WO2015008930A1 - Résine d'une émulsion acrylique ayant une excellente propriété d'adhérence, et son procédé de préparation - Google Patents

Résine d'une émulsion acrylique ayant une excellente propriété d'adhérence, et son procédé de préparation Download PDF

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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
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Prior art keywords
acrylate
monomer
meth
acrylic emulsion
emulsion resin
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PCT/KR2014/004512
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English (en)
Korean (ko)
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이금형
김영민
하재웅
한정섭
송공주
김미영
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주식회사 엘지화학
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Priority to CN201480013397.6A priority Critical patent/CN105189580B/zh
Publication of WO2015008930A1 publication Critical patent/WO2015008930A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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.

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

Abstract

La présente invention porte sur une résine d'une émulsion acrylique ayant une excellente propriété d'adhérence, et sur un procédé de préparation de cette résine, et plus précisément sur une résine d'une émulsion acrylique, caractérisée en ce qu'un monomère mixte et un agent de réticulation sont copolymérisés, le monomère mixte comprenant i) un monomère acrylique ayant un groupe alkyle ayant de 1 à 18 atomes de carbone, et ii) au moins un monomère acrylique modifié choisi dans le groupe consistant en un monomère acrylique modifié représenté par la formule 1 (le même que la formule 1 présentée dans la revendication 1) et un monomère acrylique modifié représenté par la formule 2 (le même que la formule 2 présentée dans la revendication 1), et comprenant en option iii) au moins un monomère choisi dans le groupe consistant en un ester allylique, un ester vinylique, un acétate insaturé et un nitrile insaturé, et iv) au moins un monomère choisi dans le groupe consistant en un acide carboxylique insaturé et un monomère insaturé hydroxylé ; et sur un procédé de préparation de cette résine.
PCT/KR2014/004512 2013-07-19 2014-05-21 Résine d'une émulsion acrylique ayant une excellente propriété d'adhérence, et son procédé de préparation WO2015008930A1 (fr)

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CN105199581A (zh) * 2015-10-26 2015-12-30 刘朝辉 一种低成本耐海水涂料及其制备方法
CN115477900A (zh) * 2022-10-18 2022-12-16 深圳市高仁电子新材料有限公司 一种三层结构的丙烯酸类光学胶及其制备方法

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KR102516241B1 (ko) * 2016-12-27 2023-03-29 주식회사 엘지화학 아크릴계 에멀젼 점착제 및 이의 제조 방법
CN110563881A (zh) * 2019-09-29 2019-12-13 陕西科技大学 一种双键化香草醇改性苯丙乳液及其制备方法
CN110563880A (zh) * 2019-09-29 2019-12-13 陕西科技大学 一种双键化香草醛改性苯丙乳液及其制备方法
CN110627948A (zh) * 2019-09-29 2019-12-31 陕西科技大学 一种双键化丁香酚改性苯丙乳液及其制备方法

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KR20070059981A (ko) * 2005-12-06 2007-06-12 닛토덴코 가부시키가이샤 차광 감압성 접착제 시이트
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CN105199581A (zh) * 2015-10-26 2015-12-30 刘朝辉 一种低成本耐海水涂料及其制备方法
CN115477900A (zh) * 2022-10-18 2022-12-16 深圳市高仁电子新材料有限公司 一种三层结构的丙烯酸类光学胶及其制备方法
CN115477900B (zh) * 2022-10-18 2023-06-30 深圳市高仁电子新材料有限公司 一种三层结构的丙烯酸类光学胶及其制备方法

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TW201509965A (zh) 2015-03-16
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TWI516508B (zh) 2016-01-11
CN105189580B (zh) 2017-04-19
KR101614341B1 (ko) 2016-04-21

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