# US 9,040,155 B2 · Pressure sensitive adhesive composition for protective film having anti-static property and manufacturing process thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,155 B2 - Document ID: US9040155B2 - Status: Granted - Kind: B2 - Application number: 14/346,277 - Filed: 2012-10-22 - Published: 2015-01-08 - Granted: 2015-05-26 - Earliest claimed: 2011-11-08 - Assignees: LG Chem, Ltd. - Applicants: LG Chem. Ltd. - Inventors: Jae Woung Ha; Young-Min Kim; Jung Sup Han; Kong Ju Song; Kumhyoung Lee - Web page: https://patentgrep.com/patent/US9040155B2 ## CPC - C09J 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen - C09J 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00 - C09J 7/385: {Acrylic polymers} - C09J 133/04: Homopolymers or copolymers of esters {(C09J143/04 takes precedence)} - C09J 2433/00: Presence of (meth)acrylic polymer - Y10T 428/2848: Three or more layers - 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) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Provided is an adhesive composition for a protective film including an acrylic emulsion resin capable of providing contamination resistance on the film and low peel strength and minimizing generation of static electricity during peeling of the protective film. The acrylic emulsion resin includes a mixture including 80 to 99.9% by weight of a polymer of a (meth)acrylic acid ester monomer including a C1-C14 alkyl group and a (meth)acrylic acid ester monomer including an alkylene oxide unit, and 0.1 to 20% by weight of a monomer including a carboxyl group and/or a hydroxyl group or a combination thereof, and 5 to 30 parts by weight of a reactive emulsifier having a double bond structure radical-polymerizable with the polymer and including an alkylene oxide unit based on 100 parts by weight of the mixture. ## Claims ### Claim 1 An adhesive composition for a protective film comprising acrylic emulsion resin particles and 0.5 to 5 parts by weight of an external cross-linking agent based on 100 parts by weight of the acrylic emulsion resin particles, wherein the acrylic emulsion resin particles comprise a polymer of a mixture comprising 80 to 99.9% by weight of a (meth)acrylic acid ester monomer comprising a C1-C14 alkyl group and a (meth)acrylic acid ester monomer comprising an alkylene oxide unit, and 0.1 to 20% by weight of a monomer comprising a carboxyl group and/or a hydroxyl group or a combination thereof; and 5 to 30 parts by weight of a reactive emulsifier of Formula 2 based on 100 parts by weight of the mixture, wherein Formula 2 is as follows: wherein R is a C1-C9 alkylene group, and m in Formula 2 is in the range of 5 to 50. ### Claim 2 (depends on 1) The adhesive composition according to claim 1, wherein the (meth)acrylic acid ester monomer comprising a C1-C14 alkyl group comprises at least one compound selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl (meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, and lauryl(meth)acrylate. ### Claim 3 (depends on 1) The adhesive composition according to claim 1, wherein the (meth)acrylic acid ester monomer comprising an alkylene oxide unit comprises at least one compound selected from the group consisting of polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acrylate, polyethylene glycol-polypropylene glycol(meth)acrylate, polyethylene glycol-polybutylene glycol(meth)acrylate, polypropylene glycol-polybutylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, ethoxypolyethylene glycol(meth)acrylate, butoxypolyethylene glycol(meth)acrylate, octoxypolyethylene glycol(meth)acrylate, lauroxypolyethylene glycol(meth)acrylate, stearoxypolyethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, methoxypolypropylene glycol(meth)acrylate, and octoxypolyethylene glycol-polypropylene glycol(meth)acrylate. ### Claim 4 (depends on 1) The adhesive composition according to claim 1, wherein the (meth)acrylic acid ester monomer comprising an alkylene oxide unit is alkoxypolyalkylene glycol mono(meth)acrylic acid ester monomer represented by Formula 1 below: wherein R1 is a hydrogen atom or a methyl group, R2O comprises one or more C2-C4 ethylene oxides, which may be attached in blocks or randomly if there are two or more, R3 is a C1-C4 alkyl group, and m in Formula 1, as an average addition number of moles of ethylene oxide, is an integer of 6 to 17. ### Claim 5 (depends on 1) The adhesive composition according to claim 1, wherein the monomer comprising a carboxyl group comprises at least one compound selected from the group consisting of maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid, and the monomer comprising a hydroxyl group comprises at least one compound selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyhexyl(meth)acrylate, hydroxyoctyl(meth)acrylate, hydroxylauryl(meth)acrylate, and hydroxypropyl glycol(meth)acrylate. ### Claim 6 (depends on 1) The adhesive composition according to claim 1, wherein the mixture comprises 80 to 99.9% by weight of the (meth)acrylic acid ester monomer comprising a C1-C14 alkyl group and a (meth)acrylic acid ester monomer comprising an alkylene oxide unit, 0.1 to 19.9% by weight of the monomer comprising a carboxyl group and/or a hydroxyl group or a combination thereof, and 0.1 to 10% by weight of an internal cross-linking agent comprising an acrylate group or a vinyl group. ### Claim 7 (depends on 6) The adhesive composition according to claim 6, wherein the internal cross-linking agent comprises at least one compound selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, hexanediol ethoxylate diacrylate, ethylene glycol dimethacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylpropane ethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene. ### Claim 8 (depends on 1) The adhesive composition according to claim 1, wherein the reactive emulsifier is an ammonium nonylene ether polyethylene oxide sulfonate having a carbon-carbon double bond structure. ### Claim 9 (depends on 1) The adhesive composition according to claim 1, wherein the external cross-linking agent is an organic cross-linking agent or an inorganic cross-linking agent. ### Claim 10 (depends on 9) The adhesive composition according to claim 9, wherein the organic cross-linking agent is an aziridine cross-linking agent. ### Claim 11 (depends on 9) The adhesive composition according to claim 9, wherein the inorganic cross-linking agent comprises at least one compound selected from the group consisting of aluminum acetylacetonate, aluminum acetate, zinc acetate, chromium acetate, zinc ammonium carbonate, and zirconium ammonium carbonate. ### Claim 12 A method of manufacturing an adhesive composition for a protective film, the method comprising: preparing a monomer mixture comprising 80 to 99.9% by weight of a (meth)acrylic acid ester monomer comprising a C1-C14 alkyl group and a (meth)acrylic acid ester monomer comprising an alkylene oxide unit, and 0.1 to 20% by weight of a monomer comprising a carboxyl group and/or a hydroxyl group or a combination thereof; performing a polymerization by adding 5 to 30 parts by weight of a reactive surfactant of Formula 2 and 0.1 to 3 parts by weight of a polymerization initiator to 100 parts by weight of the monomer mixture; and dispersing 0.5 to 5 parts by weight of an external cross-linking agent in 100 parts by weight of the monomer mixture, wherein Formula 2 is as follows: wherein R is a C1-C9 alkylene group, and m in Formula 2 is in the range of 5 to 50. ### Claim 13 (depends on 12) The method according to claim 12, wherein the monomer mixture comprises 80 to 99.9% by weight of the (meth)acrylic acid ester monomer comprising a C1-C14 alkyl group and a (meth)acrylic acid ester monomer comprising an alkylene oxide unit, 0.1 to 19.9% by weight of the monomer comprising a carboxyl group and/or a hydroxyl group or a combination thereof, and 0.1 to 10% by weight of an internal cross-linking agent comprising an acrylate group or a vinyl group. ### Claim 14 (depends on 12) The method according to claim 12, wherein the polymerization initiator comprises at least one compound selected from the group consisting of ammonium persulfate or persulfate of an alkali metal and hydrogen peroxide. ### Claim 15 (depends on 1) A protective film formed by coating an adhesive composition according to claim 1 on one or both surfaces of a film.