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WO2020130285A1 - Acrylic emulsion pressure-sensitive adhesive composition - Google Patents

Acrylic emulsion pressure-sensitive adhesive composition Download PDF

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Publication number
WO2020130285A1
WO2020130285A1 PCT/KR2019/011396 KR2019011396W WO2020130285A1 WO 2020130285 A1 WO2020130285 A1 WO 2020130285A1 KR 2019011396 W KR2019011396 W KR 2019011396W WO 2020130285 A1 WO2020130285 A1 WO 2020130285A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
monomer
sensitive adhesive
adhesive composition
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.)
Ceased
Application number
PCT/KR2019/011396
Other languages
French (fr)
Korean (ko)
Inventor
이승모
양승훈
박용수
황윤태
김효민
서성종
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020190109115A external-priority patent/KR102332742B1/en
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP19899654.8A priority Critical patent/EP3722387B1/en
Priority to US16/963,712 priority patent/US20210079271A1/en
Priority to CN201980009181.5A priority patent/CN111684035B/en
Publication of WO2020130285A1 publication Critical patent/WO2020130285A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/06—Vinyl formate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1805—C5-(meth)acrylate, e.g. pentyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/1809—C9-(meth)acrylate
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to an acrylic emulsion pressure-sensitive adhesive composition.
  • PSA Pressure-Sensitive Adhesive
  • PSA is a material that has the property of adhering to an adhesive under a small pressure. It is a viscoelastic material different from the adhesive, and has the basic properties of initial adhesion, adhesion, and cohesion, and is used in various industries such as printing, chemicals, pharmaceuticals, home appliances, automobiles, and stationery.
  • the pressure-sensitive adhesive can be classified into acrylic, rubber, silicone, EVA, and the like according to the monomer used during manufacture, and can be classified into a solvent type, an emulsion type, and a hot melt type depending on the type.
  • Solvent-free pressure-sensitive adhesives are typically produced by water-based emulsion polymerization, and in terms of improving economic efficiency and processability, there are few aggregates and characteristics capable of stably realizing excellent adhesive properties are required.
  • the aqueous pressure-sensitive adhesive prepared by water-based emulsion polymerization uses a hydrophilic emulsifier, and in general, a bipolar single molecule having both hydrophilicity and hydrophobicity is used as a hydrophilic emulsifier.
  • a bipolar single molecule containing a hydrophilic group having strong polarity, such as sulfonate is used for particle formation and retention stability in an aqueous system.
  • the present invention is to provide a pressure-sensitive adhesive composition that does not leave a residue on the adherend, while showing excellent adhesion to both hydrophilic and hydrophobic substrates and a method for manufacturing the same.
  • the monomer mixture containing the (meth)acrylic acid ester-based monomer, vinyl-based monomer, and unsaturated carboxylic acid-based monomer is represented by the following formula (1), and has a hydration degree of 75 to 99% represented by the following formula (1).
  • It provides an acrylic emulsion pressure-sensitive adhesive composition comprising a copolymer emulsion-polymerized in the presence of a polymer emulsifier having a number average molecular weight of 1,000 to 8,000 g/mol.
  • the (meth) acrylic acid ester monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth) )Acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and lauryl (meth)acrylate It may be one or more selected from the group.
  • the vinyl-based monomer includes an alkyl group having 1 to 5 carbon atoms, a vinyl ester-based monomer; And it may be one or more selected from the group consisting of an aromatic vinyl-based monomer.
  • the unsaturated carboxylic acid-based monomer may be at least one selected from the group consisting of maleic anhydride, fumaric acid, crotanic acid, itaconic acid, and (meth)acrylic acid.
  • the present invention (meth) acrylic acid ester-based monomer, vinyl-based monomer and a monomer mixture containing an unsaturated carboxylic acid-based monomer; Crosslinking agents; And preparing a pre-emulsion comprising a polymer emulsifier represented by Formula 1, wherein the hydration degree represented by Formula 1 is 75 to 99%, and the number average molecular weight is 1,000 to 8,000 g/mol.
  • It provides a method for producing an acrylic emulsion pressure-sensitive adhesive composition comprising the step of emulsion polymerization of the pre-emulsion in the presence of an initiator.
  • the polymer emulsifier may be included in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the monomer mixture.
  • the (meth) acrylic acid ester-based monomer may be included in 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture.
  • the vinyl-based monomer may be included in 1 to 25 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester-based monomer.
  • the unsaturated carboxylic acid-based monomer may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester-based monomer.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • a monomer mixture comprising a (meth)acrylic acid ester-based monomer, a vinyl-based monomer, and an unsaturated carboxylic acid-based monomer is represented by the following Chemical Formula 1, and the degree of hydration represented by the following Chemical Formula 1
  • an acrylic emulsion pressure sensitive adhesive composition comprising a copolymer that is 75 to 99% and emulsion polymerized in the presence of a polymer emulsifier having a number average molecular weight of 1,000 to 8,000 g/mol.
  • m and n are the number of moles of repeating units constituting the polymer.
  • a bipolar single molecule containing a hydrophilic group having a strong polarity, such as sulfonate and sulfate, is used as an emulsifier.
  • an acrylic emulsion pressure-sensitive adhesive composition containing an emulsion of a copolymer, that is, an emulsion of latex particles using such an emulsifier, there is a problem of leaving a residue due to too strong adhesion to a hydrophilic substrate, and conversely, hydrophobicity of polyethylene, polypropylene, etc. There is a problem that the adhesion to the substrate is poor.
  • the present inventors have repeatedly studied the pressure-sensitive adhesive composition that exhibits excellent adhesion to both hydrophobic and hydrophilic substrates, but does not leave a residue on the adherend, and as a result, when using a polymer emulsifier such as Chemical Formula 1, adhesion properties are obtained.
  • the present invention was completed by confirming that it can be improved.
  • the polymer emulsifier is a modified polyvinyl alcohol-based polymer in which vinyl alcohol and methyl vinyl ketone monomer are copolymerized, and can be any of alternating, random, and block copolymers.
  • the hydroxy group which is a hydrophilic group, plays a role in maintaining particle stability in the water phase, and the polymer chain portion may serve as a space where polymerization occurs during emulsion polymerization.
  • the polymer emulsifier has a hydration degree of 75 to 99%, or 78 to 95%, represented by Equation 1 below.
  • the hydration degree is a percentage of repeating units derived from vinyl alcohol in the polymer, and the higher the hydration degree, the higher the hydrophilicity of the polymer. If the degree of hydration is less than 75%, there may be a problem of generation of residues due to too many carboxylic acid functional groups, and if it exceeds 99%, it is substantially polyvinyl alcohol, which is rapidly lowered in solubility in water and is suitable as an emulsifier. Since it does not, it is preferable to satisfy the hydration range.
  • the number average molecular weight of the polymer emulsifier is preferably in the range of 1,000 to 8,000 g/mol. If the number average molecular weight of the polymer emulsifier is less than 1,000 g/mol, there is a problem that the length of the polymer chain is excessively short, so that it does not function as an emulsifier. There may be a problem. At this time, the number-average molecular weight of the polymer emulsifier can be measured using gel permeation chromatography (GPC), as specified in the examples below.
  • GPC gel permeation chromatography
  • the polymer emulsifier is used in an amount of 0.1 to 5 parts by weight, or 0.5 to 3 parts by weight based on 100 parts by weight of the monomer mixture.
  • the content of the polymer emulsifier is less than 0.1 part by weight based on 100 parts by weight of the monomer mixture, the emulsifier is insufficient, so it is difficult to emulsify and polymerize through micelle formation, and there may be a problem that agglomerates are largely generated, and when it exceeds 5 parts by weight There may be a problem that adhesive properties are reduced due to the use of excessive emulsifiers.
  • the acrylic emulsion pressure-sensitive adhesive composition of the present invention is used by mixing (meth)acrylic acid ester-based monomer, vinyl-based monomer, and unsaturated carboxylic acid monomer as a monomer.
  • the acrylic emulsion pressure-sensitive adhesive composition of the present invention can have an effect of improving the overall adhesion and retention.
  • monomer mixture refers to a mixture of all monomers used for polymerization, and based on the monomers, as long as it can be used in an emulsion polymerization reaction to make an acrylic emulsion resin, there is no particular limitation.
  • the monomers may be added to the polymerization reaction in a mixed state, and the monomers may be sequentially added to the polymerization reaction.
  • the (meth)acrylic acid ester-based monomer may include a chain alkyl group having 1 to 10 carbon atoms, specifically methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (Meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate , Octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, iso It may be one or more selected from the group consisting of carbonyl (meth) acrylate, and lauryl (
  • the (meth)acrylic acid ester-based monomer may be included in 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture.
  • the vinyl-based monomer includes an alkyl group having 1 to 5 carbon atoms, a vinyl ester-based monomer; And it may be one or more selected from the group consisting of an aromatic vinyl-based monomer.
  • the vinyl ester-based monomer includes a vinyl group at one end of the molecule, and an ester-type monomer including an alkyl group having 1 to 5 carbon atoms at the other end.
  • an ester-type monomer including an alkyl group having 1 to 5 carbon atoms at the other end.
  • acetic acid And one or more types selected from the group consisting of vinyl, vinyl propanoate, vinyl butanoate, and vinyl pentacarbonate.
  • the aromatic vinyl monomer is selected from the group consisting of styrene, methylstyrene, methylstyrene, butylstyrene, chlorostyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene and divinylbenzene. 1 or more types are mentioned.
  • the vinyl monomer is used in an amount of 1 to 25 parts by weight, or 5 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester monomer, and accordingly, the repeating unit derived from the vinyl monomer in the emulsifying polymer is the ( Met) about 1 to 25 parts by weight, or 5 to 20 parts by weight based on 100 parts by weight of the acrylic ester monomer.
  • the unsaturated carboxylic acid monomer may be at least one selected from the group consisting of maleic anhydride, fumaric acid, crotanic acid, itaconic acid, and (meth)acrylic acid, but is not limited thereto.
  • the unsaturated carboxylic acid-based monomer is used in an amount of 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester-based monomer.
  • the unit is contained in about 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer.
  • the unsaturated carboxylic acid-based monomer is used too much, a problem may arise in which the viscosity of the emulsion polymerized copolymer particles rapidly increases, and too many cross-links outside the particles are formed, which may cause gelation. If used too little, the stability of the resulting copolymer particles may be degraded.
  • the additive in addition to the monomer mixture and emulsifier during the emulsion polymerization, it may further include other additives within a range that does not inhibit the desired effect of the invention.
  • the additive may include at least one crosslinking agent, polymerization initiator, buffer, wetting agent, reducing agent, chain transfer agent, and the like.
  • the crosslinking agent is polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylpropane triacrylate, tripropylene glycol diacrylate, 1, 3-butanediol diacrylate, pentatritol triacrylate, 3-trimethoxysilyl propyl methacrylate, vinyltrimethoxysilane, divinylbenzene, methacrylamide, methacrylamidoethyl ethyleneurea, methacryl ester 1 selected from the group consisting of ethylene urea, allyl ether ethylene urea, or [N-(2-(2-oxoimidazolin-1-yl)ethyl)(4-allylether)(3-hydroxy)butylamine] It may be more than a species.
  • the crosslinking agent may be used in an amount of 0 to 1.5% by weight
  • water-soluble polymerization initiators such as ammonium or alkali metal persulfate (ex.APS, ammonium persulfate), hydrogen peroxide, peroxide, and hydroxyl oxide can be used, and in order to perform an emulsion polymerization reaction at low temperature It may be used with one or more reducing agents, but is not limited thereto.
  • the content of the polymerization initiator may be used in an amount of 0.1 to 2.0% by weight based on the monomer mixture.
  • the polymerization initiator may be divided into one or more times during the polymerization step of the monomer mixture and appropriately divided within the above-described range.
  • the buffer examples include sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, sodium chloride, sodium hydroxide, and the like, but are not limited thereto. Further, these may be used alone or in combination of two or more.
  • the buffer may serve to adjust the pH in the polymerization reaction and impart polymerization stability.
  • the buffer may be used in an amount of 0.1 to 0.8% by weight based on 100% by weight of the monomer mixture.
  • the wetting agent serves as an emulsifier that lowers the surface tension for coating properties, and its content can be used within a range well known in the art.
  • the wetting agent may include a dioctyl sodium sulfosuccinate (DOSS)-based compound.
  • the wetting agent may be used in an amount of 0.1 to 2% by weight based on 100% by weight of the monomer mixture.
  • the chain transfer agent serves to introduce homopolymers, which are polymers composed of only one type of monomer, into micelles, and may include sodium carbonate, sodium methylallyl sulfonate, n-dodecyl mercaptan, and the like. It is not.
  • the chain transfer agent may be used in an amount of 0.01 to 0.50% by weight based on 100% by weight of the monomer mixture.
  • a method of preparing an acrylic emulsion pressure sensitive adhesive composition comprising the step of emulsion polymerization of the free emulsion in the presence of an initiator.
  • the acrylic emulsion pressure-sensitive adhesive composition of the present invention described above may be specifically prepared by the following method, but is not limited thereto.
  • a pre-emulsion is prepared by first mixing a monomer mixture and a polymer emulsifier represented by Chemical Formula 1 with water.
  • a polymer emulsifier represented by Chemical Formula 1 represented by Chemical Formula 1
  • the formation of agglomerates can be reduced by forming a free emulsion before the emulsion polymerization reaction.
  • the (meth) acrylic acid ester-based monomer, vinyl-based monomer, unsaturated carboxylic acid-based monomer, and polymer emulsifier represented by Chemical Formula 1 used in preparing the free emulsion are as described above.
  • one or more other additives described above, that is, a crosslinking agent, a buffering agent, a wetting agent, a reducing agent, and a chain transfer agent may be added.
  • the pre-emulsion and the polymerization initiator are continuously added for a predetermined period of time in an equal ratio, and the pre-emulsion is subjected to emulsion polymerization.
  • water-soluble polymerization initiators such as ammonium or alkali metal persulfate (ex.APS, ammonium persulfate), hydrogen peroxide, peroxide, and hydroxyl oxide can be used, and an emulsion polymerization reaction is performed at low temperature. In order to do so, it may be used together with one or more reducing agents, but is not limited thereto. At this time, the content of the polymerization initiator may be used in an amount of 0.1 to 2.0% by weight based on the monomer mixture. In addition, the polymerization initiator may be divided into one or more times during the polymerization step of the monomer mixture and appropriately divided within the above-described range.
  • ammonium or alkali metal persulfate ex.APS, ammonium persulfate
  • hydrogen peroxide peroxide
  • peroxide peroxide
  • hydroxyl oxide hydroxyl oxide
  • the content of the polymerization initiator may be used in an amount of 0.1 to 2.0% by weight based on the
  • the time to continuously input the pre-emulsion and the polymerization initiator may be 3 to 5 hours.
  • the emulsion polymerization may be carried out in the presence of a polymerization initiator, or by stirring at a temperature of 70 to 90 °C for 3 to 8 hours. Specifically, the emulsion polymerization may be performed at a temperature of about 75 to 90° C. for about 3 hours to about 6 hours. And, considering the physical properties of the pressure-sensitive adhesive may be a polymerization temperature of about 75 to about 85 °C.
  • the acrylic emulsion pressure-sensitive adhesive composition of the present invention prepared according to the above-described method exhibits excellent adhesion properties to both hydrophilic and hydrophobic substrates, and can be applied to an adhesive sheet.
  • the adhesive sheet may be a building interior and exterior material, interior materials, advertising films, or adhesive films or sheets for labels, but the present invention is not necessarily limited to these.
  • An acrylic emulsion pressure-sensitive adhesive composition was prepared by the following method using a modified polyvinyl alcohol emulsifier of Formula 1 having a number average molecular weight (Mn) of 1,000 g/mol and a hydration degree of 99% represented by Equation 1 below. .
  • the number average molecular weight was measured by gel permeation chromatography (GPC), and specifically evaluated using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column. Tetrahydrofuran was used as a solvent and the flow rate was measured at a rate of 1 mL/min. Samples were prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 20 ⁇ L. The values of Mw and Mn were derived using an assay curve formed using polystyrene standards. As for the molecular weight (g/mol) of the polystyrene standard, 8 types of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 were used.
  • aqueous 20% by weight aqueous ammonium persulfate solution was added and dissolved by stirring for 5 minutes.
  • the pre-emulsion and 70 g of a 3% by weight aqueous ammonium persulfate solution were uniformly continuously added for a total of 5 hours and a total of 5.5 hours, respectively, and heated to 85° C. to perform an emulsion polymerization reaction.
  • the temperature was raised to 85° C. and maintained for about 1 hour to complete the reaction of unreacted monomers, and then cooled to room temperature to prepare an acrylic emulsion resin.
  • an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 1,500 g/mol and a hydration degree of 78% was used.
  • an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 4,000 g/mol and a hydration degree of 85% was used.
  • an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 6,000 g/mol and a hydration degree of 78% was used.
  • an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 7,500 g/mol and a hydration degree of 95% was used.
  • an acrylic emulsion resin was prepared in the same manner as in Example 1, except that 22 g of 30% by weight of sodium polyoxyethylene lauryl ether sulfate was used.
  • the acrylic adhesives prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were respectively coated on a silicone coated release paper, and dried in an oven at 120° C. for 1 minute so that the adhesive resin coating layer had a thickness of 20 ⁇ m.
  • An adhesive sheet was made by laminating an adhesive resin coated on silicone release paper with art paper. The adhesive sheet was cut to a size of 25 mm ⁇ 200 mm to prepare an adhesive tape specimen.
  • the specimens prepared above were measured according to FTM 9 in the FINAT test method.
  • the adhesive sheet prepared above was measured according to FTM 9 among the FINAT test methods.
  • the acrylic emulsion pressure-sensitive adhesive composition of the present invention while using a polymer emulsifier having the structure of Formula 1, compared to Comparative Example 1 using a single-molecule emulsifier, while showing excellent adhesion and peel strength to the hydrophobic substrate It can be confirmed that the residual ratio is remarkably low.

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Abstract

The present invention relates to an acrylic emulsion pressure-sensitive adhesive composition. According to the present invention, it is possible to provide a pressure-sensitive adhesive composition having less residue and exhibiting excellent adhesion to both hydrophobic and hydrophilic substrates.

Description

아크릴계 에멀젼 점착제 조성물Acrylic emulsion adhesive composition

관련 출원(들)과의 상호 인용Cross-citation with relevant application(s)

본 출원은 2018년 12월 18일자 한국 특허 출원 제10-2018-0164124호 및 2019년 9월 3일자 한국 특허 출원 제10-2019-0109115호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0164124 dated December 18, 2018 and Korean Patent Application No. 10-2019-0109115 dated September 3, 2019. All content disclosed in the literature is incorporated as part of this specification.

본 발명은 아크릴계 에멀젼 점착제 조성물에 관한 것이다.The present invention relates to an acrylic emulsion pressure-sensitive adhesive composition.

점착제(Pressure-Sensitive Adhesive, PSA)는 작은 압력으로 피착제에 접착하는 성질을 가진 물질이다. 접착제와는 다른 점탄성적인 물질로 초기 점착력, 점착력, 응집력의 기본적인 성질을 가지고 있으며, 인쇄, 화학, 의약품, 가전제품, 자동차, 문구 등 다양한 산업 분야에서 사용되고 있다.Pressure-Sensitive Adhesive (PSA) is a material that has the property of adhering to an adhesive under a small pressure. It is a viscoelastic material different from the adhesive, and has the basic properties of initial adhesion, adhesion, and cohesion, and is used in various industries such as printing, chemicals, pharmaceuticals, home appliances, automobiles, and stationery.

점착제는 제조 시 사용하는 모노머에 따라 아크릴계, 고무계, 실리콘계, EVA계 등으로 분류할 수 있고, 형태에 따라 용제형, 에멀젼형, 핫멜트형으로 분류할 수 있다.The pressure-sensitive adhesive can be classified into acrylic, rubber, silicone, EVA, and the like according to the monomer used during manufacture, and can be classified into a solvent type, an emulsion type, and a hot melt type depending on the type.

과거에는, 대부분 고무계 점착제 또는 용제형 점착제 등이 점착 테이프와 점착 라벨 등에 사용되었으나, 친환경적인 점착제에 대한 수요가 증가하면서 무용제형 점착제에 대한 관심이 높아졌으며, 이에 대한 기술 개발이 진행되었다. 현재는 무용제형 점착제의 사용 및 생산량이 크게 증가되었고, 앞으로도 지속적으로 증가할 것으로 예상된다.In the past, most rubber-based adhesives or solvent-based adhesives were used in adhesive tapes and adhesive labels, etc., but as the demand for eco-friendly adhesives increased, interest in solvent-free adhesives increased, and technology development progressed. Currently, the use and production of solvent-free adhesives has increased significantly and is expected to continue to increase in the future.

무용제형 점착제는 대표적으로 수계 유화 중합에 의해서 제조되는데, 경제성 및 가공성 향상의 측면에서, 응집물 발생이 적고 우수한 점착 물성을 안정적으로 구현할 수 있는 특성이 요구된다.Solvent-free pressure-sensitive adhesives are typically produced by water-based emulsion polymerization, and in terms of improving economic efficiency and processability, there are few aggregates and characteristics capable of stably realizing excellent adhesive properties are required.

이렇게 수계 유화 중합으로 제조되는 수성 점착제는 친수성 유화제를 사용하는데, 일반적으로 친수성과 소수성을 동시에 지니는 양극성 단분자가 친수성 유화제로서 사용된다. 특히 수계에서의 입자 형성 및 유지 안정성을 위하여 설포네이트와 같이 극성이 강한 친수성기를 포함하는 양극성 단분자가 사용된다.The aqueous pressure-sensitive adhesive prepared by water-based emulsion polymerization uses a hydrophilic emulsifier, and in general, a bipolar single molecule having both hydrophilicity and hydrophobicity is used as a hydrophilic emulsifier. Particularly, a bipolar single molecule containing a hydrophilic group having strong polarity, such as sulfonate, is used for particle formation and retention stability in an aqueous system.

한편, 유화제의 친수성기가 너무 많거나, 친수성의 정도가 너무 강할 경우 소수성 기재인 폴리에틸렌, 폴리프로필렌 등의 소재에 대한 점착력이 약한 문제가 있다. 또한, 친수성 소재에 적용하는 경우 지나치게 강한 점착력으로 인하여 점착제의 탈착 시 잔사가 남을 수 있다.On the other hand, if the emulsifier has too many hydrophilic groups, or if the degree of hydrophilicity is too strong, there is a problem in that adhesion to materials such as polyethylene and polypropylene, which are hydrophobic substrates, is weak. In addition, when applied to a hydrophilic material, residues may remain when the adhesive is desorbed due to excessively strong adhesive force.

이러한 문제를 해결하기 위하여 점착제 조성물의 단량체 조성을 소수성으로 하거나, 가교도를 높이는 방법이 제시되었으나, 이 경우 친수성 기재에 대한 점착력이 떨어지는 문제가 있다.In order to solve this problem, a method of making the monomer composition of the pressure-sensitive adhesive composition hydrophobic or increasing the degree of crosslinking has been proposed, but in this case, there is a problem in that adhesion to a hydrophilic substrate is poor.

따라서, 소수성 기재에 대해 개선된 점착력을 나타내면서도, 친수성 소재에 대한 점착력이 유지되며, 잔사 현상이 발생하지 않는 새로운 점착제의 개발이 요구되고 있다.Accordingly, there is a need to develop a new adhesive that exhibits improved adhesion to a hydrophobic substrate, maintains adhesion to a hydrophilic material, and does not generate residue.

본 발명은 친수성 및 소수성 기재 모두에 우수한 점착력을 나타내면서, 피착제에 잔사를 남기지 않는 점착제 조성물 및 이를 제조하는 방법을 제공하고자 한다.The present invention is to provide a pressure-sensitive adhesive composition that does not leave a residue on the adherend, while showing excellent adhesion to both hydrophilic and hydrophobic substrates and a method for manufacturing the same.

본 발명은, (메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물이, 하기 화학식 1로 표시되며, 하기 수학식 1로 표시되는 수화도가 75 내지 99 %이고, 수평균분자량이 1,000 내지 8,000 g/mol인 고분자 유화제 존재 하에 유화 중합된 공중합체를 포함하는, 아크릴계 에멀젼 점착제 조성물을 제공한다.In the present invention, the monomer mixture containing the (meth)acrylic acid ester-based monomer, vinyl-based monomer, and unsaturated carboxylic acid-based monomer is represented by the following formula (1), and has a hydration degree of 75 to 99% represented by the following formula (1). , It provides an acrylic emulsion pressure-sensitive adhesive composition comprising a copolymer emulsion-polymerized in the presence of a polymer emulsifier having a number average molecular weight of 1,000 to 8,000 g/mol.

[화학식 1][Formula 1]

Figure PCTKR2019011396-appb-I000001
Figure PCTKR2019011396-appb-I000001

[수학식 1][Equation 1]

Figure PCTKR2019011396-appb-I000002
Figure PCTKR2019011396-appb-I000002

상기 (메트) 아크릴산 에스테르계 단량체는, 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, 이소프로필 (메트)아크릴레이트, 부틸 (메트)아크릴레이트, 이소부틸 (메트)아크릴레이트, t-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 헵틸 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 2-에틸헥실 (메트)아크릴레이트, 데실 (메트)아크릴레이트, 이소데실 (메트)아크릴레이트, 도데실 (메트)아크릴레이트, 이소보닐 (메트)아크릴레이트, 및 라우릴 (메트)아크릴레이트로 이루어진 군에서 선택된 1종 이상일 수 있다.The (meth) acrylic acid ester monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth) )Acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and lauryl (meth)acrylate It may be one or more selected from the group.

상기 비닐계 단량체는 탄소수 1 내지 5의 알킬 그룹을 포함하는, 비닐 에스테르계 단량체; 및 방향족 비닐계 단량체로 이루어진 군에서 선택된 1종 이상일 수 있다.The vinyl-based monomer includes an alkyl group having 1 to 5 carbon atoms, a vinyl ester-based monomer; And it may be one or more selected from the group consisting of an aromatic vinyl-based monomer.

상기 불포화 카르복실산계 단량체는 무수말레인산, 푸마르산, 크로탄산, 이타콘산, 및 (메트)아크릴산으로 이루어진 군에서 선택된 1종 이상일 수 있다.The unsaturated carboxylic acid-based monomer may be at least one selected from the group consisting of maleic anhydride, fumaric acid, crotanic acid, itaconic acid, and (meth)acrylic acid.

또한, 본 발명은, (메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물; 가교제; 및 상기 화학식 1로 표시되며, 상기 수학식 1로 표시되는 수화도가 75 내지 99 %이고, 수평균분자량이 1,000 내지 8,000 g/mol인 고분자 유화제를 포함하는 프리 에멀젼을 제조하는 단계, 및In addition, the present invention, (meth) acrylic acid ester-based monomer, vinyl-based monomer and a monomer mixture containing an unsaturated carboxylic acid-based monomer; Crosslinking agents; And preparing a pre-emulsion comprising a polymer emulsifier represented by Formula 1, wherein the hydration degree represented by Formula 1 is 75 to 99%, and the number average molecular weight is 1,000 to 8,000 g/mol.

개시제의 존재 하에, 상기 프리 에멀젼을 유화 중합하는 단계를 포함하는, 아크릴계 에멀젼 점착제 조성물의 제조방법을 제공한다.It provides a method for producing an acrylic emulsion pressure-sensitive adhesive composition comprising the step of emulsion polymerization of the pre-emulsion in the presence of an initiator.

상기 고분자 유화제는 단량체 혼합물 100 중량부에 대하여 0.1 내지 5.0 중량부로 포함될 수 있다.The polymer emulsifier may be included in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the monomer mixture.

상기 (메트)아크릴산 에스테르계 단량체는 단량체 혼합물 100 중량부에 대하여 70 내지 99 중량부로 포함될 수 있다.The (meth) acrylic acid ester-based monomer may be included in 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture.

상기 비닐계 단량체는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 1 내지 25 중량부로 포함될 수 있다.The vinyl-based monomer may be included in 1 to 25 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester-based monomer.

상기 불포화 카르복실산계 단량체는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 0.1 내지 5 중량부로 포함될 수 있다.The unsaturated carboxylic acid-based monomer may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester-based monomer.

본 발명에 따르면, 친수성 및 소수성 기재 모두에 우수한 점착력을 나타내면서도 피착제에 잔사를 남기지 않는 점착제 조성물 및 그 제조방법을 제공할 수 있다.According to the present invention, it is possible to provide a pressure-sensitive adhesive composition that does not leave a residue on the adherend, while exhibiting excellent adhesion to both hydrophilic and hydrophobic substrates.

본 발명에서, 제1, 제2 등의 용어는 다양한 구성요소들을 설명하는 데 사용되며, 상기 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만 사용된다.In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

또한, 본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다", "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 숫자, 단계, 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.In addition, the terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include", "have" or "have" are intended to indicate the presence of implemented features, numbers, steps, elements, or combinations thereof, one or more other features or It should be understood that the existence or addition possibilities of numbers, steps, elements, or combinations thereof are not excluded in advance.

본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood that all modifications, equivalents, and substitutes included in the spirit and scope of the present invention are included.

이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 일 구현예에 따르면, (메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물이, 하기 화학식 1로 표시되며, 하기 수학식 1로 표시되는 수화도가 75 내지 99%이고, 수평균분자량이 1,000 내지 8,000 g/mol인 고분자 유화제 존재 하에 유화 중합된 공중합체를 포함하는, 아크릴계 에멀젼 점착제 조성물이 제공된다.According to an embodiment of the present invention, a monomer mixture comprising a (meth)acrylic acid ester-based monomer, a vinyl-based monomer, and an unsaturated carboxylic acid-based monomer is represented by the following Chemical Formula 1, and the degree of hydration represented by the following Chemical Formula 1 Provided is an acrylic emulsion pressure sensitive adhesive composition comprising a copolymer that is 75 to 99% and emulsion polymerized in the presence of a polymer emulsifier having a number average molecular weight of 1,000 to 8,000 g/mol.

[화학식 1][Formula 1]

Figure PCTKR2019011396-appb-I000003
Figure PCTKR2019011396-appb-I000003

[수학식 1][Equation 1]

Figure PCTKR2019011396-appb-I000004
Figure PCTKR2019011396-appb-I000004

상기 화학식 1 및 수학식 1에서, m 및 n은 상기 고분자를 구성하는 반복단위의 몰수이다.In Formula 1 and Formula 1, m and n are the number of moles of repeating units constituting the polymer.

통상 수성 아크릴계 에멀젼 점착제 조성물의 제조 시 유화제로는 설포네이트, 설페이트와 같이 극성이 강한 친수성기를 포함하는 양극성 단분자가 사용된다. 그러나 이러한 유화제를 사용하여 제조된 공중합체, 즉, 라텍스 입자의 에멀젼을 포함하는 아크릴계 에멀젼 점착제 조성물의 경우, 친수성 기재에 대한 점착력이 지나치게 강하여 잔사를 남기는 문제가 있고, 반대로 폴리에틸렌, 폴리프로필렌 등의 소수성 기재에 대한 점착력은 떨어지는 문제가 있다.When preparing an aqueous acrylic emulsion pressure sensitive adhesive composition, a bipolar single molecule containing a hydrophilic group having a strong polarity, such as sulfonate and sulfate, is used as an emulsifier. However, in the case of an acrylic emulsion pressure-sensitive adhesive composition containing an emulsion of a copolymer, that is, an emulsion of latex particles, using such an emulsifier, there is a problem of leaving a residue due to too strong adhesion to a hydrophilic substrate, and conversely, hydrophobicity of polyethylene, polypropylene, etc. There is a problem that the adhesion to the substrate is poor.

이에, 본 발명자들은 소수성 및 친수성 기재 모두에 우수한 점착력을 나타내면서도, 피착제에 잔사를 남기지 않는 점착제 조성물에 관하여 연구를 거듭하였으며, 그 결과, 상기 화학식 1과 같은 고분자 유화제를 사용하는 경우 점착 특성을 향상시킬 수 있음을 확인하여 본 발명을 완성하였다.Accordingly, the present inventors have repeatedly studied the pressure-sensitive adhesive composition that exhibits excellent adhesion to both hydrophobic and hydrophilic substrates, but does not leave a residue on the adherend, and as a result, when using a polymer emulsifier such as Chemical Formula 1, adhesion properties are obtained. The present invention was completed by confirming that it can be improved.

상기 고분자 유화제는 비닐 알코올 및 메틸 비닐 케톤 단량체가 공중합된 변성 폴리비닐알코올계 고분자로서, 교대, 랜덤, 블록 공중합체의 어느 것이든 가능하다. 상기 고분자 유화제에서 친수기인 히드록시기는 수상에서 입자 안정성을 유지하는 역할을 하며, 고분자 사슬 부분은 유화 중합 시 중합이 이루어지는 공간으로 역할 할 수 있다.The polymer emulsifier is a modified polyvinyl alcohol-based polymer in which vinyl alcohol and methyl vinyl ketone monomer are copolymerized, and can be any of alternating, random, and block copolymers. In the polymer emulsifier, the hydroxy group, which is a hydrophilic group, plays a role in maintaining particle stability in the water phase, and the polymer chain portion may serve as a space where polymerization occurs during emulsion polymerization.

바람직하기로, 상기 고분자 유화제는 하기 수학식 1로 표시되는 수화도가 75 내지 99 %, 또는 78 내지 95 %이다.Preferably, the polymer emulsifier has a hydration degree of 75 to 99%, or 78 to 95%, represented by Equation 1 below.

[수학식 1][Equation 1]

Figure PCTKR2019011396-appb-I000005
Figure PCTKR2019011396-appb-I000005

상기 수화도는 고분자 내 비닐알코올로부터 유래된 반복 단위의 퍼센티지로, 수화도가 높을수록 고분자의 친수성이 높음을 의미한다. 만일 수화도가 75 % 미만이면 지나치게 많은 카르복실산 기능기에 의한 잔사 발생 문제가 있을 수 있고, 99 %를 초과하면 실질적으로 폴리비닐알코올에 해당하는데, 이는 물에 대한 용해도가 급격하게 낮아져 유화제로서 적합하지 않으므로 상기 수화도 범위를 만족함이 바람직하다.The hydration degree is a percentage of repeating units derived from vinyl alcohol in the polymer, and the higher the hydration degree, the higher the hydrophilicity of the polymer. If the degree of hydration is less than 75%, there may be a problem of generation of residues due to too many carboxylic acid functional groups, and if it exceeds 99%, it is substantially polyvinyl alcohol, which is rapidly lowered in solubility in water and is suitable as an emulsifier. Since it does not, it is preferable to satisfy the hydration range.

상기 고분자 유화제의 수평균분자량은 1,000 내지 8,000 g/mol 범위가 바람직하다. 만일 고분자 유화제의 수평균분자량이 1,000 g/mol 미만이면 고분자 사슬의 길이가 과도하게 짧아 유화제로서의 역할을 하지 못하게 되는 문제가 있고, 8,000 g/mol을 초과하면 물에 대한 용해도가 낮아 적용이 어렵게 되는 문제가 있을 수 있다. 이때, 상기 고분자 유화제의 수평균분자량은 후술하는 실시예에서 구체화되는 바와 같이, 겔투과 크로마토그래피(GPC)를 이용하여 측정될 수 있다.The number average molecular weight of the polymer emulsifier is preferably in the range of 1,000 to 8,000 g/mol. If the number average molecular weight of the polymer emulsifier is less than 1,000 g/mol, there is a problem that the length of the polymer chain is excessively short, so that it does not function as an emulsifier. There may be a problem. At this time, the number-average molecular weight of the polymer emulsifier can be measured using gel permeation chromatography (GPC), as specified in the examples below.

한편, 상기 고분자 유화제는 단량체 혼합물 총 100 중량부에 대하여 0.1 내지 5 중량부, 또는 0.5 내지 3 중량부로 사용된다. 고분자 유화제의 함량이 단량체 혼합물 100 중량부에 대하여 0.1 중량부 미만인 경우 유화제가 부족하여 미셀 형성을 통한 유화중합이 정상적으로 일어나기 어려우며, 또한 응집물이 크게 발생하는 문제가 있을 수 있고, 5 중량부를 초과하는 경우 과도한 유화제 사용으로 접착물성이 감소하는 문제가 있을 수 있다.On the other hand, the polymer emulsifier is used in an amount of 0.1 to 5 parts by weight, or 0.5 to 3 parts by weight based on 100 parts by weight of the monomer mixture. When the content of the polymer emulsifier is less than 0.1 part by weight based on 100 parts by weight of the monomer mixture, the emulsifier is insufficient, so it is difficult to emulsify and polymerize through micelle formation, and there may be a problem that agglomerates are largely generated, and when it exceeds 5 parts by weight There may be a problem that adhesive properties are reduced due to the use of excessive emulsifiers.

한편, 본 발명의 아크릴계 에멀젼 점착제 조성물은 단량체로 (메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산 단량체를 혼합하여 사용한다. 이와 같이 3종의 단량체를 사용함에 따라, 본 발명의 아크릴계 에멀젼 점착제 조성물은 점착력과 유지력을 전반적으로 향상시키는 효과를 가질 수 있다.Meanwhile, the acrylic emulsion pressure-sensitive adhesive composition of the present invention is used by mixing (meth)acrylic acid ester-based monomer, vinyl-based monomer, and unsaturated carboxylic acid monomer as a monomer. As such, by using three types of monomers, the acrylic emulsion pressure-sensitive adhesive composition of the present invention can have an effect of improving the overall adhesion and retention.

본 명세서에서, "단량체 혼합물"은 중합에 사용되는 모든 단량체를 혼합한 혼합물을 의미하는 것으로, 상기 단량체들을 기반으로 하여, 아크릴계 에멀젼 수지를 만들기 위한 유화 중합 반응에 사용될 수 있는 것이면 특별한 제한이 없는 바, 예를 들어, 상기 단량체들이 함께 혼합된 상태로 중합 반응에 투입될 수도 있고, 상기 단량체들이 순차적으로 중합 반응에 투입될 수도 있다.In the present specification, "monomer mixture" refers to a mixture of all monomers used for polymerization, and based on the monomers, as long as it can be used in an emulsion polymerization reaction to make an acrylic emulsion resin, there is no particular limitation. , For example, the monomers may be added to the polymerization reaction in a mixed state, and the monomers may be sequentially added to the polymerization reaction.

상기 (메트)아크릴산 에스테르계 단량체는 탄소수 1 내지 10의 사슬형 알킬 그룹을 포함하는 것일 수 있으며, 구체적으로 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, 이소프로필 (메트)아크릴레이트, 부틸 (메트)아크릴레이트, 이소부틸 (메트)아크릴레이트, t-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 헵틸 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 2-에틸헥실 (메트)아크릴레이트, 데실 (메트)아크릴레이트, 이소데실 (메트)아크릴레이트, 도데실 (메트)아크릴레이트, 이소보닐 (메트)아크릴레이트, 및 라우릴 (메트)아크릴레이트로 이루어진 군에서 선택된 1종 이상일 수 있다.The (meth)acrylic acid ester-based monomer may include a chain alkyl group having 1 to 10 carbon atoms, specifically methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (Meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate , Octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, iso It may be one or more selected from the group consisting of carbonyl (meth) acrylate, and lauryl (meth) acrylate.

상기 (메트)아크릴산 에스테르계 단량체는, 단량체 혼합물 100 중량부에 대하여 70 내지 99 중량부로 포함될 수 있다.The (meth)acrylic acid ester-based monomer may be included in 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture.

상기 비닐계 단량체는 탄소수 1 내지 5의 알킬 그룹을 포함하는, 비닐 에스테르계 단량체; 및 방향족 비닐계 단량체로 이루어진 군에서 선택된 1종 이상일 수 있다.The vinyl-based monomer includes an alkyl group having 1 to 5 carbon atoms, a vinyl ester-based monomer; And it may be one or more selected from the group consisting of an aromatic vinyl-based monomer.

구체적으로, 상기 비닐 에스테르계 단량체는 분자의 일 말단에 비닐 그룹을 포함하고, 반대쪽 말단에는 탄소수 1 내지 5의 알킬 그룹을 포함하는, 에스테르 형태의 단량체를 들 수 있으며, 구체적으로 예를 들어, 아세트산 비닐, 프로판산 비닐, 부탄산 비닐, 및 펜탄산 비닐로 이루어진 군에서 선택된 1종 이상을 들 수 있다.Specifically, the vinyl ester-based monomer includes a vinyl group at one end of the molecule, and an ester-type monomer including an alkyl group having 1 to 5 carbon atoms at the other end. Specifically, for example, acetic acid And one or more types selected from the group consisting of vinyl, vinyl propanoate, vinyl butanoate, and vinyl pentacarbonate.

그리고, 상기 방향족 비닐계 단량체는, 스티렌, 메틸스티렌, 메틸스티렌, 부틸스티렌, 클로로스티렌, 비닐벤조산, 비닐벤조산메틸, 비닐나프탈렌, 클로로메틸스티렌, 히드록시메틸스티렌 및 디비닐벤젠으로 이루어진 군에서 선택된 1종 이상을 들 수 있다.In addition, the aromatic vinyl monomer is selected from the group consisting of styrene, methylstyrene, methylstyrene, butylstyrene, chlorostyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene and divinylbenzene. 1 or more types are mentioned.

상기 비닐계 단량체는, 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 1 내지 25 중량부, 또는 5 내지 20 중량부로 사용되며, 이에 따라 상기 유화 중합체 내에서 비닐계 단량체 유래 반복 단위는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 약 1 내지 25 중량부, 또는 5 내지 20 중량부로 포함된다.The vinyl monomer is used in an amount of 1 to 25 parts by weight, or 5 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester monomer, and accordingly, the repeating unit derived from the vinyl monomer in the emulsifying polymer is the ( Met) about 1 to 25 parts by weight, or 5 to 20 parts by weight based on 100 parts by weight of the acrylic ester monomer.

만일 비닐계 단량체가 너무 많이 사용되는 경우 반응속도 차이에 의하여 고분자 사슬의 형성이 방해되어 요구수준의 점착력을 확보하지 못하며, 또한 잔류단량체가 크게 발생할 수 있다. 반면 너무 적게 사용되는 경우, 점착력이 저하되는 문제가 발생할 수 있다.If too many vinyl-based monomers are used, the formation of polymer chains is hindered by the difference in reaction rate, so that the required level of adhesion cannot be secured, and residual monomers can also be generated. On the other hand, if it is used too little, a problem that the adhesive strength is lowered may occur.

상기 불포화 카르복실산 단량체는 무수말레인산, 푸마르산, 크로탄산, 이타콘산, 및 (메트)아크릴산으로 이루어진 군에서 선택된 1종 이상일 수 있으나, 이에 제한되는 것은 아니다.The unsaturated carboxylic acid monomer may be at least one selected from the group consisting of maleic anhydride, fumaric acid, crotanic acid, itaconic acid, and (meth)acrylic acid, but is not limited thereto.

상기 불포화 카르복실산계 단량체는, 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 0.1 내지 5 중량부, 또는 0.5 내지 2 중량부로 사용되며, 이에 따라 상기 유화 중합체 내에서 불포화 카르복실산계 단량체 유래 반복 단위는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 약 0.1 내지 5 중량부, 또는 0.5 내지 2 중량부로 포함된다.The unsaturated carboxylic acid-based monomer is used in an amount of 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester-based monomer. The unit is contained in about 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer.

만일 불포화 카르복실산계 단량체가 너무 많이 사용되는 경우, 유화 중합된 공중합체 입자의 점도가 급격히 증가하는 문제점이 발생할 수 있고, 입자 외부의 가교 결합이 너무 많이 형성되어, 겔화를 유발할 수 있다. 너무 적게 사용되는 경우, 생성되는 공중합체 입자의 안정성이 저하될 수 있다.If the unsaturated carboxylic acid-based monomer is used too much, a problem may arise in which the viscosity of the emulsion polymerized copolymer particles rapidly increases, and too many cross-links outside the particles are formed, which may cause gelation. If used too little, the stability of the resulting copolymer particles may be degraded.

한편, 본 발명의 일 실시예에 따르면, 상기 유화 중합 시 단량체 혼합물 및 유화제 외에, 발명이 목적하는 효과를 저해하지 않는 범위 내에서 기타 첨가제를 더 포함할 수 있다. 일례로, 상기 첨가제로는 가교제, 중합 개시제, 완충제, 습윤제, 환원제, 사슬 이동제 등을 1 이상 포함할 수 있다.On the other hand, according to an embodiment of the present invention, in addition to the monomer mixture and emulsifier during the emulsion polymerization, it may further include other additives within a range that does not inhibit the desired effect of the invention. In one example, the additive may include at least one crosslinking agent, polymerization initiator, buffer, wetting agent, reducing agent, chain transfer agent, and the like.

상기 가교제는 폴리에틸렌글리콜 디아크릴레이트, 폴리프로필렌글리콜 디아크릴레이트, 1,6-헥산디올 디아크릴레이트, 트리메틸올프로판 트리아크릴레이트, 에톡시화 트리메틸프로판 트리아크릴레이트, 트리프로필렌글리콜 디아크릴레이트, 1,3-부탄디올디아크릴레이트, 펜타트리톨트리아크릴레이트, 3-트리메톡시실릴 프로필메타크릴레이트, 비닐트리메톡시실란, 디비닐벤젠, 메타크릴아미드, 메타크릴아미도에틸 에틸렌우레아, 메타크릴에스테르 에틸렌우레아, 알릴 에테르 에틸렌우레아, 또는 [N-(2-(2-옥소이미다졸린-1-일)에틸)(4-알릴에테르)(3-히드록시)부틸아민]으로 이루어진 군에서 선택된 1종 이상일 수 있다. 상기 가교제는 상기 단량체 혼합물 기준으로 0 내지 1.5 중량%로 사용할 수 있다.The crosslinking agent is polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylpropane triacrylate, tripropylene glycol diacrylate, 1, 3-butanediol diacrylate, pentatritol triacrylate, 3-trimethoxysilyl propyl methacrylate, vinyltrimethoxysilane, divinylbenzene, methacrylamide, methacrylamidoethyl ethyleneurea, methacryl ester 1 selected from the group consisting of ethylene urea, allyl ether ethylene urea, or [N-(2-(2-oxoimidazolin-1-yl)ethyl)(4-allylether)(3-hydroxy)butylamine] It may be more than a species. The crosslinking agent may be used in an amount of 0 to 1.5% by weight based on the monomer mixture.

상기 중합 개시제로는, 암모늄 또는 알칼리 금속의 과황산염(ex. APS, ammonium persulfate), 과산화수소, 퍼옥시드, 히드록퍼옥시드 등의 수용성 중합 개시제를 사용할 수 있으며, 저온 하에 유화 중합 반응을 실시하기 위하여 환원제 1종 이상과 함께 사용할 수도 있으나, 이에 한정되는 것은 아니다. 이때, 상기 중합 개시제의 함량은, 상기 단량체 혼합물 기준으로 0.1 내지 2.0 중량% 로 사용할 수 있다. 또한, 상기 중합 개시제는 상기 단량체 혼합물의 중합 단계 시, 1회 이상 분할하여 상술한 범위 내에서 적절히 분할하여 사용할 수도 있다.As the polymerization initiator, water-soluble polymerization initiators such as ammonium or alkali metal persulfate (ex.APS, ammonium persulfate), hydrogen peroxide, peroxide, and hydroxyl oxide can be used, and in order to perform an emulsion polymerization reaction at low temperature It may be used with one or more reducing agents, but is not limited thereto. At this time, the content of the polymerization initiator may be used in an amount of 0.1 to 2.0% by weight based on the monomer mixture. In addition, the polymerization initiator may be divided into one or more times during the polymerization step of the monomer mixture and appropriately divided within the above-described range.

상기 완충제(buffer)로는, 소듐 바이카보네이트, 소듐 카보네이트, 소듐 포스페이트, 소듐 설페이트, 소듐 클로라이드, 소듐 하이드록사이드 등을 들 수 있으나, 이에 한정되는 것은 아니다. 또한, 이들은 단독으로 또는 2종 이상 혼합되어 사용될 수 있다. 상기 완충제는 중합 반응에서 pH를 조절하고, 중합 안정성을 부여하는 역할을 수행할 수 있다. 상기 완충제는 단량체 혼합물 100 중량%를 기준으로 0.1 내지 0.8 중량%로 사용할 수 있다.Examples of the buffer include sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, sodium chloride, sodium hydroxide, and the like, but are not limited thereto. Further, these may be used alone or in combination of two or more. The buffer may serve to adjust the pH in the polymerization reaction and impart polymerization stability. The buffer may be used in an amount of 0.1 to 0.8% by weight based on 100% by weight of the monomer mixture.

상기 습윤제 (wetting agent)는 코팅성을 위해 표면 장력을 낮춰주는 유화제의 역할을 수행하는 것으로, 그 함량은 이 분야에 잘 알려진 범위 내에서 사용 가능하다. 일 예로, 상기 습윤제로는, 디옥틸 소듐 설포숙시네이트(DOSS, dioctyl sodium sulfosuccinate)계 화합물을 들 수 있다. 상기 습윤제는 단량체 혼합물 100 중량%를 기준으로 0.1 내지 2 중량%로 사용할 수 있다.The wetting agent serves as an emulsifier that lowers the surface tension for coating properties, and its content can be used within a range well known in the art. As an example, the wetting agent may include a dioctyl sodium sulfosuccinate (DOSS)-based compound. The wetting agent may be used in an amount of 0.1 to 2% by weight based on 100% by weight of the monomer mixture.

상기 사슬 이동제는, 한 종류의 단량체로만 구성된 중합체인 호모 폴리머들을 마이셀 내로 들여보내는 역할을 하는 것으로, 소듐 카보네이트, 소듐 메틸알릴 설포네이트, n-도데실 머캅탄 등을 포함할 수 있으나, 이에 한정되는 것은 아니다. 상기 사슬 이동제는 단량체 혼합물 100 중량%를 기준으로 0.01 내지 0.50 중량%로 사용할 수 있다.The chain transfer agent serves to introduce homopolymers, which are polymers composed of only one type of monomer, into micelles, and may include sodium carbonate, sodium methylallyl sulfonate, n-dodecyl mercaptan, and the like. It is not. The chain transfer agent may be used in an amount of 0.01 to 0.50% by weight based on 100% by weight of the monomer mixture.

한편, 본 발명의 다른 일 구현예에 따르면,Meanwhile, according to another embodiment of the present invention,

(메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물; 및 상기 화학식 1로 표시되는 고분자 유화제를 포함하는 프리 에멀젼을 제조하는 단계, 및A monomer mixture containing a (meth)acrylic acid ester-based monomer, a vinyl-based monomer, and an unsaturated carboxylic acid-based monomer; And preparing a pre-emulsion comprising a polymer emulsifier represented by Chemical Formula 1, and

개시제의 존재 하에, 상기 프리 에멀젼을 유화 중합하는 단계를 포함하는, 아크릴계 에멀젼 점착제 조성물의 제조방법이 제공된다.A method of preparing an acrylic emulsion pressure sensitive adhesive composition is provided, comprising the step of emulsion polymerization of the free emulsion in the presence of an initiator.

상술한 본 발명의 아크릴계 에멀젼 점착제 조성물은 구체적으로 하기와 같은 방법에 의하여 제조될 수 있으나, 반드시 이에 한정되는 것은 아니다.The acrylic emulsion pressure-sensitive adhesive composition of the present invention described above may be specifically prepared by the following method, but is not limited thereto.

본 발명의 제조방법에서는 먼저 단량체 혼합물 및 화학식 1로 표시되는 고분자 유화제를 물과 함께 혼합하여 프리 에멀전(pre-emulsion)을 제조한다. 이와 같이 유화 중합 반응 전 프리 에멀젼을 형성함으로써 응집물의 생성을 감소시킬 수 있다.In the production method of the present invention, a pre-emulsion is prepared by first mixing a monomer mixture and a polymer emulsifier represented by Chemical Formula 1 with water. Thus, the formation of agglomerates can be reduced by forming a free emulsion before the emulsion polymerization reaction.

이때, 프리 에멀젼 제조에 사용되는 (메트) 아크릴산 에스테르계 단량체, 비닐계 단량체, 불포화 카르복실산계 단량체, 및 화학식 1로 표시되는 고분자 유화제는 전술한 바와 같다. 또한, 프리 에멀젼 제조 시, 상술한 기타 첨가제, 즉, 가교제, 완충제, 습윤제, 환원제, 사슬 이동제 등을 1종 이상 첨가할 수 있다.In this case, the (meth) acrylic acid ester-based monomer, vinyl-based monomer, unsaturated carboxylic acid-based monomer, and polymer emulsifier represented by Chemical Formula 1 used in preparing the free emulsion are as described above. In addition, in the preparation of the pre-emulsion, one or more other additives described above, that is, a crosslinking agent, a buffering agent, a wetting agent, a reducing agent, and a chain transfer agent, may be added.

다음으로, 상기 프리 에멀젼 및 중합 개시제를 균등한 비율로 소정의 시간 동안 연속 투입하여, 상기 프리 에멀젼을 유화 중합한다.Next, the pre-emulsion and the polymerization initiator are continuously added for a predetermined period of time in an equal ratio, and the pre-emulsion is subjected to emulsion polymerization.

상기 중합 개시제는 전술한 바와 같이 암모늄 또는 알칼리 금속의 과황산염(ex. APS, ammonium persulfate), 과산화수소, 퍼옥시드, 히드록퍼옥시드 등의 수용성 중합 개시제를 사용할 수 있으며, 저온 하에 유화 중합 반응을 실시하기 위하여 환원제 1종 이상과 함께 사용할 수도 있으나, 이에 한정되는 것은 아니다. 이때, 상기 중합 개시제의 함량은, 상기 단량체 혼합물 기준으로 0.1 내지 2.0 중량% 로 사용할 수 있다. 또한, 상기 중합 개시제는 상기 단량체 혼합물의 중합 단계 시, 1회 이상 분할하여 상술한 범위 내에서 적절히 분할하여 사용할 수도 있다.As the above-described polymerization initiator, water-soluble polymerization initiators such as ammonium or alkali metal persulfate (ex.APS, ammonium persulfate), hydrogen peroxide, peroxide, and hydroxyl oxide can be used, and an emulsion polymerization reaction is performed at low temperature. In order to do so, it may be used together with one or more reducing agents, but is not limited thereto. At this time, the content of the polymerization initiator may be used in an amount of 0.1 to 2.0% by weight based on the monomer mixture. In addition, the polymerization initiator may be divided into one or more times during the polymerization step of the monomer mixture and appropriately divided within the above-described range.

상기 프리 에멀젼 및 중합 개시제를 연속 투입하는 시간은 3 내지 5 시간일 수 있다.The time to continuously input the pre-emulsion and the polymerization initiator may be 3 to 5 hours.

상기 유화 중합은 중합 개시제 존재 하에서, 또는 70 내지 90 ℃의 온도에서 3 시간 내지 8 시간 동안 교반하여 수행할 수 있다. 구체적으로 상기 유화 중합은 약 75 내지 90 ℃의 온도에서 약 3 시간 내지 약 6 시간 동안 수행할 수 있다. 그리고, 점착제의 물성을 고려할 때 중합온도는 약 75 내지 약 85 ℃일 수 있다.The emulsion polymerization may be carried out in the presence of a polymerization initiator, or by stirring at a temperature of 70 to 90 ℃ for 3 to 8 hours. Specifically, the emulsion polymerization may be performed at a temperature of about 75 to 90° C. for about 3 hours to about 6 hours. And, considering the physical properties of the pressure-sensitive adhesive may be a polymerization temperature of about 75 to about 85 ℃.

전술한 방법에 따라 제조된 본 발명의 아크릴계 에멀젼 점착제 조성물은 친수성 및 소수성 기재 모두에 우수한 점착 특성을 나타내는 바, 점착 시트에 적용될 수 있다. 상기 점착 시트는 건축 내외장재, 인테리어 재료, 광고용 필름, 또는 라벨의 점착용 필름이나 시트일 수 있지만, 본 발명이 반드시 이들만으로 한정되는 것은 아니다.The acrylic emulsion pressure-sensitive adhesive composition of the present invention prepared according to the above-described method exhibits excellent adhesion properties to both hydrophilic and hydrophobic substrates, and can be applied to an adhesive sheet. The adhesive sheet may be a building interior and exterior material, interior materials, advertising films, or adhesive films or sheets for labels, but the present invention is not necessarily limited to these.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 상세한 설명이 한정되는 것은 아니다.Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the detailed description of the present invention is not limited thereby.

[실시예][Example]

실시예 1Example 1

수평균분자량(Mn)이 1,000 g/mol이고, 하기 수학식 1로 표시되는 수화도가 99 %인 하기 화학식 1의 변성 폴리비닐 알코올 유화제를 이용하여, 하기의 방법으로 아크릴계 에멀젼 점착제 조성물을 제조하였다.An acrylic emulsion pressure-sensitive adhesive composition was prepared by the following method using a modified polyvinyl alcohol emulsifier of Formula 1 having a number average molecular weight (Mn) of 1,000 g/mol and a hydration degree of 99% represented by Equation 1 below. .

[화학식 1][Formula 1]

Figure PCTKR2019011396-appb-I000006
Figure PCTKR2019011396-appb-I000006

[수학식 1][Equation 1]

Figure PCTKR2019011396-appb-I000007
Figure PCTKR2019011396-appb-I000007

이때, 상기 수평균분자량은 겔 투과 크로마토그래피(GPC)에 의하여 측정되었으며, 구체적으로 Polymer Laboratories PLgel MIX-B 300mm 길이 칼럼을 이용하여 Waters PL-GPC220 기기를 이용하여 평가하였다. 테트라하이드로퓨란을 용매로서 사용하였으며 유속은 1mL/min의 속도로 측정하였다. 샘플은 10mg/10mL의 농도로 조제한 다음, 20 μL 의 양으로 공급하였다. 폴리스티렌 표준을 이용하여 형성된 검정 곡선을 이용하여 Mw 및 Mn 의 값을 유도하였다. 폴리스티렌 표준품의 분자량(g/mol)은 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 의 8종을 사용하였다.At this time, the number average molecular weight was measured by gel permeation chromatography (GPC), and specifically evaluated using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column. Tetrahydrofuran was used as a solvent and the flow rate was measured at a rate of 1 mL/min. Samples were prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 20 μL. The values of Mw and Mn were derived using an assay curve formed using polystyrene standards. As for the molecular weight (g/mol) of the polystyrene standard, 8 types of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 were used.

3 L 용량의 유리 반응기에 물 138 g을 넣고 질소 분위기 하에서 85 ℃로 승온하고 유지하였다.138 g of water was added to a 3 L glass reactor, and the temperature was raised and maintained at 85° C. under a nitrogen atmosphere.

별도로, 프리 에멀젼(pre-emelsion) 제조를 위해 2-에틸헥실아크릴레이트 557 g, 메틸메타아크릴레이트 56 g, 비닐아세테이트 57 g, 스티렌 14 g, 아크릴산 14 g, 히드록시에틸아크릴레이트 14 g, 메타아크릴아미도에틸 에틸렌 우레아(methacrylamidoethyl ethylene urea, 또는 N-(2-(2-oxoimidazolidin-1-yl)ethyl)methacrylamide, Sipomer® WAMII) 1.5 g의 혼합물에, 상기 변성 폴리비닐 알코올 유화제 14 g, 60 중량%의 소듐 디옥틸 설포석시네이트 수용액 6 g 소듐하이드록사이드 1.5 g, 및 물 176 g으로 이루어진 용액을 투입하고 교반기로 섞어 백탁의 프리 에멀젼을 제조하였다.Separately, 557 g of 2-ethylhexyl acrylate, 56 g of methyl methacrylate, 57 g of vinyl acetate, 14 g of styrene, 14 g of acrylic acid, 14 g of hydroxyethyl acrylate, meta for preparation of pre-emelsion To a mixture of 1.5 g of acrylamidoethyl ethylene urea (methacrylamidoethyl ethylene urea, or N-(2-(2-oxoimidazolidin-1-yl)ethyl)methacrylamide, Sipomer ® WAMII), the modified polyvinyl alcohol emulsifier 14 g, 60 A solution of 6% sodium hydroxide 1.5 g, and 176 g water was added by weight% sodium dioctyl sulfosuccinate aqueous solution and mixed with a stirrer to prepare a white emulsion free emulsion.

상기 물이 담긴 유리 반응기에 20 중량%의 과황산 암모늄 수용액 3 g을 투입하고 5 분 동안 교반하여 용해시켰다. 상기 유리 반응기에 상기 프리 에멀젼과 3 중량%의 과황산 암모늄 수용액 70 g을 각각 총 5 시간 및 총 5.5 시간 동안 균등하게 연속 투입하고, 85 ℃로 승온하여 유화 중합 반응을 수행하였다.To the glass reactor containing water, 3 g of an aqueous 20% by weight aqueous ammonium persulfate solution was added and dissolved by stirring for 5 minutes. To the glass reactor, the pre-emulsion and 70 g of a 3% by weight aqueous ammonium persulfate solution were uniformly continuously added for a total of 5 hours and a total of 5.5 hours, respectively, and heated to 85° C. to perform an emulsion polymerization reaction.

이렇게 프리 에멀젼과 과황산 암모늄 수용액을 모두 투입하고 나서 85 ℃로 승온하여 약 1 시간 동안 유지하며 미반응 단량체들의 반응을 완료한 다음, 상온으로 냉각하여 아크릴계 에멀젼 수지를 제조하였다.Thus, after adding both the free emulsion and the aqueous ammonium persulfate solution, the temperature was raised to 85° C. and maintained for about 1 hour to complete the reaction of unreacted monomers, and then cooled to room temperature to prepare an acrylic emulsion resin.

실시예 2Example 2

상기 화학식 1의 유화제로, 수평균분자량이 1,500 g/mol이고, 수화도가 78 %인 변성 폴리비닐 알코올 유화제를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 수지를 제조하였다.As the emulsifier of Formula 1, an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 1,500 g/mol and a hydration degree of 78% was used.

실시예 3Example 3

상기 화학식 1의 유화제로, 수평균분자량이 4,000 g/mol이고, 수화도가 85 %인 변성 폴리비닐 알코올 유화제를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 수지를 제조하였다.As the emulsifier of Formula 1, an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 4,000 g/mol and a hydration degree of 85% was used.

실시예 4Example 4

상기 화학식 1의 유화제로, 수평균분자량이 6,000 g/mol이고, 수화도가 78 %인 변성 폴리비닐 알코올 유화제를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 수지를 제조하였다.As the emulsifier of Formula 1, an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 6,000 g/mol and a hydration degree of 78% was used.

실시예 5Example 5

상기 화학식 1의 유화제로, 수평균분자량이 7,500 g/mol이고, 수화도가 95 %인 변성 폴리비닐 알코올 유화제를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 수지를 제조하였다.As the emulsifier of Chemical Formula 1, an acrylic emulsion resin was prepared in the same manner as in Example 1, except that a modified polyvinyl alcohol emulsifier having a number average molecular weight of 7,500 g/mol and a hydration degree of 95% was used.

비교예 1Comparative Example 1

상기 화학식 1의 유화제 대신, 30 중량%의 소듐 폴리옥시에틸렌 라우릴 에테르설페이트 22 g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 수지를 제조하였다.Instead of the emulsifier of Formula 1, an acrylic emulsion resin was prepared in the same manner as in Example 1, except that 22 g of 30% by weight of sodium polyoxyethylene lauryl ether sulfate was used.

실험예Experimental Example

점착 시트의 제조Preparation of adhesive sheet

실시예 1 내지 5와 비교예 1 내지 2에서 제조된 아크릴 점착제를 각각 실리콘 코팅 이형지 위에 도포하고, 120 ℃의 오븐에서 1 분간 건조하여 점착 수지 코팅층이 20 ㎛ 두께를 갖도록 하였다. 실리콘 이형지 위에 도포된 점착 수지를 아트지와 라미네이션하여 점착 시트를 만들었다. 이 점착 시트를 25 mm × 200 mm 크기로 재단하여 점착 테이프 시편을 제조하였다.The acrylic adhesives prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were respectively coated on a silicone coated release paper, and dried in an oven at 120° C. for 1 minute so that the adhesive resin coating layer had a thickness of 20 μm. An adhesive sheet was made by laminating an adhesive resin coated on silicone release paper with art paper. The adhesive sheet was cut to a size of 25 mm×200 mm to prepare an adhesive tape specimen.

물성평가Property evaluation

1) 초기 점착력(loop tack) 측정 방법1) How to measure the initial adhesion (loop tack)

상기에서 제조된 시편에 대하여, FINAT 테스트 방법 중 FTM 9에 준하여 측정하였다.The specimens prepared above were measured according to FTM 9 in the FINAT test method.

1 inch x 20 cm의 크기로 시편을 준비한 후, 이형지를 제거하고 시트의 양쪽을 접어 루프(loop) 모양을 만든 후 양 끝단을 고정한다. 이 루프(Loop)를 HDPE재질로 구성된 사각판 모양의 점착기재 표면에 순간적으로 부착한 후, 5초 후 분리할 때 최고치에 해당하는 힘을 23 ℃, 50% 습도의 측정 환경에서 측정한다. 측정 시편을 5 개 이상 준비하여 측정한 후 평균한다. (단위: N/in)After preparing the specimen to a size of 1 inch x 20 cm, remove the release paper, fold both sides of the sheet to form a loop, and fix both ends. When the loop is instantaneously attached to the surface of a rectangular plate-shaped adhesive base material made of HDPE material, and then separated after 5 seconds, the force corresponding to the highest value is measured in a measurement environment of 23°C and 50% humidity. Prepare and measure 5 or more test specimens and average them. (Unit: N/in)

2) 박리력(peel) 측정 방법2) Peel measurement method

상기에서 제조된 점착 시트는 FINAT 테스트 방법 중 FTM 9에 준하여 측정하였다.The adhesive sheet prepared above was measured according to FTM 9 among the FINAT test methods.

1 inch x 20 cm의 크기로 시편을 준비한 후, HDPE 재질로 구성된 사각판 모양의 점착기재 표면과 부착면이 1 inch x 1 inch 이상이 되도록 부착한 후 2 kg 롤러로 2 회 왕복하여 압착한다. 20 분 후, 300 mm/min의 속도로 90°부착면의 방향으로 분리할 때 해당하는 힘의 평균을 23 ℃, 50% 습도의 측정 환경에서 측정한다. 측정 시편을 5 개 이상 준비하여 측정한 후 평균한다.After preparing the specimen to a size of 1 inch x 20 cm, attach it so that the surface and the attachment surface of a square plate shape made of HDPE material are 1 inch x 1 inch or more, and then press and repress twice with a 2 kg roller. After 20 minutes, when separating in the direction of the 90° attachment surface at a speed of 300 mm/min, the average of the corresponding forces is measured in a measurement environment of 23° C. and 50% humidity. Prepare and measure 5 or more test specimens and average them.

3) 잔사율 측정 방법3) Residual rate measurement method

스테인리스 스틸(SUS)에 제조한 점착 시트를 부착시킨 후 60 ℃ 온도 및 60RH% 상대습도에서 24 시간 숙성한 후 180도 방향으로 박리하면서 박리력 테스트를 진행하여, 박리 후에 전체 면적 중 SUS에 점착제가 묻어 있는 부분의 비율을 육안으로 확인하여 잔사율을 측정하였다.After attaching the adhesive sheet made of stainless steel (SUS), aged for 24 hours at 60° C. temperature and 60 RH% relative humidity, the peel strength test was conducted while peeling in the 180-degree direction. The proportion of the buried part was visually checked to measure the residual ratio.

상기 방법으로 측정된 각 실시예 및 비교예의 점착 시트의 초기 점착력(loop tack), 박리력(peel), 및 잔사율을 하기 표 1에 나타내었다.The initial adhesive strength (loop tack), peel strength (peel), and the residual ratio of the adhesive sheet of each of the Examples and Comparative Examples measured by the above method are shown in Table 1 below.

Figure PCTKR2019011396-appb-T000001
Figure PCTKR2019011396-appb-T000001

상기 표 1을 참조하면, 본 발명의 아크릴계 에멀젼 점착제 조성물은 화학식 1의 구조를 갖는 고분자 유화제를 사용함에 따라, 단분자 유화제를 사용한 비교예 1에 비하여 소수성 기재에 대한 우수한 점착력과 박리력을 나타내면서도 잔사율이 현저히 낮은 것을 확인할 수 있다. Referring to Table 1, the acrylic emulsion pressure-sensitive adhesive composition of the present invention, while using a polymer emulsifier having the structure of Formula 1, compared to Comparative Example 1 using a single-molecule emulsifier, while showing excellent adhesion and peel strength to the hydrophobic substrate It can be confirmed that the residual ratio is remarkably low.

Claims (9)

(메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물이, 하기 화학식 1로 표시되며, 하기 수학식 1로 표시되는 수화도가 75 내지 99 %이고, 수평균분자량이 1,000 내지 8,000 g/mol인 고분자 유화제 존재 하에 유화 중합된 공중합체를 포함하는, 아크릴계 에멀젼 점착제 조성물:A monomer mixture comprising a (meth)acrylic acid ester-based monomer, a vinyl-based monomer, and an unsaturated carboxylic acid-based monomer is represented by the following formula (1), the hydration degree represented by the following formula (1) is 75 to 99%, and the number average molecular weight Acrylic emulsion pressure-sensitive adhesive composition comprising a copolymer that is emulsion polymerized in the presence of a polymer emulsifier of 1,000 to 8,000 g/mol: [화학식 1][Formula 1]
Figure PCTKR2019011396-appb-I000008
Figure PCTKR2019011396-appb-I000008
 [수학식 1][Equation 1]
Figure PCTKR2019011396-appb-I000009
Figure PCTKR2019011396-appb-I000009
 제1항에 있어서,According to claim 1, 상기 (메트) 아크릴산 에스테르계 단량체는, 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, 이소프로필 (메트)아크릴레이트, 부틸 (메트)아크릴레이트, 이소부틸 (메트)아크릴레이트, t-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 헵틸 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 2-에틸헥실 (메트)아크릴레이트, 데실 (메트)아크릴레이트, 이소데실 (메트)아크릴레이트, 도데실 (메트)아크릴레이트, 이소보닐 (메트)아크릴레이트, 및 라우릴 (메트)아크릴레이트로 이루어진 군에서 선택된 1종 이상인, 아크릴계 에멀젼 점착제 조성물.The (meth) acrylic acid ester monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth) )Acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and lauryl (meth)acrylate At least one selected from the group, acrylic emulsion pressure-sensitive adhesive composition. 제1항에 있어서,According to claim 1, 상기 비닐계 단량체는 탄소수 1 내지 5의 알킬 그룹을 포함하는, 비닐 에스테르계 단량체; 및 방향족 비닐계 단량체로 이루어진 군에서 선택된 1종 이상인, 아크릴계 에멀젼 점착제 조성물.The vinyl-based monomer includes an alkyl group having 1 to 5 carbon atoms, a vinyl ester-based monomer; And at least one selected from the group consisting of aromatic vinyl monomers, acrylic emulsion pressure-sensitive adhesive composition. 제1항에 있어서,According to claim 1, 상기 불포화 카르복실산계 단량체는 무수말레인산, 푸마르산, 크로탄산, 이타콘산, 및 (메트)아크릴산으로 이루어진 군에서 선택된 1종 이상인, 아크릴계 에멀젼 점착제 조성물.The unsaturated carboxylic acid monomer is at least one selected from the group consisting of maleic anhydride, fumaric acid, crotanic acid, itaconic acid, and (meth)acrylic acid, acrylic emulsion pressure-sensitive adhesive composition. (메트)아크릴산 에스테르계 단량체, 비닐계 단량체 및 불포화 카르복실산계 단량체를 포함하는 단량체 혼합물; 및 하기 화학식 1로 표시되며, 하기 수학식 1로 표시되는 수화도가 75 내지 99 %이고, 수평균분자량이 1,000 내지 8,000 g/mol인 고분자 유화제를 포함하는 프리 에멀젼을 제조하는 단계, 및A monomer mixture containing a (meth)acrylic acid ester-based monomer, a vinyl-based monomer, and an unsaturated carboxylic acid-based monomer; And preparing a pre-emulsion comprising a polymer emulsifier having a hydration degree of 75 to 99% and a number average molecular weight of 1,000 to 8,000 g/mol, represented by the following Chemical Formula 1, and 상기 프리 에멀젼과 개시제를 혼합하여 유화 중합하는 단계를 포함하는, 아크릴계 에멀젼 점착제 조성물의 제조방법:Method for producing an acrylic emulsion pressure-sensitive adhesive composition comprising the step of emulsion polymerization by mixing the pre-emulsion and the initiator: [화학식 1][Formula 1]
Figure PCTKR2019011396-appb-I000010
Figure PCTKR2019011396-appb-I000010
 [수학식 1][Equation 1]
Figure PCTKR2019011396-appb-I000011
Figure PCTKR2019011396-appb-I000011
 제5항에 있어서,The method of claim 5, 상기 고분자 유화제는 단량체 혼합물 100 중량부에 대하여 0.1 내지 5.0 중량부로 포함되는, 아크릴계 에멀젼 점착제 조성물의 제조방법.The polymer emulsifier is contained in 0.1 to 5.0 parts by weight based on 100 parts by weight of the monomer mixture, a method for producing an acrylic emulsion pressure-sensitive adhesive composition. 제5항에 있어서,The method of claim 5, 상기 (메트)아크릴산 에스테르계 단량체는 단량체 혼합물 100 중량부에 대하여 70 내지 99 중량부로 포함되는, 아크릴계 에멀젼 점착제 조성물의 제조방법.The (meth) acrylic acid ester-based monomer is contained in 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture, a method for producing an acrylic emulsion pressure-sensitive adhesive composition. 제5항에 있어서,The method of claim 5, 상기 비닐계 단량체는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 1 내지 25 중량부로 포함되는, 아크릴계 에멀젼 점착제 조성물의 제조방법.The vinyl-based monomer is included in 1 to 25 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester-based monomer, a method for producing an acrylic emulsion pressure-sensitive adhesive composition. 제5항에 있어서,The method of claim 5, 상기 불포화 카르복실산계 단량체는 상기 (메트) 아크릴산 에스테르계 단량체 100 중량부에 대하여 0.1 내지 5 중량부로 포함되는, 아크릴계 에멀젼 점착제 조성물의 제조방법.The unsaturated carboxylic acid monomer is contained in 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer, a method for producing an acrylic emulsion pressure-sensitive adhesive composition.
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