WO2020091467A1 - Procédé de fabrication d'adhésif aqueux pour vêtements - Google Patents

Procédé de fabrication d'adhésif aqueux pour vêtements Download PDF

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Publication number
WO2020091467A1
WO2020091467A1 PCT/KR2019/014619 KR2019014619W WO2020091467A1 WO 2020091467 A1 WO2020091467 A1 WO 2020091467A1 KR 2019014619 W KR2019014619 W KR 2019014619W WO 2020091467 A1 WO2020091467 A1 WO 2020091467A1
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WIPO (PCT)
Prior art keywords
weight
parts
emulsifier
monomer
clothing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/KR2019/014619
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English (en)
Korean (ko)
Inventor
서성종
양승훈
조현주
박규연
여정은
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020190135680A external-priority patent/KR102267592B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US17/051,058 priority Critical patent/US12024653B2/en
Priority to CN201980026506.0A priority patent/CN112004896B/zh
Priority to EP19877968.8A priority patent/EP3763794A4/fr
Publication of WO2020091467A1 publication Critical patent/WO2020091467A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F220/10—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
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • the present invention relates to a method of manufacturing an aqueous pressure-sensitive adhesive composition for clothing, which maintains aging peel strength even when stored at high temperature for a long time and significantly improves residue characteristics when removing the pressure-sensitive adhesive from a clothing fabric or the like.
  • Aqueous emulsion adhesives can use polymers having a higher molecular weight than solvent-based polymers, regardless of the viscosity of the adhesive and the molecular weight of the dispersion polymer, and can obtain a wide range of solids concentrations, small aging resistance, low viscosity, low It has good adhesiveness in the solid content region and good compatibility with other polymers.
  • the present invention has excellent adhesion strength to the garment fabric itself even when stored at a high temperature for a long time, while maintaining high physical properties, and when removing the adhesive from the garment fabric substrate, the residue characteristic of the adhesive remaining on the garment fabric substrate is greatly improved It is intended to provide a method of manufacturing an aqueous pressure-sensitive adhesive composition for clothing.
  • the present invention also provides an aqueous acrylic pressure-sensitive adhesive for clothes comprising the composition thus prepared.
  • an emulsifier in the presence of an emulsifier, together with the (meth) acrylic acid ester-based monomer containing an alkyl group having 1 to 14 carbon atoms, a vinyl ester-based monomer, a styrene-based monomer, a (meth) acrylic acid-based monomer, and the following formula Emulsifying and polymerizing a monomer mixture containing at least one comonomer selected from the group consisting of monomers represented by 1,
  • the (meth) acrylic acid-based monomer is included at 0.1% by weight to 2.5% by weight, and the monomer represented by the following Chemical Formula 1 is included at 0.1% by weight to 0.3% by weight,
  • a dialkyl sodium sulfosuccinate-based compound containing an alkyl group of 14 to 14, and one or more second emulsifiers selected from the group consisting of a sodium alkyl sulfate-based compound containing an alkyl group having 1 to 14 carbon atoms are used, provided that The second emulsifier includes at least one of the diaryl oxide disulfonate-based compound or the sodium alkyl sulfate-based compound,
  • the emulsifier is used in 0.5 parts by weight to 1.6 parts by weight based on 100 parts by weight of the monomer mixture, and based on the weight of the first emulsifier, the second emulsifier is used in a weight ratio of 0.3 to 0.6,
  • a method of manufacturing an aqueous pressure-sensitive adhesive composition for clothing is provided.
  • R 1 and R 2 are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
  • X is a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of the hydrogens of the alkylene group is substituted with a hydroxy group
  • Y is a single bond or an oxygen atom, or -NR 4-
  • Z is a single bond or carbon number 1 to 10 alkylene groups, or X and Y are one single bond, X, Y, and Z are one single bond,
  • R 3 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • a water-based acrylic pressure-sensitive adhesive for clothing comprising a composition prepared by the method as described above is provided.
  • the present invention by optimizing and using the monomer composition and the composition of the emulsifier in the process of polymerizing the resin for water-based adhesives for clothing, it maintains properties equal to or higher than the existing ones and removes the adhesives with effective adhesiveness even in clothing fabrics even when stored at high temperatures for a long time. It has the effect of realizing the stable residue characteristics.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.
  • the same or higher physical properties are maintained, even when stored at high temperature for a long time. It can exhibit stable residue characteristics when removing the adhesive with effective adhesion.
  • the method for producing an aqueous pressure-sensitive adhesive composition for clothing includes, in the presence of an emulsifier, a (meth) acrylic acid ester-based monomer containing an alkyl group having 1 to 14 carbon atoms, a vinyl ester-based monomer, and a styrene-based monomer.
  • It comprises the step of emulsion polymerization of a monomer mixture comprising at least one comonomer selected from the group consisting of a monomer, a (meth) acrylic acid-based monomer, and a monomer represented by Formula 1 below, and (meth) acrylic acid-based in the monomer mixture
  • the monomer is included in 0.1% to 2.5% by weight, and the monomer represented by the following Chemical Formula 1 is included in 0.1% to 0.3% by weight, and as the emulsifier, sodium polyoxyethylene containing an alkyl group having 1 to 14 carbon atoms.
  • a first emulsifier that is an alkyl ether sulfate-based compound
  • the second emulsifier contains at least one of the diaryl oxide disulfonate-based compound or the sodium alkyl sulfate-based compound, and the emulsifier is 0.5 weight based on 100 parts by weight of the monomer mixture It is used in parts to 1.6 parts by weight, and based on the weight of the first emulsifier, the second emulsifier is used in an amount of 0.3 to 0.6 parts by weight to produce an acrylic emulsion resin.
  • R 1 and R 2 are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
  • X is a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of the hydrogens of the alkylene group is substituted with a hydroxy group
  • Y is a single bond or an oxygen atom, or -NR 4-
  • Z is a single bond or carbon number 1 to 10 alkylene groups, or X and Y are one single bond, X, Y, and Z are one single bond,
  • R 3 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • the method according to an embodiment of the present invention uses a (meth) acrylic acid-based monomer and a monomer of Formula 1 in a specific composition range in a comonomer used with a (meth) acrylic acid-ester-based monomer, and upon polymerization
  • the emulsifier is selected from the group consisting of a diphenyl oxide disulfonate-based compound, a dioctyl sodium sulfosuccinate-based compound, and a sodium lauryl sulfate-based compound, together with a first emulsifier that is a sodium polyoxyethylene lauryl ether sulfate-based compound. It is characterized in that one or more second emulsifiers are used in a specific composition range.
  • part by weight refers to the relative concept of the weight of the rest of the material based on the weight of a certain material. For example, in a mixture containing material A having a weight of 50 g, material B having a weight of 20 g, and material C having a weight of 30 g, the amount of material B and material C based on 100 parts by weight of material A is 40 It is parts by weight and 60 parts by weight.
  • % by weight means the absolute concept of the weight of the weight of a certain substance in the total weight.
  • contents of substances A, B, and C in 100% of the total weight of the mixture are 50%, 20%, and 30% by weight, respectively.
  • (meth) acrylate is meant to include both acrylate and methacrylate.
  • the emulsifier is used for initial particle formation during polymerization reaction of the monomer mixture, size control of the resulting particles, and stability of the particles.
  • a sodium polyoxyethylene alkyl ether sulfate sodium polyoxyethylene alkyl ether sulfate, various types according to EO group
  • the first emulsifier and the second emulsifier are used by mixing at least one selected from the group consisting of sulfate alkyl compounds.
  • the second emulsifier is the diaryl oxide disulfonate-based compound or the sodium alkyl sulfate in terms of securing excellent coating properties while increasing adhesive properties through effective mutual compatibility between the interface of the garment fabric and the adhesive composition, which is an adherend. At least one of the compounds must be included.
  • the emulsifier should be used in an amount of about 0.5 to about 1.6 parts by weight based on 100 parts by weight of the monomer mixture.
  • the emulsifier content should be at least about 0.5 parts by weight in terms of coating properties, specifically at least about 0.5 parts by weight, or at least about 0.6 parts by weight, or at least about 0.7 parts by weight, or at least about 0.8 parts by weight, or about 0.9 It can be used in parts by weight or more.
  • the content of the emulsifier is about 1.5 parts by weight or less in terms of preventing deterioration in physical properties such as initial adhesive strength and peel strength because the emulsifier interferes with adhesion when the emulsifier is distributed to the coating surface after drying of the latex, that is, the acrylic emulsion resin. It should be, and specifically, may be used in an amount of about 1.55 parts by weight or less, or about 1.5 parts by weight or less, and in some cases, about 1.3 parts by weight or less, or about 1.2 parts by weight or less.
  • the composition of the first emulsifier and the second emulsifier in the emulsifier is based on the weight of the first emulsifier
  • the second emulsifier is used in a weight ratio of about 0.3 to about 0.6, specifically about 0.4 to about 0.55 in weight ratio Or, it may be used in a weight ratio of about 0.425 to about 0.535.
  • the content of the second emulsifier should be at least about 0.3% by weight based on the weight of the first emulsifier in terms of particle size, and should be less than or equal to about 0.6% by weight in terms of water solubility. .
  • the first emulsifier may be used in an amount of about 0.5 part to about 1.1 part by weight, or about 0.6 to about 1.05 part by weight, or about 0.65 part to about 1 part by weight based on 100 parts by weight of the monomer mixture
  • the total amount of the second emulsifier may be used in an amount of about 0.2 parts to about 0.6 parts by weight, or about 0.25 to about 0.55 parts by weight, or about 0.3 parts to about 0.5 parts by weight based on 100 parts by weight of the monomer mixture.
  • emulsifier about 0.8 parts by weight to about 1.1 parts by weight of sodium polyoxyethylene alkyl ether sulfate-based compound containing an alkyl group having 1 to 14 carbon atoms, based on 100 parts by weight of the monomer mixture Diaryl oxide disulfonate-based compound containing 6 to 20 alkyl groups of about 0.1 parts by weight to about 0.25 parts by weight of dialkyl sodium sulfosuccinate containing alkyl groups having 1 to 14 carbon atoms (dialkyl sodium sulfosuccinate) about 0.2 parts by weight to about 0.35 parts by weight; Sodium polyoxyethylene alkyl ether sulfate-based compound containing an alkyl group having 1 to 14 carbon atoms, about 0.8 parts by weight to about 1.1 parts by weight, and a diaryl oxide disulfonate containing an alkyl group having 6 to 20 carbon atoms (diaryl) oxide disulfonate) compound about 0.4 parts by weight to about
  • a sodium polyoxyethylene alkyl ether sulfate-based compound containing an alkyl group having 1 to 14 carbon atoms with respect to 100 parts by weight of the monomer mixture, and 6 to 20 carbon atoms.
  • the first emulsifier is a C1-C14 alkyl group, that is, sodium polyoxyethylene alkyl ether sulfate having 1 to 14 carbon atoms, and is not limited as long as it is a material known in the art.
  • the sodium polyethylene alkyl ether sulfate-based compound may be a compound containing an alkyl group having 8 to 14 carbon atoms, preferably a sodium polyoxyethylene lauryl ether sulfate-based compound. .
  • the diaryl oxide disulfonate-based compound is a C6-C20 aryl group, that is, a diaryl oxide disulfonate-based compound comprising an aryl group having 6 to 20 carbon atoms, which is known in the art.
  • the diaryl oxide disulfonate-based compound may be a compound containing an aryl group having 6 to 12 carbon atoms, and may be preferably diphenyl oxide disulfonate.
  • the dialkyl sodium sulfosuccinate-based compound in the second emulsifier is a C1-C14 alkyl group, that is, a dialkyl sodium sulfosuccinate-based compound having an alkyl group having 1 to 14 carbon atoms, in the art.
  • the dialkyl sodium sulfosuccinate-based compound may be a compound containing an alkyl group having 8 to 14 carbon atoms, and preferably a dioctyl sodium sulfosuccinate-based compound.
  • Sodium alkyl sulfate-based compound in the second emulsifier is a C1-C14 alkyl group, that is, a sodium alkyl sulfate (sodium alkyl sulfate) -based compound containing an alkyl group having 1 to 14 carbon atoms, there is no limitation as long as it is a material known in the art.
  • the sodium alkyl sulfate-based compound may be a compound containing an alkyl group having 8 to 14 carbon atoms, and preferably, may be a sodium lauryl sulfate-based compound.
  • sodium polyoxyethylene lauryl ether sulfate sodium polyoxyethylene lauryl ether sulfate from about 0.8 parts to about 1.1 parts by weight of diphenyl oxide disulfonate (diphenyl oxide disulfonate) about 0.1 parts by weight to about 0.25 parts by weight, about 0.2 parts by weight to about 0.35 parts by weight of a dioctyl sodium sulfosuccinate compound;
  • sodium polyoxyethylene lauryl ether sulfate sodium polyoxyethylene lauryl ether sulfate from about 0.8 parts to about 1.1 parts by weight of diphenyl oxide disulfonate (diphenyl oxide dis
  • the monomer mixture as the emulsifier about 1 part by weight of sodium polyoxyethylene lauryl ether sulfate and about diphenyl oxide disulfonate 0.2 parts by weight, about 0.3 parts by weight of a dioctyl sodium sulfosuccinate compound; About 1 part by weight of sodium polyoxyethylene lauryl ether sulfate and about 0.5 part by weight of diphenyl oxide disulfonate; Alternatively, about 0.65 parts by weight to about 0.7 parts by weight of sodium polyoxyethylene lauryl ether sulfate and about 0.3 parts by weight of sodium lauryl sulfate may be used.
  • the monomer mixture for performing the polymerization process in the presence of the emulsifier as described above in the present invention together with the (meth) acrylic acid ester-based monomer containing an alkyl group having 1 to 14 carbon atoms, vinyl ester-based monomer, styrene-based monomer, ( Meth) acrylic acid monomer, and at least one comonomer selected from the group consisting of monomers represented by the following formula (1).
  • the term "monomer mixture” refers to a state in which one or more monomers described below are mixed together based on acrylic monomers, and the one or more monomers may be prepared by being injected together, and sequentially It can be produced by being injected, the manufacturing method is not limited.
  • the (meth) acrylic acid ester monomer is a C1-C14 alkyl group, that is, a (meth) acrylic acid ester monomer having an alkyl group having 1 to 14 carbon atoms, and is not limited as long as it is a material known in the art.
  • the (meth) acrylic acid ester monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, t-octyl (meth) acrylate, n-ethylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Acrylate, tridecyl (
  • methyl (meth) acrylate ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate can be preferably used.
  • the (meth) acrylic acid ester monomer may include from about 55% to about 99.8% by weight, or from about 58% to about 99% by weight, or from about 62% to about 97% by weight of the total content of the monomer mixture. .
  • the content of the meta) acrylic acid ester monomer is contained in less than about 55% by weight, an initial adhesion may not be secured, and thus a problem that adhesion to the garment may not appear.
  • the (meth) acrylic acid ester monomer exceeds about 99.8% by weight, the transfer of the pressure-sensitive adhesive to the adherend occurs largely when removed after use, and is not preferable since the washability is poor.
  • methyl (meth) acrylate in the (meth) acrylic acid ester monomer is included in an amount of about 5 to 20% by weight in the total amount of the monomer mixture, butyl (meth) acrylate and 2-ethyl
  • the remaining (meth) acrylic acid ester monomers such as hexyl (meth) acrylate may be included in about 30 to 50% by weight in the monomer mixture.
  • the glass transition temperature (Tg) of the acrylic emulsion resin is very low and soft (soft).
  • One polymer is formed, and in this case, since residues are largely generated, it is preferable that an appropriate composition of monomers and comonomers is achieved.
  • the properties of the pressure-sensitive adhesive are a result of the glass transition temperature (Tg) of the acrylic emulsion resin, the content ratio of each of the monomer and comonomer becomes important. It is preferable to adjust the proportion of the remaining monomers to obtain suitable adhesive properties.
  • the monomer mixture is at least one comonomer selected from the group consisting of the (meth) acrylate monomer, a vinyl ester monomer, a styrene monomer, a (meth) acrylic acid monomer, and a monomer represented by the following formula (1). It further includes.
  • the comonomers as described above may be manufactured by being injected together, or sequentially manufactured by being injected with each other, and thus the manufacturing method is not limited.
  • the (meth) acrylic acid-based monomer is a comonomer used in combination with the (meth) acrylic acid-ester-based monomer to maintain the aging peel strength during long-term storage under high temperature and humidity conditions while maintaining adhesive properties and residue properties.
  • the monomer represented by the formula (1) is characterized in that it comprises from about 0.1 to about 0.3% by weight.
  • the (meth) acrylic acid-based monomer comprises from about 0.2% to about 2% by weight, from about 0.5% to about 1.8% by weight, or from about 0.7% to about 1.5% by weight, represented by Formula 1
  • the monomer is characterized in that it comprises from about 0.15 to about 0.25% by weight or from about 0.18% to about 0.23% by weight.
  • the (meth) acrylic acid-based maleic anhydride, fumaric acid, crotanic acid, itaconic acid and may be one or more selected from the group consisting of (meth) acrylic acid, these may be used alone or in combination of two or more.
  • the (meth) acrylic acid-based monomer should be about 0.1% by weight or more in terms of enhancing retention or internal bond strength and enhancing molecular weight, and about 2.5% by weight or less in terms of not significantly increasing the aging peel strength even when stored at a high temperature for a long time Should be
  • the monomer represented by the formula (1) ethylene urea (ethyleneurea) -based substituent or N- (2- (2-oxoimidazolidin-1-yl) [N- (2- (2- oxoimidazolidin-1-yl)], and has the characteristic of effectively forming an internal crosslink.
  • the alkyl group may be a straight chain or a branched chain, and carbon number may be 1 to 10. According to an exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 4 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • R 1 and R 2 may each independently be hydrogen or methyl.
  • X is a single bond or an alkylene group having 2 to 5 carbon atoms, and one of hydrogens of the alkylene group may be substituted with a hydroxy group, for example, a 2-hydroxy butylene group.
  • Y may be a single bond or an oxygen atom, -NH-, or -NCH 3- .
  • Z may be a single bond or an alkyl group having 1 to 6 carbon atoms, and may be, for example, an ethylene group.
  • X and Y may be one single bond, or X, Y, and Z may be one single bond.
  • the monomer represented by Formula 1 is methacrylamidoethyl ethyleneurea, methacrylate ester ethyleneurea, allyl ether ethyleneurea, and N- (2) -(2-oxoimidazolidin-1yl) ethyl) (4-allyl ether) (3-hydroxy) butylamine [N- (2- (2-oxoimidazolidin-1-yl) ethyl) (4-allyl ether) (3-hydroxy) butylamine], and may be used alone or in combination of two or more. Specifically, methacrylamidoethyl ethyleneurea can be used.
  • the monomer represented by Formula 1 should be about 0.1% by weight or more in terms of molecular weight, and about 0.3% by weight or less in terms of physical properties. Particularly, when the monomer represented by Chemical Formula 1 is used in an amount of less than about 0.1% by weight, a large amount of residue occurs due to a large internal cross-linking role, and when used in excess of about 0.3% by weight, the residue is improved, but initial adhesion and peeling are improved. The intensity is reduced by more than half.
  • examples of one of the comonomers include vinyl ester monomers and styrene monomers.
  • the vinyl ester monomers include, but are not limited to, vinyl acetate, ethylene vinyl acetate, or vinyl ethylene acetate.
  • the vinyl ester-based monomer may be included in about 0 to about 35% by weight, or from about 10% to about 25% by weight based on the monomer mixture.
  • the styrene-based monomer may include styrene and alpha ( ⁇ ) -methyl styrene, but is not limited thereto.
  • the vinyl ester-based monomer may be included from about 0 to about 5% by weight, or from about 0 to about 3% by weight based on the monomer mixture.
  • the comonomer may be added in an amount of about 0.2 wt% to 45 wt%, or about 0.1 wt% to 42 wt%, or about 3 wt% to 38 wt% based on the monomer mixture.
  • the content of the comonomer is included in excess of about 45% by weight, it is not preferable because it is excessively stiff and deterioration in adhesion may occur.
  • the pressure-sensitive adhesive becomes so soft that excessive adhesive properties appear and transfer may occur, it is preferable to include a comonomer at about 0.2% by weight or more.
  • the monomer mixture 2-ethylhexyl acrylate (2-EHA) about 45% to about 70% by weight, butyl acrylate (BA) about 0 to about 40% by weight, methyl methacrylate (MMA) About 0 to about 25 weight percent, vinyl acetate (VAc) about 0 to about 40 weight percent, styrene (SM) about 0 to about 10 weight percent, acrylic acid (AA) about 0.1 weight percent to about 2.5 weight percent, and the formula It may include about 0.1% to 0.3% by weight of the monomer represented by 1.
  • the monomer mixture containing the (meth) acrylic acid ester-based monomer and one or more comonomers is made in a range such that the sum of each component content is 100% by weight.
  • the monomer mixture 2-ethylhexyl acrylate (2-EHA) about 45% to about 70% by weight, vinyl acetate (VAc) about 30% to about 40% by weight %, Acrylic acid (AA) about 0.1% to 2.5% by weight, and about 0.1% to about 0.3% by weight of the monomer represented by Formula 1, and the emulsifier, based on 100 parts by weight of the monomer mixture, Sodium polyoxyethylene lauryl ether sulfate about 0.8 parts to about 1.1 parts by weight of diphenyl oxide disulfonate about 0.1 to 0.25 parts by weight, dioctyl sodium sulfosuccinate about 0.2 parts to about 0.35 parts by weight; Or about 0.8 part by weight to about 1.1 part by weight of sodium polyoxyethylene lauryl ether sulfate and about 0.4 part by weight to about 0.6 part by weight of diphenyl oxide disulfonate.
  • 2-EHA 2-ethylhexyl acrylate
  • VAc vinyl a
  • the monomer mixture 2-ethylhexyl acrylate (2-EHA) about 45% to about 70% by weight, butyl acrylate (BA) about 25% to about 40% by weight, about 10% to about 25% by weight of methyl methacrylate (MMA), about 0.5% to about 10% by weight of styrene (SM), about 0.1% to about 2.5% by weight of acrylic acid (AA), and It comprises about 0.1% to about 0.3% by weight of the monomer represented by the formula (1), the emulsifier, with respect to 100 parts by weight of the monomer mixture, sodium polyoxyethylene lauryl ether sulfate about 0.5 parts to about 0.8 parts by weight Bu and sodium lauryl sulfate may be used in an amount of about 0.2 to about 0.4 parts by weight.
  • the monomer mixture may include other additives without particular limitation within a range not deteriorating the desired effect of the invention in addition to the above-described components.
  • the additive may include an internal crosslinking agent, a polymerization initiator, an external crosslinking agent, a buffer, a wetting agent, a neutralizing agent, a polymerization terminator, and an tackifier, and may further include one or more of them.
  • the internal crosslinking agent is allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-N-methyllocarbamate, 1,6-hexanediol diacrylate, hexanediol ethoxylate diacrylate, hexanediol Propoxylate diacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyl trimethoxysilane, and divinylbenzene. have.
  • the internal crosslinking agent may be used in an amount of about 0.2 parts by weight or less or about 0 to 0.2 parts by weight, or about 0.15 parts by weight or less, or about 0.01 parts by weight to about 0.15 parts by weight based on the monomer mixture.
  • ammonium or alkali metal persulfate (ex.APS, ammonium persulfate), hydrogen peroxide, peroxide, hydroxyl oxide, etc.
  • water-soluble polymerization initiator can be used, and emulsification polymerization reaction at low temperature In order to do so, it may be used together with one or more reducing agents, but is not limited thereto.
  • the content of the polymerization initiator based on the monomer mixture, about 1.0 part by weight or less, or about 0 to about 1.0 part by weight, or about 0.6 part by weight or less, or about 0.01 part by weight to about 0.6 part by weight, or about 0.45 part by weight It may be used in the following or about 0.1 parts by weight to about 0.45 parts by weight, or about 0.4 parts by weight or less or about 0.5 parts by weight to about 0.4 parts by weight.
  • the polymerization initiator may be divided into one or more times during the polymerization step of the monomer mixture and appropriately divided within the above-described range.
  • the polymerization initiator when the polymerization initiator is added at the initial stage of polymerization prior to the injection of the prill emulsion in which the emulsifier is added to the monomer mixture, about 0.2 parts by weight or less or about 0 to about 0.2 so as to minimize the possibility of residue problems. It is preferred to add in parts by weight, or about 0.1 parts by weight or less, or about 0 to about 0.1 parts by weight, about 0.05 parts by weight or less, or about 0 to about 0.05 parts by weight or less.
  • the polymerization initiator may be added simultaneously or in a divided manner over a period of time up to about 70% of the total polymerization time in a manner that is simultaneously introduced with the pre-emulsion.
  • the external crosslinking agent which is added later in the terminal portion of the polymerization process, and serves as an intercross linker connecting the polymer and the polymer, may be further used.
  • the external crosslinking agent diacetone acrylamide (DAAM) and adipic acid dihydride (ADH) may be used to design a crosslinking reaction from the outside.
  • the external crosslinking agent may be added later in the terminal portion of the polymerization process, and may also serve as an intercross linker connecting the polymer and the polymer.
  • the external crosslinking agent may be used in an amount of about 1.2 parts by weight or less or about 0 to about 1.2 parts by weight, or about 0.7 parts by weight or less, or about 0.01 parts by weight to about 0.7 parts by weight based on the monomer mixture.
  • the buffer examples include sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, and sodium chloride, but are not limited thereto. Further, these may be used alone or in combination of two or more.
  • the buffer may serve to adjust the pH in the polymerization reaction and impart polymerization stability.
  • the buffer may be used in an amount of about 1.0 part by weight or less, or about 0 to about 1.0 part by weight, or about 0.5 part by weight or less, or about 0.1 part by weight to about 0.5 part by weight based on the monomer mixture.
  • the wetting agent serves as an emulsifier that lowers the surface tension for coating properties, and its content can be used within a range well known in the art.
  • the wetting agent may include a dioctyl sodium sulfosuccinate compound.
  • the wetting agent may be used in an amount of about 1.0 part by weight or less, or about 0 to about 1.5 parts by weight, or about 1.2 parts by weight or less, or about 0.1 parts by weight to about 1.2 parts by weight based on the monomer mixture.
  • the neutralizing agent examples include NaOH, NH 4 OH, and KOH.
  • the neutralizing agent may be used in an amount of about 1.0 part by weight or less, or 0 to about 1.0 part by weight, or about 0.5 part by weight or less, or about 0.1 part by weight to about 0.5 part by weight based on the monomer mixture.
  • the polymerization terminator is a latex, that is, is added to suppress the side reaction of the remaining radical and residual monomer after the acrylic emulsion resin is prepared, and is an additive that removes radicals and eliminates additional reactions.
  • Such polymerization terminators are also referred to as radical inhibitors. It is also referred to simply as a ban.
  • inhibitors are hydroquinone and p-tert-phthalatechol. Others include benzonkinone, croranyl, m-dinitrobenzene, nitrobenzene P-phenylziamine sulfur, etc. These are substances that react and stabilize easily with radicals. In addition, the stabilized radicals diphenylpicrihydrazyl-P-pulolphenylamine and tri-P-nitrophenylmethyl are also used as inhibitors. Preferably, NaNO 2 may be used as the polymerization terminator.
  • the polymerization terminator may be used in an amount of about 1.0 part by weight or less or about 0 to about 1.0 part by weight, or about 0.5 part by weight or less or about 0.1 part by weight to about 0.5 part by weight based on the monomer mixture.
  • the tackifier is added as an additional emulsifier to lower the surface tension.
  • a dioctyl sodium sulfosuccinate compound may be used as a surface tension can be greatly reduced by using a small amount.
  • the tackifier is about 1.5 parts by weight or less, or about 0 to about 1.5 parts by weight, or about 1.2 parts by weight or less, or about 0 to about 1.2 parts by weight, or about 0.8 parts by weight or less, or about 0 to about, based on the monomer mixture. 0.8 parts by weight, or less than about 0.6 parts by weight, or about 0.1 parts by weight to about 0.6 parts by weight.
  • the monomer mixture serves as a chain transfer agent (CTA) during the polymerization reaction of the acrylic emulsion resin, and may further include a molecular weight modifier that specifically attaches to the ends of the molecule and serves to move radicals to other places.
  • CTA chain transfer agent
  • the residue may be generated when used as an adhesive for clothing, it is rarely used or a small amount is used to lower the molecular weight to improve initial adhesion.
  • a very short amount of 3-mercaptopropionic acid, such as n-DDM (1-dodecanethiol) which can be adjusted with only a small amount, may be used in a very small amount.
  • n-DDM (1-dodecanethiol 3-mercaptopropionic acid
  • it is preferable to hardly use it for the adhesive for clothing.
  • the order in which each component is input may be performed differently.
  • a mixture of a monomer such as a (meth) acrylic acid ester monomer and a comonomer, an emulsifier, and an internal crosslinking agent is added while stirring and dissolving an additive such as a surfactant and a buffer in water first. It may be desirable.
  • the emulsion polymerization may be performed at a temperature of about 70 °C to about 90 °C for about 3 hours to about 6 hours.
  • considering the physical properties of the pressure-sensitive adhesive may be a polymerization temperature of about 75 °C to about 85 °C.
  • the polymerization initiator may be controlled alone or by a method of mixing one or more of the polymerization initiator and the reducing agent. Components such as polymerization initiators and reducing agents used in the polymerization reaction may be applied without particular limitation to the components and contents used in the acrylic emulsion resin of the present invention described above.
  • a method of removing the water with water using a pressure-reducing device was applied by applying a stripping process, but in recent years, the polymerization initiator was added to increase the time for aging to further proceed with aging. The time was extended to be an additional reaction. If the reaction is continued at a high temperature, the change over time is greatly reduced and a more stable product can be supplied.
  • the method of manufacturing the aqueous pressure-sensitive adhesive composition for clothing optimizes and uses the monomer composition and the composition of the emulsifier together during polymerization, so that when applied as an aqueous acrylic pressure-sensitive adhesive for clothing, properties equal to or greater than those of the prior art are applied. It can be maintained and stored at high temperature for a long time, and it can exhibit stable residue characteristics when removing adhesives with effective adhesive strength even in clothing fabrics.
  • a water-based acrylic pressure-sensitive adhesive for clothing comprising a composition prepared by the method as described above.
  • the water-based acrylic adhesive according to the present invention can be specifically applied as an adhesive sheet for clothing. Therefore, the water-based acrylic pressure-sensitive adhesive can be effectively applied to the fabric base material for clothing, and then, when removing the pressure-sensitive adhesive, it is possible to reduce the residual ratio of the pressure-sensitive adhesive while satisfying properties equal to or greater than the existing ones.
  • the acrylic pressure-sensitive adhesive according to the present invention can reduce the residual ratio of the fabric for clothing to at least about 10% or less, or about 0 to 10%, and more preferably, the residual ratio of the acrylic pressure-sensitive adhesive is about 8% or less or about 0 to 8%, or about 5% or less, or about 0-5%.
  • the residual ratio can be applied to the KOTITI clothing testing laboratory in the same way as the analysis method, and after pressing the label sample on the selected clothing fabric 5 times with a roller of about 5 kg of load, insert it between the glass using a glass specimen ( Lamination of 4 to 5 samples), press the attached sample with a load of about 5 kg in a thermo-hygrostat at a temperature of about 60 ° C and a relative humidity of 95%, and then age for 3 days (5 kg on glass specimens when stored) Weight).
  • 100% polyester or 100% cotton fabric, or 52% polyester and 48% cotton blend fabric is used as the garment fabric.
  • the water-based acrylic adhesive may also have an initial adhesive force (loop tack) of about 7.5 N / inch to about 11.0 N / inch, or about 7.6 N / inch to about 10 N / inch.
  • the initial adhesion (Loop tack) can be measured by using a glass or HDPE, a stainless steel plate (Bright Stainless steel plate) as an adherend.
  • the specimen is looped and fixed to a clamp, and the specimen is attached to a glass or HDPE film at a constant speed. After about 5 seconds, when applying the measurement speed of about 300 mm / min and separating in the opposite direction, the force corresponding to the highest value is measured by the loop tack peel force.
  • the target value is about 6.0 N / inch or more for stainless steel plate, preferably about 9.0 N / inch or more, and about 2.5 N / inch or more for HDPE film, preferably about 3.0 N / inch or more Can be done with
  • the aqueous acrylic adhesive may also have a peel strength (90 ° peel) of about 3.1 to 5.5 N / inch, or about 3.8 to 5.4 N / inch.
  • the peel force (peel) is the test method FINAT TEST METHOD NO. It can measure according to 2.
  • the acrylic emulsion adhesive clothing label specimen is reciprocated one or more times at a rate of about 300 mm / min with a roller of about 2 kg, attached to a glass or HDPE, bright stainless steel plate adhesive, and about 20 minutes. After aging at room temperature, it is measured while peeling at 90 degrees (90 °) at a rate of about 300 mm / min using a TA Texture Analyzer instrument.
  • the target value may be about 2.4 N / inch or more, preferably about 3.0 N / inch or more, for a stainless steel plate.
  • the water-based acrylic pressure-sensitive adhesive also has a shear force of about 30 minutes / 0.5 inch ⁇ 1 kg to about 320 minutes / 0.5 inch ⁇ 1 kg, or about 31 min / 0.5 inch ⁇ 1 kg to about 200 minutes / 0.5 inch ⁇ 1 kg, or It may be about 32 minutes / 0.5 inch ⁇ 1 kg to 150 minutes / 0.5 inch ⁇ 1 kg.
  • the holding force can be measured by the Holding Power test (Shear test) method.
  • Shear test Holding Power test
  • the aqueous acrylic pressure-sensitive adhesive according to the present invention is characterized by maintaining basic physical properties and maintaining aging peel strength even when stored for a long time under high temperature and high humidity conditions. For example, measured after elapse of 24 hours or more under conditions of a temperature of 50 ° C. and a relative humidity of 90%, for example, after attaching a stainless steel (SUS) substrate, the aging peel strength is about 5.7 N / inch or less, and the aging residual rate is about. 20% or less.
  • SUS stainless steel
  • Emulsion polymerization was performed by mixing a monomer mixture with an emulsifier and water as follows, and an acrylic adhesive composition was prepared.
  • an internal crosslinking agent of polyethylene glycol 400 diacrylate PEGDA, Polyethylene glycol 400 Diacrylate, M280
  • sodium polyoxyethylene lauryl ether sulfate sodium polyoxyethylene lauryl ether sulfate
  • a second emulsifier a solution composed of about 2 g of diphenyl oxide disulfonate, about 3 g of dioctyl sodium sulfosuccinate, and about 230 g of water is added. And mixed with a stirrer to prepare a pre-emulsion of cloudiness.
  • an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the internal crosslinking agent was not used and the monomer and emulsifier contents were varied.
  • Emulsion polymerization was performed by mixing a monomer mixture with an emulsifier and water as follows, and an acrylic adhesive composition was prepared.
  • Dioctyl sodium sulfosuccinate as a wetting agent that acts as an emulsifier that lowers the surface tension for coating properties to 100 g of the acrylic emulsion resin whose pH control is completed as described above, about 10 g of dioctyl sodium sulfosuccinate And stirred for about 60 minutes at a temperature of about 25 ° C., followed by sequentially injecting a neutralizing agent, a polymerization terminator, and the like to prepare an acrylic emulsion pressure-sensitive adhesive composition.
  • an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 4, except that the monomer and emulsifier contents were varied.
  • the weight percent represents the content of each monomer as a percentage of the total amount of the monomer mixture, and the weight parts indicate the content value when the total amount of the monomer mixture is based on 100 parts by weight.
  • the content of the polymerization initiator represents the content to be input in the initial stage of polymerization before the pre-emulsion of the monomer mixture and the amount to be added simultaneously with or after the pre-emulsion injection (initial polymerization stage / free) Simultaneous with emulsion input and subsequent dose).
  • DAAM diacetone acrylamide
  • Table 2 the composition and content of the monomer, the internal crosslinking agent, and the emulsifying agent are differently applied, and after about 3 hours after polymerization is started, diacetone acrylamide (DAAM) is prepared as an external crosslinking agent in an aqueous solution of about 25%.
  • 100 parts by weight of the acrylic emulsion resin that is, the same as in Example 1, except that it was added while stirring at a content of about 29.2 g (DAAM actual weight of about 7.3 g), which is about 0.73 parts by weight based on 100 parts by weight of the monomer mixture.
  • An acrylic emulsion pressure-sensitive adhesive composition was prepared by the method.
  • an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the composition and content of the monomer and the emulsifier were different without using an internal crosslinking agent and an external crosslinking agent.
  • an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 2, except that the composition and content of the monomer and the emulsifier were different.
  • an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the composition and content of the monomer and the emulsifier were different.
  • the weight percent represents the content of each monomer in the total amount of the monomer mixture as a percentage, and the weight parts indicate the content value when the total amount of the monomer mixture is based on 100 parts by weight.
  • the content of the polymerization initiator represents the content of the monomer mixture added at the initial stage of polymerization prior to the pre-emulsion injection and the content of the pre-emulsion injection at the same time or thereafter.
  • Each of the pressure-sensitive adhesive compositions prepared in Examples and Comparative Examples was coated on a silicone coated release paper, and dried in an oven at about 120 ° C. for about 1 minute so that the pressure-sensitive adhesive layer had a thickness of about 20 ⁇ m. This was laminated with a polyethylene terephthalate film to make a garment label and cut to a size of 1 inch x 150 mm to prepare a garment label specimen.
  • the specimen was loop-shaped and fixed to a clamp, and the specimen was attached to a glass or high density polyethylene (HDPE) film at a constant speed. After about 5 seconds, the force corresponding to the highest value was measured by the loop tack peel force when separating in the opposite direction by applying a measurement speed of about 300 mm / min.
  • HDPE high density polyethylene
  • Test method FINAT TEST METHOD NO. the acrylic emulsion adhesive clothing label specimen is reciprocated once with a 2 kg roller at a rate of about 300 mm / min, attached to a stainless steel plate, aged at room temperature for about 20 minutes, and then TA Texture It was measured while peeling 90 degrees (90 °) at a rate of about 300 mm / min using an analyzer instrument.
  • Holding Power test (Shear test) was performed by the following method.
  • Clothing fabric select different types according to fabric, basic 4 or more
  • Examples 1 to 5 improve the retention force by increasing the degree of crosslinking, thereby improving the clothing residue and obtaining the aging peel strength after attaching the stainless steel (SUS) substrate, that is, peel strength over time with SUS. was confirmed.
  • SUS stainless steel
  • Comparative Example 1 had a problem in that the aging peel strength after attaching the stainless steel (SUS) substrate, that is, the peel strength over time and the aging residual rate was largely 100%.
  • Comparative Example 2 as the molecular weight of the acrylic emulsion resin was too high, storage stability of the pressure-sensitive adhesive composition was remarkably lowered, and a gelation phenomenon was observed, and the residual ratio could not be measured at room temperature, and the residual ratio with SUS was 20% to 25%. appear.
  • Comparative Example 3 a large amount of clothing residues were generated, and not only the residues measured at room temperature without an aging test, but also SUS over time residues according to the aging test were both 100%.
  • Comparative Example 4 had a problem in that the adhesive property was difficult to be produced because the adhesive property was not properly applied to the release paper, as the surface tension of the acrylic emulsion resin increased and the coating property was poor.
  • Comparative Example 7 it can be seen that the adhesive properties are improved, but the holding power is lowered and the residual ratio is increased, and the stability of the water is not good, so that the polymerization stability is greatly reduced.
  • Comparative Example 8 not only the adhesive properties of the excess were poor, but also the viscosity increased greatly during polymerization, which may cause a problem of gelation.

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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)
  • Polymerisation Methods In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un adhésif acrylique aqueux pour vêtements et un adhésif acrylique aqueux pour vêtements, comprenant une composition qui est produite à partir de celui-ci, l'adhésif acrylique aqueux conservant une résistance au pelage au vieillissement, même pendant un stockage à long terme à une température élevée, et améliorant remarquablement les caractéristiques résiduelles lors de l'élimination de l'adhésif d'un tissu de vêtement ou similaire.
PCT/KR2019/014619 2018-11-02 2019-10-31 Procédé de fabrication d'adhésif aqueux pour vêtements Ceased WO2020091467A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/051,058 US12024653B2 (en) 2018-11-02 2019-10-31 Method for preparing aqueous pressure-sensitive adhesive composition for clothing
CN201980026506.0A CN112004896B (zh) 2018-11-02 2019-10-31 用于衣物的水性压敏粘合剂组合物的制备方法
EP19877968.8A EP3763794A4 (fr) 2018-11-02 2019-10-31 Procédé de fabrication d'adhésif aqueux pour vêtements

Applications Claiming Priority (4)

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KR20180133859 2018-11-02
KR10-2018-0133859 2018-11-02
KR1020190135680A KR102267592B1 (ko) 2018-11-02 2019-10-29 의류용 수성 점착제 조성물의 제조 방법
KR10-2019-0135680 2019-10-29

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Cited By (1)

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US11613677B2 (en) 2017-12-15 2023-03-28 Lg Chem, Ltd. Water-based acrylic pressure-sensitive adhesive for clothing, and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11613677B2 (en) 2017-12-15 2023-03-28 Lg Chem, Ltd. Water-based acrylic pressure-sensitive adhesive for clothing, and preparation method thereof
EP3650513B1 (fr) * 2017-12-15 2024-01-31 Lg Chem, Ltd. Adhésif acrylique sensible à la pression à base d'eau pour vêtements et son procédé de préparation

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