WO2015008930A1 - Acrylic emulsion resin having excellent adhesive property and preparation method therefor - Google Patents

Acrylic emulsion resin having excellent adhesive property and preparation method therefor Download PDF

Info

Publication number
WO2015008930A1
WO2015008930A1 PCT/KR2014/004512 KR2014004512W WO2015008930A1 WO 2015008930 A1 WO2015008930 A1 WO 2015008930A1 KR 2014004512 W KR2014004512 W KR 2014004512W WO 2015008930 A1 WO2015008930 A1 WO 2015008930A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
monomer
meth
acrylic emulsion
emulsion resin
Prior art date
Application number
PCT/KR2014/004512
Other languages
French (fr)
Korean (ko)
Inventor
이금형
김영민
하재웅
한정섭
송공주
김미영
Original Assignee
주식회사 엘지화학
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
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201480013397.6A priority Critical patent/CN105189580B/en
Publication of WO2015008930A1 publication Critical patent/WO2015008930A1/en

Links

Classifications

    • 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
    • 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
    • C08F218/08—Vinyl acetate
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
    • C08F220/22—Esters containing halogen
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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

Definitions

  • the present invention relates to an acrylic emulsion resin having excellent tackiness and a method for preparing the same, and specifically, comprising: i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) a modified acrylic monomer represented by a specific chemical formula.
  • PSA Pressure-Sensitive Adhesive
  • PSA is a semi-solid material that has a property of adhering to the adherend with a small pressure. It is a viscoelastic material different from the adhesive and has the basic properties of initial adhesive force, adhesive force and cohesive force. It is used in almost all industries such as printing, chemicals, pharmaceuticals, home appliances, automobiles, stationery, as well as trademarks and advertisements.
  • the pressure-sensitive adhesive may be classified into acrylic, rubber, silicone, EVA, and the like according to the monomers used in the manufacture, and may be classified into a solvent type, an emulsion type, a hot melt type, and the like depending on the form.
  • Aqueous emulsion pressure sensitive adhesive can be used a polymer having a higher molecular weight than the solvent-based polymer, regardless of the viscosity of the adhesive and the molecular weight of the dispersion polymer, it can obtain a wide range of solid content concentration, small aging resistance, low viscosity, low It has the advantage of good adhesion in the solid content region and good compatibility with other polymers.
  • the drying speed is low, the hydrophobic adhesive surface, for example, the adhesion of polyolefin such as polyethylene or polypropylene having low surface tension is low, and the selection range of the curing agent is narrow.
  • the initial adhesive strength is lowered, but also because it contains an emulsifying and dispersing agent is not being replaced quickly because it does not reach the physical properties as low as the oil-based pressure-sensitive adhesive.
  • aqueous emulsion pressure-sensitive adhesive may be an acrylic emulsion resin, and the above-mentioned property degradation is caused by various additives introduced during the emulsion polymerization and the post-treatment process.
  • the surfactant imparting stability to the acrylic emulsion is present on the surface of the adhesive resin after coating, thereby affecting the adhesion to the adherend, and impairs cohesion between the acrylic emulsion particles in the adhesive during coating. Drop.
  • the wetting agent that improves the wettability on the surface of the silicone release paper by lowering the surface tension of the pressure-sensitive adhesive is also a kind of surfactant, causing problems similar to the above-mentioned surfactant, antifoaming agents and various inorganic additives, etc. This causes a decrease.
  • the rubber-based resin is mixed with the acrylic emulsion resin, or a tackifier may be further added.
  • the compatibility with the acrylic emulsion resin is low, the transparency is lowered, thermal stability, oxidation stability, weather resistance, etc. are exhibited a phenomenon, the addition of the tackifier is 50 compared to 100 parts by weight of the acrylic emulsion Up to parts by weight improves the adhesive force, but when used in more than 50 parts by weight, rather than reducing the adhesive force, there is a problem of reducing the storage stability.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the acrylic emulsion resin according to the present invention comprises i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) a modified acrylic monomer represented by Formula 1 below and a modified acrylic monomer represented by Formula 2 below. It is characterized in that the copolymer including a mixed monomer, and a crosslinking agent comprising at least one modified acrylic monomer selected from the group.
  • n 0 to 20;
  • Equation 2 n 'is 0 to 18.
  • the term mixed monomer is not particularly limited as long as the acrylic emulsion resin is polymerized based on the monomers.
  • the monomers may be polymerized by being mixed with the monomers. It can be added sequentially and polymerized, and the like.
  • the acrylic emulsion resin i) based on the total weight of the acrylic emulsion resin i) 75 to 95% by weight acrylic monomer having an alkyl group of 1 to 18 carbon atoms, ii) modified acrylic monomer represented by the formula (1) And a mixed monomer including 0.5 to 20 wt% of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 2, and 0.1 to 5 wt% of a crosslinking agent.
  • the acrylic emulsion resin according to the present invention may be copolymerized, including only the acrylic monomer and the modified acrylic monomer as described above, in detail, may be copolymerized by further including other monomers copolymerizable with the acrylic monomers. .
  • the acrylic emulsion resin is selected from the group consisting of i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, ii) a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 At least one modified acrylic monomer, iii) at least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) at least one selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers Mixed monomers including monomers, and a crosslinking agent.
  • the acrylic emulsion resin i) 60 to 80% by weight of the acrylic monomer having an alkyl group having 1 to 18 carbon atoms, ii 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 iii) allyl ester, vinyl ester, unsaturated acetate and unsaturated 0.5 to 20% by weight of at least one monomer selected from the group consisting of nitriles, iv) 0.5 to 10% by weight of at least one monomer selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers and 0.1 to 3% by weight of crosslinkers Can be.
  • the inventors of the present application confirmed that when the acrylic emulsion resin is prepared by using the modified acrylic monomer, the modified acrylic monomer is copolymerized with the acrylic monomer to improve adhesion to the adherend having a low surface tension.
  • the acrylic monomer of i) may be included in the above range based on the total weight of the acrylic emulsion resin, and when included outside the above range, the initial adhesive strength of the acrylic emulsion resin according to the present invention may be ensured. If it is included in excess of this, it is not preferable because the transfer of the pressure-sensitive adhesive to the adherend occurs largely when removed after use.
  • the number of carbon atoms of the alkyl group of the acrylic monomer of i) may be 1 to 18 in detail, and when it exceeds 18, the acrylic emulsion resin is too flexible and the adhesive properties are not preferable.
  • the acryl-based monomer of i) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl, for example.
  • the modified acrylic monomer of ii) represented by Formula 1 or 2 may be included in the above range based on the total weight of the acrylic emulsion resin, respectively, and when included outside the above range, the adhesive having low surface tension It cannot be expected to improve the adhesive strength to, if it is included in excess of the content of the acrylic monomer is relatively reduced, it is not preferable because the initial adhesive strength of the acrylic emulsion resin can not be secured.
  • the acrylic emulsion resin further comprises other monomers copolymerizable with the acrylic monomer and the modified acrylic monomer, the monomer of iii) as described above, based on the total weight of the acrylic emulsion resin as described above, 0.5 to 20% by weight It may be included, in detail, from 2 to 15% by weight, when included in less than 0.5% by weight is almost no change in the adhesive properties of the acrylic emulsion resin can not secure sufficient adhesive properties, 20% by weight When included in excess, the acrylic emulsion resin is excessively hard, and a significant drop in adhesive strength occurs, which is not preferable.
  • the monomer of iii) is, for example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl lauryl acid, vinyl pyrrolidone, styrene, modified vinyl monomers represented by the following formula (3), acrylonitrile and meta It may be one or more selected from the group consisting of chloronitrile, in detail may be a modified vinyl monomer represented by the formula (3).
  • n '' is 0 to 18.
  • the modified vinyl monomer represented by Chemical Formula 3 is copolymerized with the acrylic monomer and the modified acrylic monomer to contribute to further improving adhesion of the acrylic emulsion resin to the low-tension adhesive. do.
  • the monomer of iv) may be included in an amount of 0.5 to 10% by weight based on the total weight of the acrylic emulsion resin, and when it is included in less than 0.5% by weight, the acrylic emulsion resin is too flexible to secure sufficient adhesive properties. If it is not possible to include it in an amount exceeding 10% by weight, the acrylic emulsion resin is excessively hardened, so that a significant drop in adhesive strength occurs, which is not preferable.
  • the monomer of iv) is acrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotanic acid, methacrylic acid, ethyl methacrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, for example. , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxylauryl (meth) acrylate and hydroxypropylene It may be one or more selected from the group consisting of glycol (meth) acrylate.
  • the mixed monomer for the production of the acrylic emulsion resin may further include 0.1 to 3% by weight of the epoxy group-containing unsaturated monomer based on the total weight of the emulsion resin, the acrylic emulsion resin within the above range sufficient cohesion force Has
  • the said epoxy group containing unsaturated monomer is glycidyl (meth) acrylate, alphamethyl glycidyl (meth) acrylate, allyl glycidyl ether, oxocyclohexyl (meth) acrylate, 3, 4-, for example. It may be one or more selected from the group consisting of epoxycyclohexylmethyl (meth) acrylate, more specifically glycidyl (meth) acrylate or allyl glycidyl ether.
  • the crosslinking agent is an organic crosslinking agent, polyethylene glycol diacrylate, polypropylene glycol diacrylate, allyl methacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol di Acrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethyl propane ethoxylate triacrylate, Trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, divinylbenzene and the like.
  • polyethylene glycol One member selected from the group consisting of acrylate and polypropylene glycol diacrylate may be equal
  • the present invention also discloses a method for producing the acrylic emulsion resin.
  • a method of preparing an acrylic emulsion resin including only an acrylic monomer and a modified acrylic monomer may include i) 75 to 95 wt% of an acrylic monomer having an alkyl group having 1 to 18 carbon atoms based on the total weight of the acrylic emulsion resin. ii) a mixed monomer comprising 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Chemical Formula 1 and a modified acrylic monomer represented by Chemical Formula 2, and a crosslinking agent of 0.1 to 20 Polymerizing 5% by weight.
  • the method for producing an acrylic emulsion resin further comprises other monomers copolymerizable with acrylic monomers in addition to the acrylic monomer and the modified acrylic monomer, i) based on the total weight of the acrylic emulsion resin 60 to 80% by weight of the acrylic monomer having an alkyl group of 18, ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 0.5 to 20 % By weight iii) at least 0.5 to 20% by weight of at least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) at least one selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers Within monomer 0.5 It comprises the step of polymerizing a monomer mixture, a crosslinking agent and 0.1 to 3% by weight containing 10% by weight.
  • the polymerization reaction of the mixed monomer and the crosslinking agent is not particularly limited, but an emulsion polymerization that is easy to control the heat of reaction is preferable, and in detail, water, an electrolyte and a surfactant are administered to the reactor and 80 ° C. Heating to remove oxygen and dissolving the initiator to prepare a solution; Preparing an emulsion resin; a second process of preparing an emulsion by administering water, an electrolyte, and a surfactant to a mixture containing a mixed monomer and a crosslinking agent; A third process of continuously adding the emulsion and the initiator of the second process to the solution of the first process, and then raising the temperature to 80 ° C. to produce an acrylic emulsion resin; And a fourth process of adjusting the pH of the acrylic emulsion resin to 6 to 9; It can be configured as.
  • the initiator may be a water-soluble polymerization initiator such as persulfate of ammonium or an alkali metal, hydrogen peroxide, peroxide, hydroxide peroxide, or the like, and may be used together with one or more reducing agents to conduct an emulsion polymerization reaction at low temperature.
  • the reducing agent may be sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and the like.
  • the temperature of the polymerization reaction may be in detail 0 to 100 °C, more specifically in consideration of the physical properties of the adhesive may be 40 to 90 °C bar, the initiator alone or one or more of the initiator and the reducing agent It can be adjusted by a method such as using a mixture.
  • the electrolyte used in the polymerization reaction is to adjust the pH and impart stability to the acrylic emulsion resin to be polymerized, specifically 1 selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, sodium chloride, and the like. It may be a species or more, specifically sodium carbonate.
  • the surfactant is used for the initial particle generation during the polymerization reaction, the size control of the generated particles and the stability of the particles, and is composed of a hydrophilic group and a lipophilic group, and is divided into anionic, cationic and nonionic surfactants.
  • anionic and nonionic surfactants are used a lot, and they may be mixed with each other to compensate for mechanical stability and chemical stability.
  • the anionic surfactant may be sodium alkyldiphenyloxide disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium dialkyl sulfosuccinate, and the like.
  • Polyethylene oxide alkyl aryl ether, polyethylene oxide alkyl amine, polyethylene oxide alkyl ester, and the like, which may be used alone or in combination of two or more thereof, and may be more effective when an anionic surfactant and a nonionic surfactant are mixed. have.
  • the acrylic emulsion resin may have an acidity (pH) adjusted as an alkaline material, and the pH of the acrylic emulsion resin may be 6 to 9 in detail, and more specifically 7 to 8, and the alkaline material may be a monovalent metal or Inorganic substances such as hydroxides, chlorides, carbonates of divalent metals, ammonia, organic amines, and the like.
  • the present invention provides an aqueous acrylic emulsion pressure-sensitive adhesive comprising an acrylic emulsion resin thus prepared, that is, an aqueous acrylic emulsion pressure-sensitive adhesive in which the acrylic emulsion resin is dispersed in water, and applied to the pressure-sensitive adhesive film or sheet to form an adhesive layer. It provides an adhesive sheet.
  • the pressure-sensitive adhesive film or sheet may be a polyolefin-based substrate having a low surface tension, and in this case, the pressure-sensitive adhesive sheet according to the present invention may have sufficient adhesive force, and the pressure-sensitive adhesive sheet on which the pressure-sensitive adhesive layer is formed may be architectural interior and exterior materials, interior materials, It may be used in an adhesive film or sheet of an advertising film, or a label, wherein the pressure-sensitive adhesive layer may have a thickness of 10 to 100 ⁇ m, specifically 20 to 30 ⁇ m.
  • 280 g of ion-exchanged water was placed in a 3 L capacity glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen introduction tube and reflux condenser, and 20 g of 30% by weight sodium lauryl sulfate solution was injected as a surfactant. After stirring, the inside of the reactor was replaced with nitrogen, and then heated to 70 ° C. under a nitrogen atmosphere, and maintained for 60 minutes.
  • 150 g of the emulsion and 150 g of ammonium persulfate solution at a concentration of 10% by weight were continuously and evenly added to the glass reactor for 4 hours, and when the addition of the ammonium persulfate solution and the emulsion was completed, the temperature was raised to 80 ° C. for 30 minutes, followed by After maintaining the temperature, and cooled to room temperature to prepare an acrylic emulsion pressure-sensitive adhesive.
  • the pH was adjusted to 7.5 by adding a 30% by weight aqueous ammonia solution to the acrylic emulsion pressure-sensitive adhesive is completed cooling.
  • the acrylic emulsion pressure sensitive adhesive prepared above was coated on a release sheet coated with silicone, and dried in an oven at 100 ° C. for 2 minutes so that the acrylic emulsion pressure sensitive adhesive layer had a thickness of 20 ⁇ m.
  • An adhesive sheet was prepared by laminating it with art paper and cut to 1 inch x 200 mm size to prepare an adhesive tape specimen.
  • the monomer mixture is 300 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 50 g of 2-methoxy-4-allylphenol, 20 g of acrylic acid, and polypropylene glycol di. The same procedure was followed except that 10 g of acrylate was used.
  • Example 1 the monomer mixture was 338 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of phenoxyethyl acrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. It carried out in the same way except having set to.
  • Example 1 the monomer mixture was 330 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of 2-methoxy-4-allylphenol, 20 g of acrylic acid, and polypropylene glycol di. The same procedure was followed except that 10 g of acrylate was used.
  • Example 2 The same method as in Example 1 except that the monomer mixture was 358 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. was carried out.
  • Example 1 the monomer mixture was butyl acrylate 200 g, 2-ethylhexyl acrylate 570 g, methyl methacrylate 50 g, 2-methoxy-4-allylphenol 150 g, acrylic acid 20 g, polypropylene glycol di The same procedure was followed except that 10 g of acrylate was used.
  • Example 1 the monomer mixture was 308 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 50 g of ethyl acrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. Except that was carried out in the same manner.
  • Adhesion test at room temperature (90 degree peeling) test After reciprocating five times and aged at room temperature for 30 minutes, it was measured while peeling 90 degrees using a TA Texture Analyzer instrument at a rate of 5 mm / sec.
  • Initial Tack Test Initial adhesive force was measured according to the Finat test method, an official test standard. This is a method of measuring the initial adhesive force by making the adhesive tape specimen into a loop, and follows the FTM9 'loop' tack measurement.
  • Examples 1 to 4 the phenoxyethyl acrylate or 2-methoxy represented by the formula (1) or 2 of the present invention as a monomer that can increase the adhesion to high density polyethylene (HDPE) Since an acrylic emulsion resin is prepared including -4-allylphenol, it can be confirmed that the peeling force and initial adhesive strength to HDPE are higher than those of Comparative Examples 1 to 4.
  • HDPE high density polyethylene
  • Comparative Example 1 does not include a modified acrylic monomer according to the present invention, the adhesion to HDPE is low, Comparative Example 2, even though it contains a phenoxyethyl acrylate, the adhesion decreases as the content exceeds the recommended amount In Comparative Example 3, it can be seen that the aggregation failure phenomenon occurred by using 2-methoxy-4-allylphenol in excess of the recommended amount.
  • the acrylic emulsion resin is prepared by including a modified acrylic monomer such as phenoxyethyl acrylate or 2-methoxy-4-allylphenol in a predetermined content according to the present invention
  • the adhesive agent having a low surface tension is also used. It can be seen that excellent adhesion can be exhibited.
  • the acrylic emulsion resin according to the present invention is polymerized by including a modified acrylic monomer represented by a specific chemical formula, thereby improving adhesion to a low-tension adherend, acrylic emulsion prepared using the same
  • the pressure-sensitive adhesive is excellent in adhesive strength irrespective of the nature of the adhesive, and therefore, mixing with acrylic resin and the like, which is incompatible with acryl, is not necessary, and thus transparency can be maintained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an acrylic emulsion resin having an excellent adhesive property and a preparation method therefor and, specifically, to: an acrylic emulsion resin, characterized in that a mixed monomer and a crosslinking agent are co-polymerized, the mixed monomer comprising i) an acrylic monomer having an alkyl group of carbon number 1 to 18, and ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by formula 1 (the same as formula 1 indicated in claim 1) and a modified acrylic monomer represented by formula 2 (the same as formula 2 indicated in claim 1), and optionally comprising iii) at least one monomer selected from the group consisting of an allyl ester, a vinyl ester, an unsaturated acetate and an unsaturated nitrile and iv) at least one monomer selected from the group consisting of an unsaturated carboxylic acid and hydroxyl group-containing unsaturated monomer; and a preparation method therefor.

Description

점착성이 우수한 아크릴계 에멀젼 수지 및 이의 제조방법Acrylic emulsion resin excellent in adhesiveness and its manufacturing method
본 발명은 점착성이 우수한 아크릴계 에멀젼 수지 및 이의 제조방법에 관한 것으로서, 상세하게는, i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체와, ii) 특정 화학식으로 표시되는 변성 아크릴계 단량체를 포함하고, 선택적으로 iii)알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체를 포함하는 혼합 단량체, 및 가교제를 포함하여 공중합된 것을 특징으로 하는 아크릴계 에멀젼 수지 및 이의 제조방법에 관한 것이다.The present invention relates to an acrylic emulsion resin having excellent tackiness and a method for preparing the same, and specifically, comprising: i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) a modified acrylic monomer represented by a specific chemical formula. Iii) at least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) mixed monomers comprising at least one monomer selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers It relates to an acrylic emulsion resin and a method for producing the same, characterized in that copolymerized, and a crosslinking agent.
점착제(Pressure-Sensitive Adhesive, PSA)는 작은 압력으로 피착제에 접착하는 성질을 가진 반고체 상태의 물질로서, 접착제와는 다른 점탄성적인 물질로 초기 점착력, 점착력, 응집력의 기본적인 성질을 가지고 있으며, 제품의 상표, 광고는 물론 인쇄, 화학, 의약품, 가전제품, 자동차, 문구 등 거의 전 산업분야에 사용되고 있다.Pressure-Sensitive Adhesive (PSA) is a semi-solid material that has a property of adhering to the adherend with a small pressure. It is a viscoelastic material different from the adhesive and has the basic properties of initial adhesive force, adhesive force and cohesive force. It is used in almost all industries such as printing, chemicals, pharmaceuticals, home appliances, automobiles, stationery, as well as trademarks and advertisements.
상기 점착제는 제조 시 이용되는 단량체에 따라 아크릴계, 고무계, 실리콘계, EVA계 등으로 분류할 수 있고, 형태에 따라 용제형, 에멀젼형, 핫멜트형 등으로 분류할 수 있다. The pressure-sensitive adhesive may be classified into acrylic, rubber, silicone, EVA, and the like according to the monomers used in the manufacture, and may be classified into a solvent type, an emulsion type, a hot melt type, and the like depending on the form.
과거 점착테이프와 점착라벨 등에 사용되던 점착제의 대부분은 용제형 유성 점착제였으나, 이는 시공 후 장기간 동안 잔존 용매가 공기 중에 배출되기 때문에 건축물 내부에 거주하는 사람들에게 두통, 눈코목의 자극, 기침, 가려움증, 현기증, 피로감, 집중력 저하 등의 증상을 발생시키고, 오랜 기간 노출이 되면 호흡기질환, 심장병, 암 등을 유발하는 새집증후근(Sick House Syndrome)을 발생시키는 문제가 있다.In the past, most of the adhesives used in adhesive tapes and adhesive labels were solvent-type oil-based adhesives. However, since residual solvents are discharged into the air for a long time after construction, headache, irritation, coughing, itching, Symptoms such as dizziness, fatigue, decreased concentration, and when exposed for a long time there is a problem that causes a sick house syndrome (Sick House Syndrome) that causes respiratory diseases, heart disease, cancer, and the like.
이러한 이유로 물을 분산매로 사용하여 친환경적이면서 인체에 유해한 물질의 배출이 없는 무용제형 점착제로서, 수계 에멀젼 점착제에 대한 관심이 집중되고 있다. 수계 에멀젼 점착제는 점착제 점도와 분산체 폴리머의 분자량이 무관하여 용제계 폴리머에 비해 고분자량을 갖는 폴리머를 사용할 수 있고, 고형분의 농도 범위를 광범위하게 얻을 수 있으며, 내노화성이 작고, 저점도, 저고형분 영역에서의 점착성이 양호하며, 다른 폴리머와의 상용성이 좋은 장점을 가지고 있다. For this reason, water-based emulsion pressure-sensitive adhesives have been attracting attention as a solvent-free pressure-sensitive adhesive that uses water as a dispersion medium and is free of environmentally harmful substances. Aqueous emulsion pressure sensitive adhesive can be used a polymer having a higher molecular weight than the solvent-based polymer, regardless of the viscosity of the adhesive and the molecular weight of the dispersion polymer, it can obtain a wide range of solid content concentration, small aging resistance, low viscosity, low It has the advantage of good adhesion in the solid content region and good compatibility with other polymers.
그러나, 물을 용제로 사용하기 때문에 건조 속도가 느리고, 소수성의 점착면, 예를 들어, 표면 장력이 낮은 폴리에틸렌 또는 폴리프로필렌 등의 폴리올레핀의 피착제에 대한 점착성이 낮으며, 경화제의 선택 범위가 협소하고, 초기 점착력이 떨어지는 문제점을 가질 뿐만 아니라, 유화 및 분산제를 포함하고 있기 때문에 내수성이 낮은 등 유성 점착제만큼의 물성에 이르지 못하여 빠르게 대체되진 못하고 있다.However, since water is used as the solvent, the drying speed is low, the hydrophobic adhesive surface, for example, the adhesion of polyolefin such as polyethylene or polypropylene having low surface tension is low, and the selection range of the curing agent is narrow. In addition, not only has a problem that the initial adhesive strength is lowered, but also because it contains an emulsifying and dispersing agent is not being replaced quickly because it does not reach the physical properties as low as the oil-based pressure-sensitive adhesive.
이러한 수계 에멀젼 점착제의 대표적인 예로는, 아크릴계 에멀젼 수지를 들 수 있는데, 상기의 물성 저하는 유화중합 및 후첨 과정에서 투입되는 각종 첨가제가 원인이다. 구체적으로, 아크릴계 에멀젼에 안정성을 부여하는 계면활성제는 코팅 후 점착수지의 표면에 존재하여 피착제에 대한 점착력을 떨어뜨리는데 영향을 주고, 코팅 시 점착제 내의 아크릴계 에멀젼 입자간의 융화를 방해하여 응집력을 떨어뜨린다. Representative examples of such an aqueous emulsion pressure-sensitive adhesive may be an acrylic emulsion resin, and the above-mentioned property degradation is caused by various additives introduced during the emulsion polymerization and the post-treatment process. Specifically, the surfactant imparting stability to the acrylic emulsion is present on the surface of the adhesive resin after coating, thereby affecting the adhesion to the adherend, and impairs cohesion between the acrylic emulsion particles in the adhesive during coating. Drop.
또한, 점착제의 표면장력을 낮추어 실리콘이형지 표면에 대한 젖음성을 향상시키는 습윤제(wetting agent)도 계면활성제의 일종이기 때문에 상기 계면활성제와 비슷한 문제를 야기시키고, 소포제 및 각종 무기물 첨가제 등도 수성 에멀젼 점착제의 물성을 저하시키는 원인이 된다.In addition, the wetting agent that improves the wettability on the surface of the silicone release paper by lowering the surface tension of the pressure-sensitive adhesive is also a kind of surfactant, causing problems similar to the above-mentioned surfactant, antifoaming agents and various inorganic additives, etc. This causes a decrease.
이러한 상기 문제를 해결하고, 표면 장력이 낮은 피착제에 대한 점착력을 높이기 위해서 다양한 방법이 시도되고 있고, 구체적으로, 고무계 수지를 아크릴계 에멀젼 수지에 혼합하거나, 점착부여제를 추가 첨가하기도 한다.In order to solve this problem and to increase the adhesion to the adherend having a low surface tension, various methods have been attempted. Specifically, the rubber-based resin is mixed with the acrylic emulsion resin, or a tackifier may be further added.
그러나, 고무계 수지를 혼합하는 경우에는 아크릴계 에멀젼 수지와 상용성이 낮아 투명성이 저하되고, 열적 안정성, 산화 안정성, 내후성 등이 저하되는 현상을 보이며, 점착부여제의 첨가는 아크릴계 에멀젼 100 중량부 대비 50 중량부까지는 점착력을 향상시키지만 50 중량부 이상 사용될 때는 오히려 점착력을 감소시킬 뿐만 아니라 저장 안정성을 떨어뜨리는 문제가 있다.However, in the case of mixing the rubber-based resin, the compatibility with the acrylic emulsion resin is low, the transparency is lowered, thermal stability, oxidation stability, weather resistance, etc. are exhibited a phenomenon, the addition of the tackifier is 50 compared to 100 parts by weight of the acrylic emulsion Up to parts by weight improves the adhesive force, but when used in more than 50 parts by weight, rather than reducing the adhesive force, there is a problem of reducing the storage stability.
따라서, 아크릴계 단량체와 공중합이 가능하면서도 표면 장력이 낮은 피착제에 대한 점착력이 우수한 아크릴계 에멀젼 점착제의 기술에 대한 필요성이 높은 실정이다.Therefore, there is a high necessity for a technique of an acrylic emulsion pressure sensitive adhesive capable of copolymerizing with an acrylic monomer but having excellent adhesion to a low adhesive surface adhesive.
본 발명은 상기와 같은 종래기술의 문제점과 과거로부터 요청되어온 기술적 과제를 해결하는 것을 목적으로 한다.The present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
본 출원의 발명자들은 심도 있는 연구와 다양한 실험을 거듭한 끝에, 특정 화학식으로 표시되는 변성 아크릴계 단량체를 포함하여 아크릴계 에멀젼 수지를 제조하고, 이를 사용하여 아크릴계 에멀젼 점착제를 제조하는 경우, 표면 장력이 낮은 피착제에 대해서도 우수한 점착력을 나타냄을 확인하고, 본 발명을 완성하기에 이르렀다. After extensive research and various experiments, the inventors of the present application prepare an acrylic emulsion resin including a modified acrylic monomer represented by a specific chemical formula, and when using the same to prepare an acrylic emulsion pressure-sensitive adhesive, the surface tension is reduced. It confirmed that it showed the outstanding adhesive force also about agent, and came to complete this invention.
따라서, 본 발명에 따른 아크릴계 에멀젼 수지는, i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체와, ii) 하기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 하기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체를 포함하는 혼합 단량체, 및 가교제를 포함하여 공중합된 것을 특징으로 한다.Accordingly, the acrylic emulsion resin according to the present invention comprises i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) a modified acrylic monomer represented by Formula 1 below and a modified acrylic monomer represented by Formula 2 below. It is characterized in that the copolymer including a mixed monomer, and a crosslinking agent comprising at least one modified acrylic monomer selected from the group.
Figure PCTKR2014004512-appb-I000001
Figure PCTKR2014004512-appb-I000001
상기 식 1에서, n은 0 내지 20이고;In formula 1, n is 0 to 20;
상기 식 2에서, n'는 0내지 18이다.In Equation 2, n 'is 0 to 18.
본 명세서에서, 사용된 용어 혼합 단량체는 상기 단량체들을 기반으로 아크릴계 에멀젼 수지가 중합되는 것이면 특별한 제한이 없는 바, 예를 들어, 상기 단량체들이 함께 혼합된 상태로 투입되어 중합될 수도 있고, 상기 단량체들이 순차적으로 투입되어 중합될 수 있는 등 다양하다.As used herein, the term mixed monomer is not particularly limited as long as the acrylic emulsion resin is polymerized based on the monomers. For example, the monomers may be polymerized by being mixed with the monomers. It can be added sequentially and polymerized, and the like.
하나의 구체적인 예에서, 상기 아크릴계 에멀젼 수지는, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 75 내지 95 중량%, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량%를 포함하는 혼합 단량체, 및 가교제 0.1 내지 5 중량%를 포함하여 중합될 수 있다.In one specific example, the acrylic emulsion resin, i) based on the total weight of the acrylic emulsion resin i) 75 to 95% by weight acrylic monomer having an alkyl group of 1 to 18 carbon atoms, ii) modified acrylic monomer represented by the formula (1) And a mixed monomer including 0.5 to 20 wt% of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 2, and 0.1 to 5 wt% of a crosslinking agent.
한편, 본 발명에 따른 아크릴계 에멀젼 수지는, 상기와 같이 아크릴계 단량체 및 변성 아크릴계 단량체만을 포함하여 공중합될 수도 있으나, 상세하게는, 상기 아크릴계 단량체들과 공중합 가능한 그 밖의 단량체들을 더 포함하여 공중합될 수 있다.On the other hand, the acrylic emulsion resin according to the present invention may be copolymerized, including only the acrylic monomer and the modified acrylic monomer as described above, in detail, may be copolymerized by further including other monomers copolymerizable with the acrylic monomers. .
구체적으로, 상기 아크릴계 에멀젼 수지는, i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체, iii)알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체를 포함하는 혼합 단량체, 및 가교제를 포함하여 공중합될 수 있다.Specifically, the acrylic emulsion resin is selected from the group consisting of i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, ii) a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 At least one modified acrylic monomer, iii) at least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) at least one selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers Mixed monomers including monomers, and a crosslinking agent.
이와 같이, 아크릴계 단량체 및 변성 아크릴계 단량체 외의 단량체들이 포함되어 중합되는 경우에는 그것들의 함량이, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 60 내지 80 중량%, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량% iii) 알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 20 중량%, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 10 중량% 및 가교제 0.1 내지 3 중량%일 수 있다.As such, when monomers other than the acrylic monomer and the modified acrylic monomer are included and polymerized, their content is based on the total weight of the acrylic emulsion resin, i) 60 to 80% by weight of the acrylic monomer having an alkyl group having 1 to 18 carbon atoms, ii 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 iii) allyl ester, vinyl ester, unsaturated acetate and unsaturated 0.5 to 20% by weight of at least one monomer selected from the group consisting of nitriles, iv) 0.5 to 10% by weight of at least one monomer selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers and 0.1 to 3% by weight of crosslinkers Can be.
본 출원의 발명자들은 상기와 같이, 변성 아크릴계 단량체를 포함하여 아크릴계 에멀젼 수지를 제조하는 경우, 상기 변성 아크릴계 단량체가 아크릴계 단량체와 공중합되어 표면 장력이 낮은 피착제에 대한 점착력을 향상시킴을 확인하였다.As described above, the inventors of the present application confirmed that when the acrylic emulsion resin is prepared by using the modified acrylic monomer, the modified acrylic monomer is copolymerized with the acrylic monomer to improve adhesion to the adherend having a low surface tension.
이하 본 발명에 따른 각각의 단량체에 대해 상세하게 설명한다.Hereinafter, each monomer according to the present invention will be described in detail.
상기 i)의 아크릴계 단량체는 각각의 경우에, 아크릴계 에멀젼 수지 전체 중량을 기준으로 상기 범위 내로 포함될 수 있는데, 상기 범위를 벗어나 그 미만으로 포함되는 경우에는 본 발명에 따른 아크릴계 에멀젼 수지의 초기 점착력을 확보할 수 없고, 이를 초과하여 포함되는 경우에는 사용 후 제거 시 피착물에 대한 점착제의 전사가 크게 발생하므로 바람직하지 않다.In each case, the acrylic monomer of i) may be included in the above range based on the total weight of the acrylic emulsion resin, and when included outside the above range, the initial adhesive strength of the acrylic emulsion resin according to the present invention may be ensured. If it is included in excess of this, it is not preferable because the transfer of the pressure-sensitive adhesive to the adherend occurs largely when removed after use.
또한, 상기 i)의 아크릴계 단량체의 알킬기의 탄소수는 상세하게는, 1 내지 18 개일 수 있고, 18개를 초과하는 경우에는 아크릴계 에멀젼 수지가 너무 유연해져 점착 물성이 떨어지므로 바람직하지 않다.In addition, the number of carbon atoms of the alkyl group of the acrylic monomer of i) may be 1 to 18 in detail, and when it exceeds 18, the acrylic emulsion resin is too flexible and the adhesive properties are not preferable.
상기 i)의 아크릴계 단량체는, 예를 들어, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸아크릴레이트, t-부틸메타크릴레이트, 펜틸메타크릴레이트, 헥실메타크릴레이트, 헵틸아크릴레이트, 이소옥틸아크릴레이트, 옥틸메타크릴레이트, 2-에틸헥실(메타)아크릴레이트, 이소데실아크릴레이트, 데실메타크릴레이트, 도데실메타크릴레이트, 이소보닐메타크릴레이트, 스테아릴(메타)아크릴레이트 및 라우릴(메타)아크릴레이트로 이루어진 군으로부터 선택되는 하나 이상일 수 있고, 상세하게는, 상기 i)의 아크릴계 단량체 전체 중량을 기준으로 2-에틸헥실 아크릴레이트 20 내지 70 중량% 및 부틸아크릴레이트 20 내지 70 중량%, 및 메틸메타크릴레이트 2 내지 10 중량%의 혼합물일 수 있다.The acryl-based monomer of i) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl, for example. Acrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl acrylate, isooctyl acrylate, octyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl acrylate, decyl It may be at least one selected from the group consisting of methacrylate, dodecyl methacrylate, isobornyl methacrylate, stearyl (meth) acrylate and lauryl (meth) acrylate, and in detail, the i) 20 to 70% by weight of 2-ethylhexyl acrylate and 20 to 70% by weight of butyl acrylate, and 2 to methyl methacrylate, based on the total weight of the acrylic monomers 10% by weight of the mixture.
상기 화학식 1 또는 2로 표시되는 ii)의 변성 아크릴계 단량체는 각각, 아크릴계 에멀젼 수지 전체 중량을 기준으로 상기 범위 내에서 포함될 수 있고, 상기 범위를 벗어나 그 미만으로 포함되는 경우에는 표면 장력이 낮은 피착제에 대한 점착력의 향상을 기대할 수 없고, 이를 초과하여 포함되는 경우에는 상대적으로 아크릴계 단량체의 함량이 줄어드는 바, 아크릴계 에멀젼 수지의 초기 점착력을 확보할 수 없으므로 바람직하지 않다.The modified acrylic monomer of ii) represented by Formula 1 or 2 may be included in the above range based on the total weight of the acrylic emulsion resin, respectively, and when included outside the above range, the adhesive having low surface tension It cannot be expected to improve the adhesive strength to, if it is included in excess of the content of the acrylic monomer is relatively reduced, it is not preferable because the initial adhesive strength of the acrylic emulsion resin can not be secured.
한편, 상기 아크릴계 에멀젼 수지가 아크릴계 단량체 및 변성 아크릴계 단량체와 공중합 가능한 그 밖의 단량체들을 더 포함하는 경우, 상기 iii)의 단량체는 상기와 같이, 아크릴계 에멀젼 수지 전체 중량을 기준으로 0.5 내지 20 중량%로 포함될 수 있고, 상세하게는 2 내지 15 중량%로 포함될 수 있는 바, 0.5 중량% 미만으로 포함되는 경우에는 아크릴계 에멀젼 수지의 점착물성의 변화가 거의 없어 충분한 점착 물성을 확보할 수 없고, 20 중량%를 초과하여 포함되는 경우에는 아크릴계 에멀젼 수지가 과도하게 견고해져 현저한 점착력 저하가 발생하므로 바람직하지 않다.On the other hand, when the acrylic emulsion resin further comprises other monomers copolymerizable with the acrylic monomer and the modified acrylic monomer, the monomer of iii) as described above, based on the total weight of the acrylic emulsion resin as described above, 0.5 to 20% by weight It may be included, in detail, from 2 to 15% by weight, when included in less than 0.5% by weight is almost no change in the adhesive properties of the acrylic emulsion resin can not secure sufficient adhesive properties, 20% by weight When included in excess, the acrylic emulsion resin is excessively hard, and a significant drop in adhesive strength occurs, which is not preferable.
상기 iii)의 단량체는, 예를 들어, 아세트산 비닐, 부탄산 비닐, 프로피온산 비닐, 라우릴산 비닐, 비닐 피롤리돈, 스타이렌, 하기 화학식 3으로 표시되는 변성 비닐계 단량체, 아크릴로니트릴 및 메타크릴로니트릴로 이루어진 군으로부터 선택되는 하나 이상일 수 있고, 상세하게는 하기 화학식 3으로 표시되는 변성 비닐계 단량체일 수 있다.The monomer of iii) is, for example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl lauryl acid, vinyl pyrrolidone, styrene, modified vinyl monomers represented by the following formula (3), acrylonitrile and meta It may be one or more selected from the group consisting of chloronitrile, in detail may be a modified vinyl monomer represented by the formula (3).
Figure PCTKR2014004512-appb-I000002
Figure PCTKR2014004512-appb-I000002
상기 식 3에서, n''는 0 내지 18이다.In Formula 3, n '' is 0 to 18.
본 출원의 발명자들이 확인한 바에 따르면, 상기 화학식 3으로 표시되는 변성 비닐계 단량체는, 상기 아크릴계 단량체 및 변성 아크릴계 단량체와 공중합되어 아크릴계 에멀젼 수지의, 표면 장력이 낮은 피착제에 대한 점착력을 더욱 향상시키는데 기여한다.According to the inventors of the present application, the modified vinyl monomer represented by Chemical Formula 3 is copolymerized with the acrylic monomer and the modified acrylic monomer to contribute to further improving adhesion of the acrylic emulsion resin to the low-tension adhesive. do.
상기 iv)의 단량체는 상기와 같이, 아크릴계 에멀젼 수지 전체 중량을 기준으로 0.5 내지 10 중량%로 포함될 수 있는 바, 0.5 중량% 미만으로 포함되는 경우에는 아크릴계 에멀젼 수지가 너무 유연해져 충분한 점착 물성을 확보할 수 없고, 10 중량%를 초과하여 포함되는 경우에는 아크릴계 에멀젼 수지가 과도하게 견고해져 현저한 점착력 저하가 발생하므로 바람직하지 않다.As described above, the monomer of iv) may be included in an amount of 0.5 to 10% by weight based on the total weight of the acrylic emulsion resin, and when it is included in less than 0.5% by weight, the acrylic emulsion resin is too flexible to secure sufficient adhesive properties. If it is not possible to include it in an amount exceeding 10% by weight, the acrylic emulsion resin is excessively hardened, so that a significant drop in adhesive strength occurs, which is not preferable.
상기 iv)의 단량체는, 예를 들어, 아크릴산, 이타콘산, 무수말레인산, 푸마르산, 크로탄산, 메타크릴산, 에틸메타크릴산, 히드록시메틸(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 히드록시부틸(메타)아크릴레이트, 히드록시헥실(메타)아크릴레이트, 히드록시옥틸(메타)아크릴레이트, 히드록시라우릴(메타)아크릴레이트 및 히드록시프로필렌글리콜(메타)아크릴레이트로 이루어진 군으로부터 선택되는 하나 이상일 수 있다.The monomer of iv) is acrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotanic acid, methacrylic acid, ethyl methacrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, for example. , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxylauryl (meth) acrylate and hydroxypropylene It may be one or more selected from the group consisting of glycol (meth) acrylate.
하나의 구체적인 예에서, 상기 아크릴계 에멀젼 수지의 제조를 위한 혼합 단량체에는 에폭시기 함유 불포화 단량체가 에멀젼 수지 전체 중량을 기준으로 0.1 내지 3 중량%로 더 포함될 수 있고, 상기 범위 내에서 아크릴계 에멀젼 수지가 충분한 응집력을 가진다.In one specific example, the mixed monomer for the production of the acrylic emulsion resin may further include 0.1 to 3% by weight of the epoxy group-containing unsaturated monomer based on the total weight of the emulsion resin, the acrylic emulsion resin within the above range sufficient cohesion force Has
상기 에폭시기 함유 불포화 단량체는, 예를 들어, 글리시딜(메타)아크릴레이트, 알파메틸글리시딜(메타)아크릴레이트, 알릴글리시딜 에테르, 옥소시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트로 이루어진 군으로부터 선택되는 하나 이상일 수 있고, 더욱 상세하게는 글리시딜(메타)크릴레이트 또는 알릴글리시딜 에테르일 수 있다.The said epoxy group containing unsaturated monomer is glycidyl (meth) acrylate, alphamethyl glycidyl (meth) acrylate, allyl glycidyl ether, oxocyclohexyl (meth) acrylate, 3, 4-, for example. It may be one or more selected from the group consisting of epoxycyclohexylmethyl (meth) acrylate, more specifically glycidyl (meth) acrylate or allyl glycidyl ether.
하나의 구체적인 예에서, 상기 가교제는 유기 가교제인 폴리에틸렌글리콜디아크릴레이트, 폴리프로필렌글리콜디아크릴레이트, 알릴메타아크릴레이트, 1,6-헥산디올디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 에틸렌글리콜디아크릴레이트, 헥산디올에톡시레이트디아크릴레이트, 헥산디올프로폭시레이트디아크릴레이트, 네오펜틸글리콜에톡시레이트디아크릴레이트, 네오펜틸글리콜프로폭시레이트디아크릴레이트, 트리메틸프로판에톡시레이트트리아크릴레이트, 트리메틸프로판프로폭시레이트트리아크릴레이트, 펜타에리트트리톨에톡시레이트트리아크릴레이트, 펜타에리트트리톨프로폭시레이트트리아크릴레이트, 비닐트리메톡시실란 및 디비닐벤젠 등으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 상세하게는 폴리에틸렌글리콜디아크릴레이트 및 폴리프로필렌글리콜디아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.In one specific example, the crosslinking agent is an organic crosslinking agent, polyethylene glycol diacrylate, polypropylene glycol diacrylate, allyl methacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol di Acrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethyl propane ethoxylate triacrylate, Trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, divinylbenzene and the like. In detail, polyethylene glycol One member selected from the group consisting of acrylate and polypropylene glycol diacrylate may be equal to or greater than.
본 발명은 또한, 상기 아크릴계 에멀젼 수지의 제조방법을 개시한다.The present invention also discloses a method for producing the acrylic emulsion resin.
하나의 구체적인 예에서, 아크릴계 단량체 및 변성 아크릴계 단량체만을 포함하여 아크릴계 에멀젼 수지를 제조하는 방법은, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 75 내지 95 중량%와, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량%를 포함하는 혼합 단량체, 및 가교제 0.1 내지 5 중량%를 중합하는 과정을 포함한다.In one specific example, a method of preparing an acrylic emulsion resin including only an acrylic monomer and a modified acrylic monomer may include i) 75 to 95 wt% of an acrylic monomer having an alkyl group having 1 to 18 carbon atoms based on the total weight of the acrylic emulsion resin. ii) a mixed monomer comprising 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Chemical Formula 1 and a modified acrylic monomer represented by Chemical Formula 2, and a crosslinking agent of 0.1 to 20 Polymerizing 5% by weight.
또 하나의 구체적인 예에서, 상기 아크릴계 단량체 및 변성 아크릴계 단량체 이외에 아크릴계 단량체들과 공중합 가능한 그 밖의 단량체들을 더 포함하여 아크릴계 에멀젼 수지를 제조하는 방법은, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 60 내지 80 중량%, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량% iii) 알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 20 중량%, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 10 중량%을 포함하는 혼합 단량체, 및 가교제 0.1 내지 3 중량%를 중합하는 과정을 포함한다.In another specific example, the method for producing an acrylic emulsion resin further comprises other monomers copolymerizable with acrylic monomers in addition to the acrylic monomer and the modified acrylic monomer, i) based on the total weight of the acrylic emulsion resin 60 to 80% by weight of the acrylic monomer having an alkyl group of 18, ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 0.5 to 20 % By weight iii) at least 0.5 to 20% by weight of at least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) at least one selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers Within monomer 0.5 It comprises the step of polymerizing a monomer mixture, a crosslinking agent and 0.1 to 3% by weight containing 10% by weight.
하나의 구체적인 예에서, 상기 혼합 단량체 및 가교제의 중합 반응은 특별히 제한되지는 않으나, 반응열의 제어가 용이한 유화중합이 바람직하고, 상세하게는, 물, 전해질 및 계면 활성제를 반응기에 투여하고 80℃로 승온시켜 산소를 제거하고 개시제를 용해시켜 용액을 제조하는 제 1 과정; 에멀젼 수지를 제조하기 혼합 단량체 및 가교제를 배합한 혼합물에 물, 전해질 및 계면 활성제를 투여하여 유화액을 제조하는 제 2 과정; 상기 제 1 과정의 용액에 제 2 과정의 유화액 및 개시제를 연속 투입하고, 80℃ 승온 후 상온 냉각시켜 아크릴계 에멀젼 수지를 제조하는 제 3 과정; 및 상기 아크릴계 에멀젼 수지의 pH를 6 내지 9로 조절하는 제 4 과정; 으로 구성될 수 있다.In one specific example, the polymerization reaction of the mixed monomer and the crosslinking agent is not particularly limited, but an emulsion polymerization that is easy to control the heat of reaction is preferable, and in detail, water, an electrolyte and a surfactant are administered to the reactor and 80 ° C. Heating to remove oxygen and dissolving the initiator to prepare a solution; Preparing an emulsion resin; a second process of preparing an emulsion by administering water, an electrolyte, and a surfactant to a mixture containing a mixed monomer and a crosslinking agent; A third process of continuously adding the emulsion and the initiator of the second process to the solution of the first process, and then raising the temperature to 80 ° C. to produce an acrylic emulsion resin; And a fourth process of adjusting the pH of the acrylic emulsion resin to 6 to 9; It can be configured as.
상기 개시제는 암모늄 또는 알칼리 금속의 과황산염, 과산화수소, 퍼옥시드, 히드록퍼옥시드 등의 수용성 중합 개시제일 수 있고, 저온 하에 유화중합 반응을 실시하기 위하여 환원제 1종 이상과 함께 사용할 수도 있다. 상기 환원제는 소듐 바이설파이트, 소듐 메타바이설파이트, 소듐 하이드로설파이트, 소듐티오설페이트, 소듐 포름알데히드 설폭시레이트, 아스코르브산 등일 수 있다. The initiator may be a water-soluble polymerization initiator such as persulfate of ammonium or an alkali metal, hydrogen peroxide, peroxide, hydroxide peroxide, or the like, and may be used together with one or more reducing agents to conduct an emulsion polymerization reaction at low temperature. The reducing agent may be sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and the like.
상기 중합 반응의 온도는 상세하게는 0 내지 100℃일 수 있고, 더욱 상세하게는 점착제의 물성을 고려할 때 40 내지 90℃일 수 있는 바, 상기 개시제를 단독 또는 상기 개시제와 상기 환원제 중 1종 이상을 혼합하여 사용하는 방법 등으로 조절될 수 있다.The temperature of the polymerization reaction may be in detail 0 to 100 ℃, more specifically in consideration of the physical properties of the adhesive may be 40 to 90 ℃ bar, the initiator alone or one or more of the initiator and the reducing agent It can be adjusted by a method such as using a mixture.
상기 중합 반응에 사용되는 전해질은 pH를 조절하고 중합되는 아크릴계 에멀젼 수지에 안정성을 부여하는 것인데, 구체적으로는 소듐 바이카보네이트, 소듐 카보네이트, 소듐 포스페이트, 소듐 설페이트 및 소듐 클로라이드 등으로 이루어지는 군으로부터 선택되는 1종 이상일 수 있고, 상세하게는 소듐 카보네이트일 수 있다.The electrolyte used in the polymerization reaction is to adjust the pH and impart stability to the acrylic emulsion resin to be polymerized, specifically 1 selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, sodium chloride, and the like. It may be a species or more, specifically sodium carbonate.
상기 계면활성제는 상기 중합 반응 시 초기 입자 생성, 생성된 입자의 크기 조절 및 입자의 안정성 등을 위해 사용되는데, 친수성기와 친유성기로 구성되어 있고, 음이온, 양이온 및 비이온 계면활성제 등으로 나뉜다. 주로 음이온 및 비이온 계면활성제를 많이 사용하고, 기계적 안정성 및 화학적 안정성 등을 보완하기 위하여 서로 섞어 사용하기도 한다.The surfactant is used for the initial particle generation during the polymerization reaction, the size control of the generated particles and the stability of the particles, and is composed of a hydrophilic group and a lipophilic group, and is divided into anionic, cationic and nonionic surfactants. In general, anionic and nonionic surfactants are used a lot, and they may be mixed with each other to compensate for mechanical stability and chemical stability.
상기 음이온 계면활성제는, 소듐 알킬디페닐옥사이드 디설포네이트, 소듐 폴리옥시에틸렌 알킬 에테르설페이트, 소듐 폴리옥시에틸렌 라우릴 에테르설페이트, 소듐 디알킬 설포석시네이트 등일 수 있고, 상기 비이온 계면활성제는, 폴리에틸렌옥사이드 알킬 아릴 에테르, 폴리에틸렌옥사이드 알킬 아민, 폴리에틸렌옥사이드 알킬 에스테르 등일 수 있는데, 이 들은 단독 혹은 2종 이상 혼합하여 사용할 수 있고, 음이온 계면활성제와 비이온 계면활성제를 혼합하여 사용하는 경우 보다 효과적일 수 있다.The anionic surfactant may be sodium alkyldiphenyloxide disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium dialkyl sulfosuccinate, and the like. Polyethylene oxide alkyl aryl ether, polyethylene oxide alkyl amine, polyethylene oxide alkyl ester, and the like, which may be used alone or in combination of two or more thereof, and may be more effective when an anionic surfactant and a nonionic surfactant are mixed. have.
상기 아크릴계 에멀젼 수지는 알칼리성 물질로 산도(pH)가 조정될 수 있는데 아크릴계 에멀젼 수지의 pH는 상세하게는 6 내지 9일 수 있고, 더욱 상세하게는 7 내지 8일 수 있으며 상기 알칼리성 물질은 1가 금속 또는 2가 금속의 수산화물, 염화물, 탄산염 등의 무기물, 암모니아 또는 유기 아민 등일 수 있다.The acrylic emulsion resin may have an acidity (pH) adjusted as an alkaline material, and the pH of the acrylic emulsion resin may be 6 to 9 in detail, and more specifically 7 to 8, and the alkaline material may be a monovalent metal or Inorganic substances such as hydroxides, chlorides, carbonates of divalent metals, ammonia, organic amines, and the like.
본 발명은 이렇게 제조된 아크릴계 에멀젼 수지를 포함하는 수계 아크릴계 에멀젼 점착제, 즉, 상기 아크릴계 에멀젼 수지를 물에 분산시킨 수계 아크릴계 에멀젼 점착제를 제공하고, 이를 점착용 필름 또는 시트 상에 적용하여 점착제 층을 형성하는 점착시트를 제공한다.The present invention provides an aqueous acrylic emulsion pressure-sensitive adhesive comprising an acrylic emulsion resin thus prepared, that is, an aqueous acrylic emulsion pressure-sensitive adhesive in which the acrylic emulsion resin is dispersed in water, and applied to the pressure-sensitive adhesive film or sheet to form an adhesive layer. It provides an adhesive sheet.
상기 점착용 필름 또는 시트는 표면 장력이 낮은 폴리올레핀계 기재일 수 있고, 이 경우에도, 본 발명에 따른 점착시트는 충분한 점착력을 가질 수 있으며, 상기 점착제 층이 형성된 점착시트는 건축 내외장재, 인테리어 재료, 광고용 필름, 또는 라벨의 점착용 필름이나 시트에 사용될 수 있으며, 이 때, 상기 점착제 층은, 두께가 10 내지 100 ㎛, 상세하게는 20 내지 30 ㎛일 수 있다.The pressure-sensitive adhesive film or sheet may be a polyolefin-based substrate having a low surface tension, and in this case, the pressure-sensitive adhesive sheet according to the present invention may have sufficient adhesive force, and the pressure-sensitive adhesive sheet on which the pressure-sensitive adhesive layer is formed may be architectural interior and exterior materials, interior materials, It may be used in an adhesive film or sheet of an advertising film, or a label, wherein the pressure-sensitive adhesive layer may have a thickness of 10 to 100 μm, specifically 20 to 30 μm.
이하, 본 발명의 실시예를 참조하여 설명하지만, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범주가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.
<실시예 1><Example 1>
아크릴계 에멀젼 수지의 제조Preparation of Acrylic Emulsion Resin
온도계, 교반기, 적하 깔때기, 질소 도입관 및 환류 냉각기를 구비한 3L 용량의 유리 반응기에 280 g의 이온교환수를 넣고, 계면활성제로서 30 중량% 농도의 소듐 라우릴 설페이트 용액 20 g을 주입하였다. 이를 교반하면서 반응기 내부를 질소로 치환한 다음, 질소 분위기 하에서 70℃로 승온시키고 이를 60분 동안 유지하였다.280 g of ion-exchanged water was placed in a 3 L capacity glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen introduction tube and reflux condenser, and 20 g of 30% by weight sodium lauryl sulfate solution was injected as a surfactant. After stirring, the inside of the reactor was replaced with nitrogen, and then heated to 70 ° C. under a nitrogen atmosphere, and maintained for 60 minutes.
별도로, 3L 비이커에 부틸아크릴레이트 308 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 페녹시에틸아크릴레이트 50 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 3 g을 넣어 혼합한 단량체 혼합물에, 음이온 계면활성제 30 중량% 농도의 소듐 알킬디페닐옥사이드 디설포네이트 용액 50 g, 소듐 카보네이트 5 g 및 물 650 g으로 이루어진 용액을 투입하고 교반기로 섞어 백탁의 유화액을 제조하였다.Separately, 308 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 50 g of phenoxyethyl acrylate, 20 g of acrylic acid, and 3 g of polypropylene glycol diacrylate were mixed and mixed in a 3L beaker. To one monomer mixture, a solution consisting of 50 g of sodium alkyldiphenyloxide disulfonate solution at a concentration of 30% by weight of anionic surfactant, 5 g of sodium carbonate, and 650 g of water was added and mixed with a stirrer to prepare an emulsion of a cloudy.
상기 유리 반응기에 상기 유화액과 10 중량% 농도의 과황산 암모늄 용액 150 g을 4시간 동안 균등하게 연속 투입하고, 과황산 암모늄 용액과 유화액 투입이 완료되면 30분 동안 80℃로 승온하고 1시간 동안 이 온도를 유지시킨 다음, 상온으로 냉각하여 아크릴계 에멀젼 점착제를 제조하였다.150 g of the emulsion and 150 g of ammonium persulfate solution at a concentration of 10% by weight were continuously and evenly added to the glass reactor for 4 hours, and when the addition of the ammonium persulfate solution and the emulsion was completed, the temperature was raised to 80 ° C. for 30 minutes, followed by After maintaining the temperature, and cooled to room temperature to prepare an acrylic emulsion pressure-sensitive adhesive.
냉각이 완료된 상기 아크릴계 에멀젼 점착제에 30 중량% 농도의 암모니아 수용액을 첨가하여 pH를 7.5로 조절하였다The pH was adjusted to 7.5 by adding a 30% by weight aqueous ammonia solution to the acrylic emulsion pressure-sensitive adhesive is completed cooling.
점착 시트의 제조Preparation of Adhesive Sheet
상기에서 제조된 아크릴계 에멀젼 점착제를 실리콘이 코팅된 이형지 시트 위에 도포하고, 100℃의 오븐에서 2분간 건조하여 아크릴계 에멀젼 점착층이 20 ㎛ 두께를 갖도록 하였다. 이를 아트지와 라미네이션하여 점착시트을 만들고 1 inch x 200 mm 크기로 재단하여 점착테이프 시편을 제조하였다.The acrylic emulsion pressure sensitive adhesive prepared above was coated on a release sheet coated with silicone, and dried in an oven at 100 ° C. for 2 minutes so that the acrylic emulsion pressure sensitive adhesive layer had a thickness of 20 μm. An adhesive sheet was prepared by laminating it with art paper and cut to 1 inch x 200 mm size to prepare an adhesive tape specimen.
<실시예 2><Example 2>
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 300 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 2-메톡시-4-알릴페놀 50 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 10 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the monomer mixture is 300 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 50 g of 2-methoxy-4-allylphenol, 20 g of acrylic acid, and polypropylene glycol di. The same procedure was followed except that 10 g of acrylate was used.
<실시예 3><Example 3>
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 338 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 페녹시에틸아크릴레이트 20 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 2 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the monomer mixture was 338 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of phenoxyethyl acrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. It carried out in the same way except having set to.
<실시예 4><Example 4>
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 330 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 2-메톡시-4-알릴페놀 20 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 10 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the monomer mixture was 330 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of 2-methoxy-4-allylphenol, 20 g of acrylic acid, and polypropylene glycol di. The same procedure was followed except that 10 g of acrylate was used.
<비교예 1>Comparative Example 1
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 358 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 2 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.The same method as in Example 1 except that the monomer mixture was 358 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. Was carried out.
<비교예 2>Comparative Example 2
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 108 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 페녹시에틸아크릴레이트 250 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 2 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.108 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 250 g of phenoxyethyl acrylate, 20 g of acrylic acid, 2 g of polypropylene glycol diacrylate It carried out in the same way except having set to.
<비교예 3>Comparative Example 3
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 200 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 2-메톡시-4-알릴페놀 150 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 10 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the monomer mixture was butyl acrylate 200 g, 2-ethylhexyl acrylate 570 g, methyl methacrylate 50 g, 2-methoxy-4-allylphenol 150 g, acrylic acid 20 g, polypropylene glycol di The same procedure was followed except that 10 g of acrylate was used.
<비교예 4><Comparative Example 4>
상기 실시예 1에서 단량체 혼합물을 부틸아크릴레이트 308 g, 2-에틸헥실아크릴레이트 570 g, 메틸메타크릴레이트 50 g, 에틸아크릴레이트 50 g, 아크릴산 20 g, 폴리프로필렌글리콜디아크릴레이트 2 g로 한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the monomer mixture was 308 g of butyl acrylate, 570 g of 2-ethylhexyl acrylate, 50 g of methyl methacrylate, 50 g of ethyl acrylate, 20 g of acrylic acid, and 2 g of polypropylene glycol diacrylate. Except that was carried out in the same manner.
<실험예 1>Experimental Example 1
상기 실시예 1 내지 4, 및 비교예 1 내지 4에서 제조된 아크릴계 에멀젼 수지의 점착특성을 하기의 방법으로 시험하고 그 결과를 하기 표 1에 나타내었다.The adhesion characteristics of the acrylic emulsion resins prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were tested by the following method, and the results are shown in Table 1 below.
*상온 점착력(90도 박리) 시험: 아크릴계 에멀젼 점착제 점착테이프 시편을 기포가 들어가지 않도록 피착제(SUS 또는 HDPE) 위에 부착시키고, 부착된 점착테이프 시편 위를 2 kg 롤로 300 mm/min의 속도로 5회 왕복시키고 30분 동안 상온에서 숙성시킨 후 TA Texture Analyzer 기기를 사용하여 5 mm/sec의 속도로 90도 박리하면서 측정하였다. * Adhesion test at room temperature (90 degree peeling) test After reciprocating five times and aged at room temperature for 30 minutes, it was measured while peeling 90 degrees using a TA Texture Analyzer instrument at a rate of 5 mm / sec.
*초기 점착력(Loop Tack) 시험: 공인 시험 규격인 Finat test method에 준하여 초기 점착력을 측정하였다. 이는, 점착테이프 시편을 Loop로 만들어 초기점착력을 측정하는 방법으로 FTM9 'loop' tack measurement를 따른다. Initial Tack Test : Initial adhesive force was measured according to the Finat test method, an official test standard. This is a method of measuring the initial adhesive force by making the adhesive tape specimen into a loop, and follows the FTM9 'loop' tack measurement.
*내열성 시험: 500 mL의 원형 폴리에틸렌(PE) 병(bottle)에 점착테이프 시편을 부착하고 60℃ 오븐에서 2시간 동안 보관한 후 상온에서 냉각하였다. 이 때, 점착테이프 시편이 폴리에틸렌 병에서 떨어지는 시간을 측정하였다. * Heat resistance test : The adhesive tape specimen was attached to a 500 mL round polyethylene (PE) bottle and stored in an oven at 60 ° C. for 2 hours and then cooled at room temperature. At this time, the time when the adhesive tape specimen fell from the polyethylene bottle was measured.
<표 1>TABLE 1
Figure PCTKR2014004512-appb-I000003
Figure PCTKR2014004512-appb-I000003
상기 표 1에서 보는 바와 같이, 실시예 1 내지 4는, 고밀도 폴리에틸렌(HDPE)에 대한 점착력을 증가시킬 수 있는 단량체로서 본 발명의 화학식 1 또는 2로 대표되는 페녹시에틸아크릴레이트 또는 2-메톡시-4-알릴페놀을 포함하여 아크릴계 에멀젼 수지를 제조하므로 HDPE에 대한 박리력과 초기 점착력이 비교예 1 내지 4와 비교하여 높음을 확인할 수 있다. As shown in Table 1, Examples 1 to 4, the phenoxyethyl acrylate or 2-methoxy represented by the formula (1) or 2 of the present invention as a monomer that can increase the adhesion to high density polyethylene (HDPE) Since an acrylic emulsion resin is prepared including -4-allylphenol, it can be confirmed that the peeling force and initial adhesive strength to HDPE are higher than those of Comparative Examples 1 to 4.
반면에, 비교예 1은 본 발명에 따른 변성 아크릴계 단량체를 포함하지 않으므로 HDPE에 대한 점착력이 낮고, 비교예 2는 페녹시에틸아크릴레이트를 포함하고 있음에도 그 함량이 권장량을 초과함에 따라 오히려 점착력이 감소하였으며, 비교예 3은 2-메톡시-4-알릴페놀을 권장량보다 초과 사용함에 따라 응집파괴 현상이 발생한 것을 확인할 수 있다.On the other hand, Comparative Example 1 does not include a modified acrylic monomer according to the present invention, the adhesion to HDPE is low, Comparative Example 2, even though it contains a phenoxyethyl acrylate, the adhesion decreases as the content exceeds the recommended amount In Comparative Example 3, it can be seen that the aggregation failure phenomenon occurred by using 2-methoxy-4-allylphenol in excess of the recommended amount.
즉, 페녹시에틸아크릴레이트 또는 2-메톡시-4-알릴페놀 등의 변성 아크릴계 단량체를 본 발명에 따른 소정의 함량으로 포함하여 아크릴계 에멀젼 수지를 제조하는 경우에, 표면 장력이 낮은 피착제에 대해서도 우수한 점착력을 발휘할 수 있음을 알 수 있다.That is, when the acrylic emulsion resin is prepared by including a modified acrylic monomer such as phenoxyethyl acrylate or 2-methoxy-4-allylphenol in a predetermined content according to the present invention, the adhesive agent having a low surface tension is also used. It can be seen that excellent adhesion can be exhibited.
본 발명이 속한 분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.
이상에서 설명한 바와 같이, 본 발명에 따른 아크릴계 에멀젼 수지는, 특정 화학식으로 표시되는 변성 아크릴계 단량체를 포함하여 중합됨으로써, 표면 장력이 낮은 피착제에 대해 점착력을 향상시키는 바, 이를 사용하여 제조되는 아크릴계 에멀젼 점착제는 피착제의 성질에 관계 없이 점착력이 우수하고, 따라서, 아크릴과 상용성이 떨어지는 고무계 수지 등과의 혼합이 필요하지 않으므로, 투명성 또한 유지할 수 있는 효과가 있다.As described above, the acrylic emulsion resin according to the present invention is polymerized by including a modified acrylic monomer represented by a specific chemical formula, thereby improving adhesion to a low-tension adherend, acrylic emulsion prepared using the same The pressure-sensitive adhesive is excellent in adhesive strength irrespective of the nature of the adhesive, and therefore, mixing with acrylic resin and the like, which is incompatible with acryl, is not necessary, and thus transparency can be maintained.

Claims (16)

  1. i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체와, ii) 하기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 하기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체를 포함하는 혼합 단량체, 및 가교제가 공중합된 것을 특징으로 하는 아크릴계 에멀젼 수지: i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2 below: Acrylic emulsion resin, characterized in that the copolymerized mixed monomer and a crosslinking agent:
    Figure PCTKR2014004512-appb-I000004
    Figure PCTKR2014004512-appb-I000004
    상기 식 1에서, n은 0 내지 20이고;In formula 1, n is 0 to 20;
    상기 식 2에서, n'는 0내지 18이다.In Equation 2, n 'is 0 to 18.
  2. 제 1 항에 있어서, 상기 아크릴계 에멀젼 수지는, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 75 내지 95 중량%, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량%를 포함하는 혼합 단량체, 및 가교제 0.1 내지 5 중량%가 공중합된 것을 특징으로 하는 아크릴계 에멀젼 수지.According to claim 1, wherein the acrylic emulsion resin, i) 75 to 95% by weight acrylic monomer having an alkyl group having 1 to 18 carbon atoms, based on the total weight of the acrylic emulsion resin, ii) modified acrylic monomer represented by the formula (1) And a mixed monomer comprising 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of modified acrylic monomers represented by Formula 2, and 0.1 to 5% by weight of an acrylic emulsion resin copolymerized. .
  3. i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체, ii) 하기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 하기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체, iii)알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체를 포함하는 혼합 단량체, 및 가교제가 공중합된 것을 특징으로 하는 아크릴계 에멀젼 수지:i) an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by Formula 1 and a modified acrylic monomer represented by Formula 2, iii) At least one monomer selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles, iv) mixed monomers comprising at least one monomer selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers, and crosslinking agents Acrylic emulsion resin characterized in that copolymerized:
    Figure PCTKR2014004512-appb-I000005
    Figure PCTKR2014004512-appb-I000005
    상기 식 1에서, n은 0 내지 20이고;In formula 1, n is 0 to 20;
    상기 식 2에서, n'는 0내지 18이다.In Equation 2, n 'is 0 to 18.
  4. 제 3 항에 있어서, 상기 아크릴계 에멀젼 수지는, 아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 60 내지 80 중량%, ii) 상기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 상기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량% iii) 알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 20 중량%, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 10 중량%을 포함하는 혼합 단량체 및 가교제 0.1 내지 3 중량%가 공중합된 것을 특징으로 하는 아크릴계 에멀젼 수지.According to claim 3, wherein the acrylic emulsion resin, i) 60 to 80% by weight acrylic monomer having an alkyl group having 1 to 18 carbon atoms, based on the total weight of the acrylic emulsion resin, ii) modified acrylic monomer represented by the formula (1) And 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of modified acrylic monomers represented by Formula 2 iii) at least one monomer selected from the group consisting of allyl ester, vinyl ester, unsaturated acetate and unsaturated nitrile 0.5 to 20% by weight, iv) mixed monomer comprising 0.5 to 10% by weight of at least one monomer selected from the group consisting of unsaturated carboxylic acids and hydroxyl-containing unsaturated monomers and 0.1 to 3% by weight of crosslinking agent Acrylic emulsion resin.
  5. 제 1 항 또는 제 3 항에 있어서, 상기 i)의 아크릴계 단량체는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸아크릴레이트, t-부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 헵틸아크릴레이트, 이소옥틸아크릴레이트, 옥틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 이소데실아크릴레이트, 데실(메타)아크릴레이트, 도데실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 스테아릴(메타)아크릴레이트 및 라우릴(메타)아크릴레이트로 이루어진 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 아크릴계 에멀젼 수지.The acryl-based monomer according to claim 1 or 3, wherein the acryl-based monomer of i) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth). Acrylate, isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl acrylate, isooctyl acrylate, octyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, isodecyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate and lauryl (meth) acrylate Acrylic emulsion resin, characterized in that at least one selected from the group consisting of.
  6. 제 3 항에 있어서, 상기 iii)의 단량체는 아세트산 비닐, 부탄산 비닐, 프로피온산 비닐, 라우릴산 비닐, 비닐 피롤리돈, 스타이렌, 하기 화학식 3으로 표시되는 변성 비닐계 단량체, 아크릴로니트릴 및 메타크릴로니트릴로 이루어진 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 아크릴계 에멀젼 수지:According to claim 3, wherein the monomer of iii) is vinyl acetate, vinyl butyrate, vinyl propionate, vinyl lauryl acid, vinyl pyrrolidone, styrene, modified vinyl monomer represented by the following formula (3), acrylonitrile and Acrylic emulsion resin, characterized in that at least one selected from the group consisting of methacrylonitrile:
    Figure PCTKR2014004512-appb-I000006
    Figure PCTKR2014004512-appb-I000006
    상기 식 3에서, n''는 0 내지 18이다.In Formula 3, n '' is 0 to 18.
  7. 제 6 항에 있어서, 상기 iii)의 단량체는 상기 화학식 3으로 표시되는 변성 비닐계 단량체인 것을 특징으로 하는 아크릴계 에멀젼 수지:The acrylic emulsion resin according to claim 6, wherein the monomer of iii) is a modified vinyl monomer represented by Chemical Formula 3.
  8. 제 3 항에 있어서, 상기 iv)의 단량체는 아크릴산, 이타콘산, 무수말레인산, 푸마르산, 크로탄산 메타크릴산, 에틸메타크릴산, 히드록시메틸(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 히드록시부틸(메타)아크릴레이트, 히드록시헥실(메타)아크릴레이트, 히드록시옥틸(메타)아크릴레이트, 히드록시라우릴(메타)아크릴레이트, 및 히드록시프로필렌글리콜(메타)아크릴레이트로 이루어진 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 아크릴계 에멀젼 수지.The method of claim 3, wherein the monomer of iv) is acrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotanic acid methacrylic acid, ethyl methacrylic acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxylauryl (meth) acrylate, and hydroxy Acrylic emulsion resin, characterized in that at least one selected from the group consisting of propylene glycol (meth) acrylate.
  9. 제 1 항 또는 제 3 항에 있어서, 상기 가교제는 폴리에틸렌글리콜디아크릴레이트 및 폴리프로필렌글리콜디아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 아크릴계 에멀젼 수지.The acrylic emulsion resin according to claim 1 or 3, wherein the crosslinking agent is at least one member selected from the group consisting of polyethylene glycol diacrylate and polypropylene glycol diacrylate.
  10. 제 1 항에 따른 아크릴계 에멀젼 수지의 제조방법에 있어서,In the method of producing an acrylic emulsion resin according to claim 1,
    아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 75 내지 95 중량%와, ii) 하기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 하기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량%를 포함하는 혼합 단량체, 및 가교제 0.1 내지 5 중량%를 중합하는 과정을 포함하는 것을 특징으로 하는 아크릴계 에멀젼 수지의 제조방법:I) 75 to 95% by weight of an acrylic monomer having an alkyl group having 1 to 18 carbon atoms, and ii) a modified acrylic monomer represented by Formula 1 below and a modified acrylic monomer represented by Formula 2 based on the total weight of the acrylic emulsion resin Method for producing an acrylic emulsion resin comprising the step of polymerizing a mixed monomer containing 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of, and 0.1 to 5% by weight of a crosslinking agent:
    Figure PCTKR2014004512-appb-I000007
    Figure PCTKR2014004512-appb-I000007
    상기 식 1에서, n은 0 내지 20이고;In formula 1, n is 0 to 20;
    상기 식 2에서, n'는 0내지 18이다.In Equation 2, n 'is 0 to 18.
  11. 제 3 항에 따른 아크릴계 에멀젼 수지의 제조방법에 있어서,In the method for producing an acrylic emulsion resin according to claim 3,
    아크릴계 에멀젼 수지 전체 중량을 기준으로 i) 탄소수 1 내지 18의 알킬기를 가진 아크릴계 단량체 60 내지 80 중량%, ii) 하기 화학식 1로 표시되는 변성된 아크릴계 단량체 및 하기 화학식 2로 표시되는 변성된 아크릴계 단량체로 이루어진 군에서 선택되는 하나 이상의 변성 아크릴계 단량체 0.5 내지 20 중량% iii) 알릴 에스테르, 비닐 에스테르, 불포화 아세테이트 및 불포화 니트릴로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 20 중량%, iv) 불포화 카본산 및 수산기 함유 불포화 단량체로 이루어진 군으로부터 선택되는 1종 이상의 단량체 0.5 내지 10 중량%을 포함하는 혼합 단량체, 및 가교제 0.1 내지 3 중량%를 중합하는 과정을 포함하는 것을 특징으로 하는 아크릴계 에멀젼 수지의 제조방법:I) 60 to 80 wt% of an acrylic monomer having an alkyl group having 1 to 18 carbon atoms based on the total weight of the acrylic emulsion resin, ii) a modified acrylic monomer represented by Formula 1 below and a modified acrylic monomer represented by Formula 2 below 0.5 to 20% by weight of at least one modified acrylic monomer selected from the group consisting of iii) 0.5 to 20% by weight of at least one monomer selected from the group consisting of allyl ester, vinyl ester, unsaturated acetate and unsaturated nitrile, iv) unsaturated carboxylic acid and A method for producing an acrylic emulsion resin comprising the step of polymerizing a mixed monomer comprising 0.5 to 10% by weight of at least one monomer selected from the group consisting of hydroxyl-containing unsaturated monomers, and 0.1 to 3% by weight of a crosslinking agent:
    Figure PCTKR2014004512-appb-I000008
    Figure PCTKR2014004512-appb-I000008
    상기 식 1에서, n은 0 내지 20이고;In formula 1, n is 0 to 20;
    상기 식 2에서, n'는 0내지 18이다.In Equation 2, n 'is 0 to 18.
  12. 제 1 항에 따른 아크릴계 에멀젼 수지를 포함하는 것을 특징으로 하는 수계 아크릴계 에멀젼 점착제. An aqueous acrylic emulsion pressure-sensitive adhesive comprising an acrylic emulsion resin according to claim 1.
  13. 제 3 항에 따른 아크릴계 에멀젼 수지를 포함하는 것을 특징으로 하는 수계 아크릴계 에멀젼 점착제. An aqueous acrylic emulsion pressure-sensitive adhesive comprising an acrylic emulsion resin according to claim 3.
  14. 제 12 항에 따른 수계 아크릴계 에멀젼 점착제를 점착용 필름 또는 시트상에 적용하여 점착제 층을 형성하는 점착시트. An adhesive sheet for forming an adhesive layer by applying the aqueous acrylic emulsion adhesive according to claim 12 on a pressure-sensitive adhesive film or sheet.
  15. 제 13 항에 따른 수계 아크릴계 에멀젼 점착제를 점착용 필름 또는 시트상에 적용하여 점착제 층을 형성하는 점착시트. An adhesive sheet for forming an adhesive layer by applying the aqueous acrylic emulsion pressure-sensitive adhesive according to claim 13 on a pressure-sensitive adhesive film or sheet.
  16. 제 14 항 또는 제 15 항에 있어서, 상기 점착용 필름 또는 시트는 표면 장력이 낮은 폴리올레핀계 기재인 것을 특징으로 하는 점착시트The pressure-sensitive adhesive sheet of claim 14 or 15, wherein the pressure-sensitive adhesive film or sheet is a polyolefin-based substrate having a low surface tension.
PCT/KR2014/004512 2013-07-19 2014-05-21 Acrylic emulsion resin having excellent adhesive property and preparation method therefor WO2015008930A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201480013397.6A CN105189580B (en) 2013-07-19 2014-05-21 Acrylic emulsion resin having excellent adhesive property and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20130085648 2013-07-19
KR10-2013-0085648 2013-07-19

Publications (1)

Publication Number Publication Date
WO2015008930A1 true WO2015008930A1 (en) 2015-01-22

Family

ID=52346346

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/004512 WO2015008930A1 (en) 2013-07-19 2014-05-21 Acrylic emulsion resin having excellent adhesive property and preparation method therefor

Country Status (4)

Country Link
KR (1) KR101614341B1 (en)
CN (1) CN105189580B (en)
TW (1) TWI516508B (en)
WO (1) WO2015008930A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199581A (en) * 2015-10-26 2015-12-30 刘朝辉 Low-cost sea water resistant paint and preparation method thereof
CN115477900A (en) * 2022-10-18 2022-12-16 深圳市高仁电子新材料有限公司 Acrylic optical adhesive with three-layer structure and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102516241B1 (en) * 2016-12-27 2023-03-29 주식회사 엘지화학 Acrylic emulsion adhesive and method for preparing the same
CN110627948A (en) * 2019-09-29 2019-12-31 陕西科技大学 Double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof
CN110563880A (en) * 2019-09-29 2019-12-13 陕西科技大学 double-bond vanillin-modified styrene-acrylic emulsion and preparation method thereof
CN110563881A (en) * 2019-09-29 2019-12-13 陕西科技大学 double-bonded vanillyl alcohol modified styrene-acrylic emulsion and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172595A (en) * 1999-12-20 2001-06-26 Toagosei Co Ltd Removable type adhesive film or sheet
KR20070059981A (en) * 2005-12-06 2007-06-12 닛토덴코 가부시키가이샤 Light-shielding pressure-sensitive adhesive sheet
KR20080043926A (en) * 2006-11-15 2008-05-20 주식회사 에스아이켐 High solid pressure-sensitive adhesive, fabrication method of that, and the second product using that
KR20090126904A (en) * 2008-06-05 2009-12-09 주식회사 엘지화학 Acrylic pressure-sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same
JP2010159333A (en) * 2009-01-07 2010-07-22 Nitto Denko Corp Light-diffusible adhesive composition, light diffusible adhesive layer and light-diffusible adhesive sheet

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101082450B1 (en) * 2008-01-14 2011-11-11 주식회사 엘지화학 Acrylic pressure-sensitive adhesive compositions
KR101293902B1 (en) * 2008-07-01 2013-08-06 주식회사 엘지화학 Pressure-sensitive adhesive compositions, protective films for polarizer, polarizers and liquid crystal display
KR101027854B1 (en) * 2008-08-20 2011-04-07 주식회사 엘지화학 Composition for acrylic pressure-sensitive adhesive and surface finishing material comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172595A (en) * 1999-12-20 2001-06-26 Toagosei Co Ltd Removable type adhesive film or sheet
KR20070059981A (en) * 2005-12-06 2007-06-12 닛토덴코 가부시키가이샤 Light-shielding pressure-sensitive adhesive sheet
KR20080043926A (en) * 2006-11-15 2008-05-20 주식회사 에스아이켐 High solid pressure-sensitive adhesive, fabrication method of that, and the second product using that
KR20090126904A (en) * 2008-06-05 2009-12-09 주식회사 엘지화학 Acrylic pressure-sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same
JP2010159333A (en) * 2009-01-07 2010-07-22 Nitto Denko Corp Light-diffusible adhesive composition, light diffusible adhesive layer and light-diffusible adhesive sheet

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199581A (en) * 2015-10-26 2015-12-30 刘朝辉 Low-cost sea water resistant paint and preparation method thereof
CN115477900A (en) * 2022-10-18 2022-12-16 深圳市高仁电子新材料有限公司 Acrylic optical adhesive with three-layer structure and preparation method thereof
CN115477900B (en) * 2022-10-18 2023-06-30 深圳市高仁电子新材料有限公司 Acrylic optical adhesive with three-layer structure and preparation method thereof

Also Published As

Publication number Publication date
KR101614341B1 (en) 2016-04-21
TWI516508B (en) 2016-01-11
CN105189580A (en) 2015-12-23
CN105189580B (en) 2017-04-19
TW201509965A (en) 2015-03-16
KR20150010573A (en) 2015-01-28

Similar Documents

Publication Publication Date Title
WO2014073840A1 (en) Acryl-silicon based hybrid emulsion adhesive composition, and method for preparing same
US8710139B2 (en) Acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive layer, and acrylic pressure-sensitive adhesive tape
WO2015008930A1 (en) Acrylic emulsion resin having excellent adhesive property and preparation method therefor
WO2015046872A1 (en) Adhesive composition for a polypropylene film and method for preparing same
US9683145B2 (en) Pressure-sensitive adhesives with onium-epoxy crosslinking system
US20130004769A1 (en) Acrylic pressure-sensitive adhesive composition and acrylic pressure-sensitive adhesive tape
WO2014058199A1 (en) Acrylic emulsion adhesive composition comprising nano sized latex particles having a mono-modal particle size distribution, and production method for same
WO2015041403A1 (en) Acrylic emulsion adhesive, and production method for same
WO2016024729A1 (en) Acrylic emulsion adhesive with excellent low-temperature adhesive strength and retention strength and manufacturing method therefor
US20140037951A1 (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, and optical film
WO2012121547A2 (en) Adhesive composition for a wafer processing film
US9890301B2 (en) Water-based pressure-sensitive adhesive compositions
WO2011025153A2 (en) Water-based adhesive composition, method for manufacturing same, and adhesive film
KR102657938B1 (en) Process for preparing pressure sensitive adhesive composition
JP5518370B2 (en) Method for producing water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling, water-dispersed acrylic pressure-sensitive adhesive composition for re-peeling, pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet
WO2016027993A1 (en) Acrylic emulsion adhesive having excellent detergency and preparing method therefor
US10081745B1 (en) Water-based pressure-sensitive adhesive compositions
WO2014174732A1 (en) Adhesive composition, adhesive layer, adhesive sheet and optical film
WO2013085295A1 (en) Composition for foam tape base material, foam tape using same, and method for manufacturing composition for foam tape base material
JP2008133408A (en) Acrylic pressure-sensitive adhesive composition and pressure-sensitive sheet or tape using the composition
KR102332742B1 (en) Acrylic emulsion pressure sensitive adhesive composition
WO2020130285A1 (en) Acrylic emulsion pressure-sensitive adhesive composition
KR102371667B1 (en) Acrylic emulsion pressure snsitive adhesive composition
WO2013051876A2 (en) Aqueous adhesive composition that changes little over time
CN113366076B (en) Aqueous acrylic pressure-sensitive adhesive composition, method for producing the same, and pressure-sensitive adhesive sheet comprising the same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480013397.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14826081

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14826081

Country of ref document: EP

Kind code of ref document: A1