WO2023101251A1 - Tensioactif réactif non ionique, composition adhésive aqueuse le comprenant et procédés de préparation associ֤és - Google Patents

Tensioactif réactif non ionique, composition adhésive aqueuse le comprenant et procédés de préparation associ֤és Download PDF

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WO2023101251A1
WO2023101251A1 PCT/KR2022/017626 KR2022017626W WO2023101251A1 WO 2023101251 A1 WO2023101251 A1 WO 2023101251A1 KR 2022017626 W KR2022017626 W KR 2022017626W WO 2023101251 A1 WO2023101251 A1 WO 2023101251A1
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reactive surfactant
weight
sensitive adhesive
adhesive composition
water
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PCT/KR2022/017626
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English (en)
Korean (ko)
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정유진
황가은
염도영
박종목
정서현
임보규
나한아
김동환
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • 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
    • 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
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a surfactant composition for a pressure-sensitive adhesive, a method for preparing the same, and a pressure-sensitive adhesive including the same, and relates to a water-based pressure-sensitive adhesive composition including a nonionic reactive surfactant and an anionic reactive surfactant having excellent heat resistance and peel strength.
  • pressure-sensitive adhesives are solvent-type pressure-sensitive adhesives prepared by using a volatile organic solvent as a solvent.
  • environmental regulations are gradually being strengthened, whereas many environmental problems are caused when volatile organic solvents are used. Therefore, in the field of adhesives, there is an increasing demand for adhesives containing less environmentally harmful components.
  • Water-based adhesives are used for labels, electrical/electronic tapes, construction/interior tapes, automotive tapes, other tapes, and medical applications. proportion is increasing.
  • Aqueous adhesives are prepared by emulsion polymerization using monomer mixtures, initiators, surfactants, emulsifiers, and additives (tackifier, antifoaming agent, wetting agent, leveling agent, etc.) It is a method of polymerizing a monomer insoluble in water or a monomer with low solubility in water by using a dispersion function.
  • water-based adhesives have a problem in that adhesive physical properties such as initial adhesive strength, peel strength, and holding power are significantly lower than solvent-based adhesives in terms of performance, and additives such as surfactants used during emulsion polymerization are pointed out as the main cause.
  • Korean Patent Registration No. 10-2295720 relates to an adhesive composition containing an acrylic copolymer, water, and a surfactant, and suggests various sulfate-type anionic surfactants as the surfactant.
  • the nonionic reactive surfactant of the present invention has been devised to solve the above problems, and provides a nonionic reactive surfactant formed by the reaction of polyoxyethylene alkylphenyl ether and an unsaturated carboxylic acid having 4 to 6 carbon atoms. for that purpose
  • another object of the present invention is to provide an aqueous pressure-sensitive adhesive composition
  • an aqueous pressure-sensitive adhesive composition comprising the nonionic reactive surfactant, anionic reactive surfactant, acrylate monomer, aqueous solvent, and initiator of the present invention.
  • the present invention comprises the steps of (a) reacting polyoxyethylene alkylphenyl ether by adding benzene and an unsaturated carboxylic acid having 4 to 6 carbon atoms; (b) adding a catalyst to the product of step a; (c) obtaining an oily layer after layer separation of the product of step b; Another object is to provide a method for producing a non-ionic reactive surfactant comprising; and (d) removing the solvent from the oily layer.
  • the present invention (A) mixing an aqueous solvent, an anionic reactive surfactant, a nonionic reactive surfactant formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms, and acrylic acid, ( B) mixing an acrylate monomer with the mixture of step (A) to form a pre-emulsion, (C) mixing an initiator and sodium metabisulfite with a portion of the pre-emulsion, (D) the step (C) )
  • Another object is to provide a method for producing a water-based pressure-sensitive adhesive comprising the step of dropping the remaining pre-emulsion into a mixture of, and (E) neutralizing.
  • the present invention may also have as its object to achieve other objects that can be easily derived by a person of ordinary skill in the art from these objects and the overall description of this specification in addition to the above clear objects.
  • the nonionic reactive surfactant of the present invention is characterized in that it is formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms.
  • non-ionic reactive surfactant may be a surfactant for water-based pressure-sensitive adhesive.
  • alkyl may have 8 to 16, 10 to 14, or 12 to 14 carbon atoms.
  • alkyl may be linear or branched.
  • polyoxyethylene alkylphenyl ether may have 7 to 40, 20 to 30, or 24 to 30 oxyethylene repeating units.
  • nonionic reactive surfactant may have a vinyl group at the end.
  • the alpha carbon of the unsaturated carboxylic acid may have sp 3 hybridization.
  • the unsaturated carboxylic acid is 3-butenoic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-3-butenoic acid, 3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 4-methyl- 3-pentenoic acid, 4-methyl-4-pentenoic acid, 3-methyl-3-pentenoic acid, 3-methyl-4-pentenoic acid, 3-ethyl-3-butenoic acid, 2-methyl-3-pentenoic acid, 2-methyl-4-pentenoic acid, 2,2-diethyl-3-butenoic acid, 2,3-diethyl-3-butenoic acid, or 2-ethyl-3-butenoic acid.
  • nonionic reactive surfactant may be represented by Formula 1 below.
  • n is 7 to 40, 20 to 30, or 24 to 30.
  • the aqueous pressure-sensitive adhesive composition of the present invention is characterized by including the nonionic reactive surfactant, anionic reactive surfactant, acrylate monomer, aqueous solvent, and initiator of the present invention.
  • It may include 30 to 200 parts by weight of the aqueous solvent, 40 to 100 parts by weight, or 50 to 80 parts by weight.
  • anionic reactive surfactant may be a polyoxyethylene-based anionic surfactant having a vinyl group at the terminal.
  • the anionic reactive surfactant may have a sulfonic acid or sulfonate functional group.
  • anionic reactive surfactant may be represented by Formula 2 below.
  • R is alkyl
  • m is 5 to 45, 10 to 40, or 24 to 30, and
  • X is SO 3 NH 4 or SO 3 Na.
  • the acrylate monomer may be selected from the group consisting of acrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and mixtures thereof.
  • the acrylate monomer is acrylic acid 1 part by weight, 2-ethylhexyl acrylate 20 to 45 parts by weight, 22 to 40 parts by weight, or 24 to 38 parts by weight, n-butyl acrylate 25 to 70 parts by weight, 30 to 30 parts by weight 65 parts by weight, or 36 to 62 parts by weight, methyl methacrylate may include 8 to 38 parts by weight, 10 to 30 parts by weight, or 12 to 28 parts by weight.
  • the initiator may be ammonium persulfate, sodium metabisulfite, or a mixture thereof.
  • the aqueous pressure-sensitive adhesive composition may include one or more additives selected from the group consisting of a tackifier, an emulsifier, an antifoaming agent, a stabilizer, a pH adjuster, a leveling agent, a wetting agent, a biocide, and mixtures thereof. .
  • water-based adhesive may be used for labels, electric/electronic tapes, construction/interior tapes, automotive tapes, or medical adhesives.
  • step a (b) adding a catalyst to the product of step a;
  • nonionic reactive surfactant may be represented by the following Chemical Formula 1
  • polyoxyethylene alkylphenyl ether may be represented by the following Chemical Formula 3.
  • n is 7 to 40, 20 to 30, or 24 to 30.
  • the catalyst may be para-toluenesulfonic acid.
  • step (a) may be reacted for 120 to 240 minutes at 40 to 80 °C.
  • step (b) may be reacted for 18 to 36 hours at 60 to 100 °C.
  • step (B) forming a pre-emulsion by mixing an acrylate monomer with the mixture of step (A);
  • dodecylmercaptan may be added.
  • an initiator may be additionally added after dropping.
  • the acrylate monomer may be selected from the group consisting of acrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and mixtures thereof.
  • the initiator may be ammonium persulfate.
  • the neutralizing step may be neutralizing with weak acidity by introducing a mixture of an aqueous solvent and ammonia water.
  • a step of filtering may be included.
  • the surfactant according to the present invention is a nonionic surfactant, and when used in an adhesive, it has an appropriate viscosity and average particle size, and thus can exhibit excellent coating properties and adhesive properties.
  • layer separation does not occur during the preparation of the pre-emulsion, and air bubbles or agglomerates do not occur during the preparation of the pressure-sensitive adhesive emulsion, so that a pressure-sensitive adhesive composition of excellent quality can be manufactured.
  • FIG. 1 shows H-NMR results of a surfactant prepared by a manufacturing method according to an embodiment of the present invention.
  • Figure 2 shows the 13 C-NMR results of the surfactant prepared by the manufacturing method according to an embodiment of the present invention.
  • FIG. 3 shows H-NMR results of a surfactant prepared by a manufacturing method according to an embodiment of the present invention.
  • Figure 4 shows the 13 C-NMR results of the surfactant prepared by the manufacturing method according to an embodiment of the present invention.
  • FIG. 5 shows H-NMR results of a surfactant prepared by a manufacturing method according to an embodiment of the present invention.
  • FIG. 6 shows 13 C-NMR results of a surfactant prepared by a manufacturing method according to an embodiment of the present invention.
  • FIG. 7 schematically shows a method for manufacturing a pressure-sensitive adhesive composition according to an embodiment of the present invention.
  • the present invention has the advantage of being environmentally friendly, but in order to overcome the limitations of conventional water-based pressure-sensitive adhesives having low water resistance and poor adhesive properties, as a result of intensive research to prepare a surfactant for use in water-based pressure-sensitive adhesives, the present invention was completed.
  • the nonionic reactive surfactant of the present invention is characterized by being formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms.
  • the hydrophile-lipophile balance (HLB) of the nonionic reactive surfactant of the present invention shows a value of 11 to 16, considering that it has excellent efficacy as an emulsifier for aqueous adhesives when it has an HLB value within the above range, the surfactant of the present invention It can be expected that the composition will exhibit excellent physical properties when included in the pressure-sensitive adhesive.
  • a nonionic reactive surfactant may be formed by a reaction as shown in Scheme 1 below.
  • the alkyl of the polyoxyethylene alkylphenyl ether is a carbon chain having 8 to 16, 10 to 14, or 12 to 14 carbon atoms as a carbon backbone and no unsaturated bonds.
  • the alkyl of the polyoxyethylene alkylphenyl ether may be straight chain or branched chain.
  • polyoxyethylene alkylphenyl ether may have 7 to 40, 20 to 30, or 24 to 30 oxyethylene (CH 2 CH 2 O; EO) repeating units.
  • EO oxyethylene
  • the nonionic reactive surfactant of the present invention may have a vinyl group at the end.
  • the vinyl group may be derived from an unsaturated carboxylic acid, which is a reactant forming a non-ionic reactive surfactant.
  • the unsaturated carboxylic acid may be a carboxylic acid compound having 4 to 6 carbon atoms and one or more unsaturated bonds, preferably one.
  • the unsaturated bond may be present at the terminal.
  • the unsaturated carboxylic acid may be other than acrylic acid or a derivative thereof.
  • the unsaturated carboxylic acid is 3-butenoic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-3-butenoic acid, 3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 4-methyl- 3-pentenoic acid, 4-methyl-4-pentenoic acid, 3-methyl-3-pentenoic acid, 3-methyl-4-pentenoic acid, 3-ethyl-3-butenoic acid, 2-methyl-3-pentenoic acid, 2-methyl-4-pentenoic acid, 2,2-diethyl-3-butenoic acid, 2,3-diethyl-3-butenoic acid, or 2-ethyl-3-butenoic acid.
  • the nonionic reactive surfactant may be represented by Formula 1 below.
  • n may be 7 to 40, 10 to 30, 20 to 30, or 24 to 30.
  • the aqueous pressure-sensitive adhesive composition of the present invention is characterized by including the nonionic reactive surfactant, anionic reactive surfactant, acrylate monomer, aqueous solvent, and initiator of the present invention.
  • the water-based pressure-sensitive adhesive composition includes 0.01 to 5 parts by weight, 0.05 to 1 part by weight, 0.1 to 0.5 parts by weight of the nonionic reactive surfactant and 0.01 to 5 parts by weight of the anionic reactive surfactant, based on 100 parts by weight of the acrylate monomer. part, 0.05 to 1 part by weight, or 0.1 to 0.5 part by weight.
  • the content of the nonionic reactive surfactant is less than the above range, heat resistance may be deteriorated, whereas when the content exceeds the above range, emulsification failure may occur.
  • the content of the anionic reactive surfactant is less than the above range, emulsion stability may be deteriorated, whereas when the content exceeds the above range, water resistance may be deteriorated.
  • the water-based pressure-sensitive adhesive composition based on 100 parts by weight of the acrylate monomer, 0.01 to 5 parts by weight, 0.05 to 1 part by weight, 0.1 to 0.5 parts by weight of the initiator and 30 to 200 parts by weight, 40 to 100 parts by weight of the aqueous solvent , or 50 to 80 parts by weight.
  • the water-based pressure-sensitive adhesive composition according to the present invention has significantly improved adhesiveness through a combination of a nonionic reactive surfactant and an anionic reactive surfactant, and the weight ratio of the nonionic reactive surfactant to the anionic reactive surfactant is 3:7 to 7:3, It is preferably 4:6 to 6:4, or 4.5:5.5 to 5.5:4.5.
  • the anionic reactive surfactant which is one component of the aqueous pressure-sensitive adhesive composition of the present invention, may be a polyoxyethylene-based anionic surfactant having a vinyl group at the end.
  • the anionic reactive surfactant may have a sulfonic acid or sulfonate functional group.
  • the anionic reactive surfactant may be represented by Formula 2 below.
  • R is alkyl, m is 5 to 45, 10 to 40, or 24 to 30, and X is SO 3 NH 4 or SO 3 Na.
  • R may have 1 to 50, 5 to 45, or 10 to 40 carbon atoms.
  • the acrylate monomer is selected from the group consisting of acrylic acid (AA), n-butyl acrylate (BAM), 2-ethylhexyl acrylate (2-EHAM), methyl methacrylate (MMA), and mixtures thereof It can be.
  • the acrylate monomer is 1 part by weight of acrylic acid, 20 to 45 parts by weight of 2-ethylhexyl acrylate, 22 to 40 parts by weight, or 24 to 38 parts by weight, n-butyl acrylate 25 to 70 parts by weight , 30 to 65 parts by weight, or 36 to 62 parts by weight, methyl methacrylate may include 8 to 38 parts by weight, 10 to 30 parts by weight, or 12 to 28 parts by weight.
  • the acrylate monomer may include 1 part by weight of acrylic acid, 20 to 30 parts by weight of 2-ethylhexyl acrylate, 55 to 65 parts by weight of n-butyl acrylate, and 9 to 19 parts by weight of methyl methacrylate there is. It was confirmed that the adhesive peel strength can be improved by lowering the content of methyl methacrylate, a hard monomer, and the glass transition temperature of the pressure-sensitive adhesive increases and the adhesive strength increases as the content of n-butyl acrylate increases.
  • the acrylate monomer is also an acrylic acid alkyl ester or methacrylic acid having 3 or less carbon atoms in an alkyl group such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, and isopropyl methacrylate.
  • (meth)acrylic acid cyclic alkyl esters such as cyclohexyl (meth)acrylate; Aromatic (meth)acrylic acid esters, such as phenoxymethyl (meth)acrylate and benzyl (meth)acrylate; Aliphatic such as hydroxyalkyl acrylate, hydroxyalkyl methacrylate, polyoxyethylene (meth) acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, glycidyl acrylate, glycidyl methacrylate ( meth)acrylic acid ester; (meth)acrylic acid amides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, and N-methoxybutyl acrylamide; Vinyl methyl ketone, vinyl ethyl ketone, vinyl-n-propyl ketone, vinyl-i-propyl ketone, vinyl-n-butyl acrylamide
  • the initiator may be ammonium persulfate, sodium metabisulfite, or a mixture thereof, but is not limited thereto.
  • the initiator for the adhesive may be used without limitation, such as a thermal decomposition type initiator or a redox type initiator, and potassium persulfate or sodium hydrogen sulfite may be used.
  • the aqueous pressure-sensitive adhesive composition may further include one or more additives selected from the group consisting of a tackifier, an emulsifier, an antifoaming agent, a stabilizer, a pH adjusting agent, a leveling agent, a wetting agent, and a biocide.
  • additives selected from the group consisting of a tackifier, an emulsifier, an antifoaming agent, a stabilizer, a pH adjusting agent, a leveling agent, a wetting agent, and a biocide.
  • other additives or components may be further included as appropriate depending on the use of the pressure-sensitive adhesive.
  • the additive may be included in an amount of 0.001 to 30% by weight based on the total composition.
  • the water-based adhesive composition of the present invention is an adhesive composition having excellent peel strength (adhesive strength) and heat resistance retention, and the peel strength is measured using a 1 kg grip, and the distance (mm) pushed for 1 h with a 1 kg weight at 80 ° C.
  • the peel strength may be 1.4 to 2.5, 1.6 to 2.4, or 1.8 to 2.2, and the heat resistance retention may be 1 mm or less, 0.7 mm or less, or 0.4 mm or less.
  • the water-based pressure-sensitive adhesive composition of the present invention may have an average particle size of 300 to 620 nm, 400 to 600 nm, or 440 to 580 nm, and a viscosity of 150 to 400 cP, 190 to 350 cP, 200 to 330 cP can be
  • the particle size of the pressure-sensitive adhesive is influenced by the type and concentration of the surfactant, and shows monomolecularity. If the particle size is less than the above range, particle stability may be deteriorated, whereas if the particle size exceeds the above range, coating properties and adhesive properties may be deteriorated.
  • water-based adhesive may be used for labels, electric/electronic tapes, construction/interior tapes, automotive tapes, or medical adhesives.
  • the method for producing a nonionic reactive surfactant of the present invention (a) reacting by adding benzene and an unsaturated carboxylic acid having 4 to 6 carbon atoms to polyoxyethylene alkylphenyl ether; (b) adding a catalyst to the product of step a; (c) obtaining an oily layer after layer separation of the product of step b; and (d) removing the solvent from the oil phase.
  • the step (a) may be a reaction for 2 to 4 hours at 50 to 70 °C.
  • the step (b) may be to react at 70 to 90 °C for 18 to 30 hours.
  • the catalyst of step (b) may be p-TsOH (para-toluenesulfonic acid).
  • the step (c) may be fractionation by dissolving in dichloromethane (DCM) after removing the solvent and mixing with distilled water (DW) (0.1 to 1 M Na 2 CO 3 ).
  • DCM dichloromethane
  • DW distilled water
  • DW distilled water
  • DW distilled water
  • aqueous layer is washed with DCM, and the DCM layer is obtained.
  • Sodium sulfate (Na 2 SO 4 ) is added to remove residual water, and sodium sulfate can be removed by filtration under reduced pressure.
  • the solvent may be removed through a rotary evaporator at 40 to 60 °C.
  • nonionic reactive surfactant may be represented by Formula 1 below
  • polyoxyethylene alkylphenyl ether may be represented by Formula 3 below.
  • n may be 7 to 40, 10 to 30, 20 to 30, or 24 to 30.
  • a yield of 90% or more can be achieved, and the residues of polyoxyethylene alkylphenyl ether and unsaturated carboxylic acid having 4 to 6 carbon atoms, which are catalysts and reactants, are minimized. can do.
  • the manufacturing method of the water-based pressure-sensitive adhesive of the present invention (A) an aqueous solvent, an anionic reactive surfactant, a nonionic reactive surfactant formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms, and Mixing acrylic acid, (B) mixing an acrylate monomer with the mixture of step (A) to form a pre-emulsion, (C) mixing an initiator and sodium metabisulfite with a portion of the pre-emulsion, (D) dropping the remaining pre-emulsion into the mixture of step (C), and (E) neutralizing.
  • A an aqueous solvent, an anionic reactive surfactant, a nonionic reactive surfactant formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms, and Mixing acrylic acid
  • B mixing an acrylate monomer with the mixture of step (A) to form a pre-e
  • step (A) is a step of mixing an aqueous solvent such as water, an anionic reactive surfactant, a nonionic reactive surfactant formed by the reaction of polyoxyethylene alkylphenyl ether with an unsaturated carboxylic acid having 4 to 6 carbon atoms, and acrylic acid.
  • step (A) includes 10 to 40 parts by weight, 20 to 34 parts by weight, or 22 to 30 parts by weight of an aqueous solvent, 0.01 to 5 parts by weight of the nonionic reactive surfactant, 0.05 parts by weight, based on 1 part by weight of acrylic acid. to 1 part by weight, 0.1 to 0.5 parts by weight, and 0.01 to 5 parts by weight, 0.05 to 1 part by weight, or 0.1 to 0.5 parts by weight of the anionic reactive surfactant may be mixed and stirred.
  • step (B) is a step of forming a pre-emulsion by mixing and stirring the acrylate monomer in the mixture of step (A). Through this, a pre-emulsion may be formed. When a milky emulsion is formed, it can be stirred for 20 to 40 minutes.
  • dodecylmercaptan may be added in an amount of 0.01 to 0.1 parts by weight, 0.02 to 0.08 parts by weight, or 0.03 to 0.07 parts by weight based on 100 parts by weight of the acrylate monomer.
  • Acrylate monomer is 0.01 to 5 parts by weight, 0.05 to 1 part by weight, 0.1 to 0.5 parts by weight of the nonionic reactive surfactant and 0.01 to 5 parts by weight, 0.05 to 0.05 parts by weight of the anionic reactive surfactant, based on 100 parts by weight of the acrylate monomer. It is added to include 1 part by weight and 0.1 to 0.5 parts by weight.
  • the acrylate monomer may be selected from the group consisting of acrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and mixtures thereof.
  • step (C) is a step of mixing an initiator and sodium metabisulfite with a portion of the pre-emulsion.
  • the initiator may be ammonium persulfate (APS). This may be for a preliminary reaction.
  • step (C) includes (C-1) introducing a mixture of an aqueous solvent and an initiator into a portion of the pre-emulsion and stirring it, and (C-2) the product of step (C-1), the aqueous solvent and an initiator, and sodium metabisulfite (SMBS) sequentially added to a reaction vessel heated to 70 to 90 ° C., followed by stirring.
  • C-1 introducing a mixture of an aqueous solvent and an initiator into a portion of the pre-emulsion and stirring it
  • step (C-2) the product of step (C-1), the aqueous solvent and an initiator, and sodium metabisulfite (SMBS) sequentially added to a reaction vessel heated to 70 to 90 ° C., followed by stirring.
  • SMBS sodium metabisulfite
  • step (D) is a step of adding the remaining pre-emulsion dropwise to the mixture of step (C).
  • the dropping may be carried out for 1 to 3 hours or 1.5 to 2.5 hours, and after dropping, an initiator or a mixture of an initiator and an aqueous solvent may be additionally added. Thereafter, the temperature may be maintained at 32 to 35 °C.
  • step (E) is a step of neutralization, and a basic solution such as a mixture of an aqueous solvent and ammonia water may be introduced into the product of step (D) to neutralize to a weak acid (pH 5 to 6). After neutralization, it can be filtered to obtain an aqueous pressure-sensitive adhesive composition.
  • a basic solution such as a mixture of an aqueous solvent and ammonia water
  • FIGS. 2, 4, and 6 show the results of 13 C-NMR analysis of the surfactants prepared in Preparation Examples 1 to 3, respectively, confirming that the peaks of the remaining 3-butenoic acid and catalyst p -TsOH disappear. did Through this, it can be seen that the desired surfactant was synthesized.
  • 2-ethylhexyl acrylate (2-EHAM) 37.50 phr, n-butyl acrylate (BAM) 37.50 phr, methyl methacrylate (MMA) 24.00 phr, dodecylmer
  • BAM n-butyl acrylate
  • MMA methyl methacrylate
  • dodecylmer After adding 0.044 phr of dodecyl mercaptan to the beaker, the mixture was stirred. A milky pre-emulsion was formed and stirred for 30 minutes. After mixing 2.78 phr of D.W and 0.28 phr of ammonium persulfate (APS) in a beaker, it was added to the pre-emulsion and stirred for 5 minutes.
  • APS ammonium persulfate
  • 2-ethylhexyl acrylate (2-EHAM) 25.50 phr, n-butyl acrylate (BAM) 59.50 phr, methyl methacrylate (MMA) 14.00 phr, dodecylmer
  • BAM n-butyl acrylate
  • MMA methyl methacrylate
  • dodecylmer After adding 0.044 phr of dodecyl mercaptan to the beaker, the mixture was stirred. A milky pre-emulsion was formed and stirred for 30 minutes. After mixing 2.78 phr of D.W and 0.28 phr of ammonium persulfate (APS) in a beaker, it was added to the pre-emulsion and stirred for 5 minutes.
  • APS ammonium persulfate
  • Comparative Example 1 Comparative preparation of water-based pressure sensitive adhesive (1)
  • Example 2 It was prepared in the same manner as in Example 1, but a nonionic reactive surfactant (ER-10, ADEKA Co.) was used instead of the anionic reactive surfactant (SR-3025, ADEKA Co.) and the nonionic reactive surfactant prepared in Preparation Example 1 used
  • ER-10 ADEKA Co.
  • anionic reactive surfactant SR-3025, ADEKA Co.
  • Comparative Example 3 Comparative preparation of water-based pressure sensitive adhesive (3)
  • Comparative Example 4 Comparative preparation of water-based pressure sensitive adhesive (4)
  • Test Example 2 Analysis of physical properties of water-based pressure-sensitive adhesive
  • NV and conversion rates defined as follows were calculated after drying the remaining distilled water and monomers in an oven at 120 ° C.
  • peel strength was measured using a 1 kg grip, and heat resistance retention was measured through a distance (mm) pushed for 1 h with a 1 kg weight attached at 80 ° C.
  • pH was measured using a pH meter, and particle size was measured using a zetasizer.
  • Example 1 Example 2 Example 3
  • Example 4 Example 5
  • Example 6 solid content 59.92 59.9 58.11 59.31 59.3 59.92 peel strength (kg f /inch) 1.851 1.837 1.856 1.817 1.774 2.041 heat resistance (mm) 0.2 0.4 0.7 0.2 0.2 x pH 5.73 5.64 5.90 5.7 5.71 5.69 viscosity (cP, Torque) 247.33, 6.12 303.03, 7.66 332.12, 7.85 238.59, 6.02 203.09, 5.30 217.23, 5.63 particle size (nm) 486.4 ⁇ 28.91 491.3 ⁇ 17.50 447.3 ⁇ 20.96 474.3 ⁇ 29.49 496.8 ⁇ 19.83 564.0 ⁇ 42.92 NV(%) 59.92 59.31 59.9 59.3 58.11 59.92 HLB 11.43 11.43 14.54 14.54 16 16 Conversion rate (%) 97.81 96.81 97.77 96.792
  • Comparative Example 1 60.81 99.81 2.974 15 minutes later test piece separation 84.24 Comparative Example 2 A small amount of layer separation occurs during the pre-emulsion process, An adhesive emulsion was prepared, but was waxed due to poor emulsion stability. Comparative Example 3 Layer separation occurs during the pre-emulsion process Comparative Example 4 60.1 97.52 1.38 1.0 181.8 625
  • the KS M 6638 standard which is a general test method for adhesives specified in the Korean Industrial Standards, was carried out. After weighing 0.5 g of the sample on an aluminum plate to four decimal places, drying in an oven at 150 ° C for 30 minutes and drying again Calculated as a percentage (%) by dividing the dried weight, which is the value minus the weight of each aluminum dish by measuring the weight of the ordered aluminum dish, by the weight before drying peel strength kg/25mm Prepare a 50mm wide and 150mm long painted steel plate or SUS-304 cleaned with ethanol or isopropyl alcohol as an adherend, attach it to the adherend with a width of 25mm, and press it with a roller with a specified load (2kg).
  • Adhesion was measured at room temperature with a peel angle of 180° and a peel speed of 300 mm/min. Heat resistance cohesion (1kg ⁇ 1hr) °C - After attaching the test piece to ASTM D-3654 stainless steel (SUS304) with an adhesive area of 25mm ⁇ 25mm according to the standard, leave it for 60 minutes at a temperature of 23 ⁇ 2°C and a relative humidity of 50 ⁇ 5% RH.
  • ASTM D-3654 stainless steel SUS304

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition tensioactive destinée à un adhésif, une composition adhésive la comprenant et des procédés de préparation associés. Le tensioactif préparé selon la présente invention est incorporé dans un adhésif de façon à présenter tant une excellente propriété d'adhérence qu'une excellente stabilité en émulsion, de sorte qu'il peut être largement appliqué dans la préparation de l'adhésif.
PCT/KR2022/017626 2021-11-30 2022-11-10 Tensioactif réactif non ionique, composition adhésive aqueuse le comprenant et procédés de préparation associ֤és WO2023101251A1 (fr)

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