molecular weights combined with from 0.05% to 5% by weight, based on the total amount of monomers employed, of at least one emulsifier, said dispersion having a viscosity of less than 8000 mPa*s, a weight average dw of the particle sizes of 0.5 to 10 μm, and a ratio of weight average to number average of the particle sizes, dw/dn, in the range of from 2.5 to 20.0, wherein said copolymer possesses a glass transition temperature of from −20 to +5° C. and wherein an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 18 to 60 mPa*s and an aqueous solution of at least one of said at least two polyvinyl alcohols possesses a viscosity at 20° C. of from 2 to 18 mPa*s. ### Claim 23 A process comprising the step of applying an adhesive through a nozzle to a substrate, wherein said adhesive comprises an aqueous vinyl ester copolymer dispersion stabilized with at least two polyvinyl alcohols having different molecular weights combined with from 0.05% to 5% by weight, based on the total amount of monomers employed, of at least one emulsifier, said dispersion having a viscosity of less than 8000 mPa*s, a weight average dw of the particle sizes of 0.5 to 10 μm, and a ratio of weight average to number average of the particle sizes, dw/dn, in the range of from 2.5 to 20.0, wherein said copolymer possesses a glass transition temperature of from −20 to +5° C. ### Claim 24 (depends on 23) The process of claim 23, wherein said substrate is hydrophobic. ### Claim 25 (depends on 23) The process of claim 23, wherein the application of the adhesive to the substrate is dotwise or linear. ### Claim 26 (depends on 23) The process of claim 23, wherein said substrate is bonding paper used in the production-line fabrication of folding boxes, envelopes, brochures, or cigarettes. ### Claim 27 (depends on 1) The process as claimed in claim 1, wherein said at least two polyvinyl alcohols each have a degree of hydrolysis of from 70 to 100 mol %.