WO2020245690A1 - Water-based acrylate adhesive composition - Google Patents

Water-based acrylate adhesive composition Download PDF

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Publication number
WO2020245690A1
WO2020245690A1 PCT/IB2020/054845 IB2020054845W WO2020245690A1 WO 2020245690 A1 WO2020245690 A1 WO 2020245690A1 IB 2020054845 W IB2020054845 W IB 2020054845W WO 2020245690 A1 WO2020245690 A1 WO 2020245690A1
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WIPO (PCT)
Prior art keywords
water
polyacrylate
adhesive composition
emulsion
acrylate adhesive
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Application number
PCT/IB2020/054845
Other languages
French (fr)
Inventor
Shupeng WU
Lili QIE
Xiaohai SHENG
Weina WANG
Jun Nie
Xuemei Pan
Heng Liu
Original Assignee
3M Innovative Properties Company
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Publication of WO2020245690A1 publication Critical patent/WO2020245690A1/en

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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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • 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

Definitions

  • the present invention relates to the field of instant adhesives, and in particular to a water-based acrylate adhesive composition.
  • Instant adhesives are ones having adequate wet adhesion. A strong bond is quickly developed before the adhesive composition is completely dried.
  • Common types of instant adhesives include solvent-based instant adhesives and water-based instant adhesives. Solvent-based instant adhesives contain a great amount of highly volatile organic solvents, and are gradually exiting the market due to the increasingly stringent environmental regulations. Water-based instant adhesives has thus increased in market share because they are environmentally friendly.
  • chloroprene rubber adhesives At present, the most common water-based instant adhesive product is chloroprene rubber adhesives. Chloroprene rubber has fast-bonding performance because of its low glass transition temperature (about -45 °C) and it has room -temperature crystallization performance (about 35°C). However, because of the high crystallization temperature, the fast-bonding performance of Chloroprene rubber will decrease significantly when the ambient temperature is slightly lower (e.g. ⁇ 10°C). In addition, because chloroprene latex contains chlorine, it is not an environmentally friendly material. The environmental friendliness of Chloroprene rubber thus decreases to a certain extent.
  • Another type of developing water-based instant adhesive product is two-component adhesives, which contains an emulsion and a demulsifier (such as an inorganic salt solution).
  • a demulsifier such as an inorganic salt solution.
  • the emulsion is mixed with the demulsifier to demulsify the emulsion so as to achieve fast bonding performance.
  • Two-component adhesives have a relatively complex application procedures and are harder to control.
  • the present invention provides a water-based acrylate adhesive composition, comprising:
  • polyacrylate the polyacrylate being formed by copolymerization of raw materials containing at least two polymerizable monomers, the polyacrylate having a glass transition temperature within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 and
  • the pH value of the water-based acrylate adhesive composition is below 6.
  • a weight ratio of the cosolvent to the polyacrylate is within a range of 0.1 : 100 and 15: 100.
  • the weight ratio of the cosolvent to the polyacrylate is within a range of 5 : 100 and 10: 100.
  • the amount of the polyacrylate is 40 to 80 parts by weight
  • the amount of the emulsifier is 0.5 to 2 parts by weight
  • the amount of the water is 20 to 60 parts by weight.
  • polymerizable monomers for the polyacrylate comprise methacrylic acid, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, or a combination thereof.
  • polymerizable monomers for the polyacrylate comprise styrene, ethylene acetate, or a combination thereof.
  • the cosolvent is selected from the group consisting of cyclohexane, n-heptane, ethyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate and a combination thereof.
  • the glass transition temperature of the polyacrylate is above -30°C, preferably above -20°C.
  • the glass transition temperature of the polyacrylate is below 10°C.
  • the pH value of the water-based acrylate adhesive composition is below 5, preferably below 4.5.
  • the present invention provides a water-based acrylate adhesive composition that has excellent room -temperature fast-bonding performance.
  • the water-based acrylate adhesive composition provided by the present invention comprises: polyacrylate, the polyacrylate having a glass transition temperature within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 and 120,000;
  • the pH value of the water-based acrylate adhesive composition is below 6.
  • the adhesive composition provided by the present invention is based on polyacrylate rather than chloroprene rubber.
  • Polyacrylate is more environmentally friendly than chloroprene rubber.
  • the adhesive composition provided by the present invention is water-based, which does not contain a high amount of volatile solvents, thereby improving the environmental friendliness of the adhesive composition as compared with that of solvent-based fast-bonding adhesive compositions.
  • polyacrylate refers to a polymer which is mainly polymerized by (meth)acrylic acid and (meth)acrylate monomers.
  • the monomers may be acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, etc. More preferably, the monomers are methacrylic acid, acrylic acid, 2-ethylhexyl acrylate, and a combination thereof.
  • (meth)acrylic acid and (meth)acrylate monomers may also be added.
  • styrene or vinyl acetate monomers may be added. These monomers can adjust the glass transition temperature and hydrophilicity of the obtained polymers.
  • Acrylamide monomers such as methacrylamide and acryloyl morpholine may also be used.
  • the composition comprises an emulsifier.
  • Emulsifiers that can be used are non- cationic emulsifiers (i.e., anionic emulsifiers and non-ionic emulsifiers or a combination thereof), such as DS-10 (alkylbenzene sulfonate, purchased from Rhodia), SR- 10 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), SR-20 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), ER-10 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), ER-20 (Reactive nonylphenol free type anionic emulsifier, purchased from ADEKA), FES- 32 (Aliphatic alcohol ether sulfate, purchased from BASF), OP- 10 (Polyoxyethylene octylsifiers and a combination thereof), such as DS-10 (alkylbenzene sulfon
  • the adhesive composition will lost its fast bonding property when employing a cationic emulsifier.
  • the inventor of the invention discovered that when a proper amount of cosolvent was added to the composition, the emulsion composition has excellent fast-bonding performance.
  • the cosolvent in the present invention is a solvent with good compatibility with polyacrylate; that is, the solubility of the polymer and the solubility of the solvent are similar. That the solubility of the polymer and the solubility of the solvent being similar refers to that the difference between the solubility parameter of the solvent and that of the polymers is not greater than 1.5.
  • the solubility parameter of the obtained emulsion polymer is 9.30, so the solubility parameter of the selected cosolvent should be about 9.30, such as cyclohexane (8.59), isobutyl acetate (9.10), and hexyl acetate (9.15).
  • the added cosolvent may be well dispersed in polymer emulsion particles and serves as a plasticizer, so that the adhesive composition has excellent fast-bonding performance.
  • Cosolvents that can be used include cyclohexane, n-heptane, ethyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate, etc.
  • the amount of the used cosolvent is preferably in a range of 0.1- 15%, i.e., the weight ratio of the cosolvent to the polyacrylate is 0.1: 100-15: 100. More preferably, the weight ratio is within a range of 5% and 10%.
  • the glass transition temperature Tg of the polyacrylate is specifically selected to be within a range of -40°C and 15°C. In a non-theoretical sense, it is considered that when the glass transition temperature is too high, the fast-bonding performance is poor; and when the glass transition temperature is too low, the final strength is insufficient. Further, the glass transition temperature of the polyacrylate is preferably above -30°C, more preferably above -20°C. The glass transition temperature of the polyacrylate is preferably below 10°C. When the glass transition temperature is within the preferred range, the composition exhibits better fast-bonding performance at low temperature.
  • the number-average molecular weight of the polyacrylate is selected to be within a range of 30,000 and 120,000. In a non-theoretical sense, it is considered that, when the number- average molecular weight is too high, the fast-bonding performance is poor; and when the number- average molecular weight is too low, the final strength is insufficient.
  • the pH value of the emulsion As discovered by the inventor, when the pH value is too high, specifically for example higher than 6, the emulsion composition loses fast-bonding performance.
  • the pH value of the emulsion may be tested by pH meter. When the pH value of the emulsion is below 5, more preferably below 4.5, the fast-bonding performance of the emulsion composition is further improved.
  • the weight proportions of the polyacrylate, water and emulsifier may be selected appropriately.
  • the amount of the polyacrylate is 40 to 80 parts by weight
  • the amount of the emulsifier is 0.5 to 2 parts by weight
  • the amount of the water is 20 to 60 parts by weight.
  • the emulsion obtained accordingly has suitable fluidity and viscosity, and thus ensuring the fast-bonding performance.
  • 2-EHA denotes 2-ethylhexyl acrylate
  • MAA denotes methacrylic acid
  • AA denotes acrylic acid
  • VAc vinyl acetate
  • ST denotes styrene
  • IOTG denotes isooctyl thioglycolate
  • KPS denotes potassium persulfate
  • TBHP denotes tetrabutyl diphosphate.
  • the commodities mentioned in the examples and comparative examples include SIPONATE DS- 10, which is an emulsifier purchased from RHODIA; ER-20, which is an emulsifier purchased from ADEKA CHEMICAL; and T1651, which is a reducing agent purchased from BRIJGGEMANN CHEMICAL.
  • the glass transition temperature of the poly acrylate obtained through polymerization is measured by adopting a DSC thermal analysis method.
  • the pH value of the obtained emulsion is measured by adopting a pH meter.
  • a piece of 10 cm c 10 cm c 5 cm cuboid thick PU foam sheet (polyurethane, with density of 19 kg/m 3 ) and a piece of 10 cm c 10 cm c 1.5 cm cuboid thin PU foam sheet (with density of 19 kg/m 3 ) are used for performing a 90-degree bonding test to evaluate the fast-bonding performance.
  • Five grams of the adhesive composition to be tested are sprayed evenly on two adjacent surfaces of the thick PU foam sheet (10 cm c 1.5 cm surface and 10 cm c 10 cm surface).
  • the thin PU foam sheet is immediately bent for 90 degrees and then attached to the two surfaces of the thick PU foam sheet just sprayed with adhesive, and the thin PU foam sheet is then pressed with just the right force for fitting.
  • the hand After a period of time, the hand lets go of the PU foam sheet. If the PU foam sheets seperate, the hand continue to press on the PU foam sheet until the thin PU foam sheet does not seperate with the thick PU foam sheet, and the time needed to complete the bonding is recorded. After that, the bonded foam is let stand, and the duration to the time at which the thin PU foam sheet is warped from the thick PU foam sheet is recorded. If no warping occurs within 24h, it is evaluated as "non-debonded".
  • the temperature was set to 60°C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • NH3 ⁇ 2O was added to the emulsion obtained in example 1 to regulate the pH value to 3.52.
  • the glass transition temperature, the number-average molecular weight and the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • NH3 ⁇ 2O was added to the emulsion obtained in example 1 to regulate the pH value to 5.02.
  • the glass transition temperature, the number-average molecular weight and the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60°C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the pH value of the obtained emulsion was 3.42.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, cyclohexane (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, hexyl acetate (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, isobutyl acetate (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (68.7 g), MA (16.44 g), AA (4.12 g), ST (41.22 g), VAc (6.85 g) and IOTG (0.27 g) was added, nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymer
  • the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (79.46 g), MA (16.44 g), AA (6.85 g), ST (27.4 g), VAc (6.85 g) and IOTG (0.14 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymer
  • the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (79.46 g), MA (16.44 g), AA (6.85 g), ST (27.4 g), VAc (6.85 g) and IOTG (0.54 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na 2 S 2 0 > (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C
  • the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
  • the glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
  • An anionic emulsifier SIPONATETM DS-10 (1.37 g), ER-20 (0.27 g) and NaaHPCE (0.27 g) were added to deionized water (160.67 g); stirring was performed in a five-neck botle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (93.16 g), MA (16.44 g), AA (6.85 g), ST (13.70 g), VAc (6.85 g) and IOTG (0.27 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na 2 S 2 0 > (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization
  • the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
  • Table 1 shows that the various parameters of the water-based emulsion compositions in Examples 1-10 meet the requirements of the present invention.
  • the bonding can be finished within 5s; debonding does not occur within 24h. It can be seen that the composition can form bonds fast.
  • the emulsion in comparative examples 1-3 do not contain any cosolvent, the emulsion fails to create a bond, or debonding occurs very quickly after bonding.
  • the pH value of the emulsion in comparative example 4 is higher than pH 6; the number-average molecular weight of the polyacrylate in comparative example 5 is greater than 120,000; the number-average molecular weight of the polyacrylate in comparative example 6 is less than 30,000; the glass transition temperature of the polyacrylate in comparative example 7 is above 15°C; and the glass transition temperature of the polyacrylate in comparative example 8 is below -40°C.
  • the emulsions in these comparative examples have poor fast bonding performance.

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Abstract

The present invention provides a water-based acrylate adhesive composition, which comprises: polyacrylate, the polyacrylate having a glass transition temperature within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 and 120,000; a cosolvent; an emulsifier; and water, wherein the water-based acrylate adhesive composition has a pH value of less than 6. The water-based acrylate adhesive composition provided by the present invention is highly environment-friendly and has excellent fast-bonding performance.

Description

WATER-BASED ACRYLATE ADHESIVE COMPOSITION
TECHNICAL FIELD
The present invention relates to the field of instant adhesives, and in particular to a water-based acrylate adhesive composition.
BACKGROUND
Instant adhesives are ones having adequate wet adhesion. A strong bond is quickly developed before the adhesive composition is completely dried. Common types of instant adhesives include solvent-based instant adhesives and water-based instant adhesives. Solvent-based instant adhesives contain a great amount of highly volatile organic solvents, and are gradually exiting the market due to the increasingly stringent environmental regulations. Water-based instant adhesives has thus increased in market share because they are environmentally friendly.
At present, the most common water-based instant adhesive product is chloroprene rubber adhesives. Chloroprene rubber has fast-bonding performance because of its low glass transition temperature (about -45 °C) and it has room -temperature crystallization performance (about 35°C). However, because of the high crystallization temperature, the fast-bonding performance of Chloroprene rubber will decrease significantly when the ambient temperature is slightly lower (e.g. <10°C). In addition, because chloroprene latex contains chlorine, it is not an environmentally friendly material. The environmental friendliness of Chloroprene rubber thus decreases to a certain extent.
Another type of developing water-based instant adhesive product is two-component adhesives, which contains an emulsion and a demulsifier (such as an inorganic salt solution). When the two- component adhesives applied, the emulsion is mixed with the demulsifier to demulsify the emulsion so as to achieve fast bonding performance. Two-component adhesives have a relatively complex application procedures and are harder to control.
Therefore, there is still a need for the development of a one-component non-chloroprene rubber water- based fast-bonding adhesive composition.
SUMMARY
The present invention provides a water-based acrylate adhesive composition, comprising:
polyacrylate, the polyacrylate being formed by copolymerization of raw materials containing at least two polymerizable monomers, the polyacrylate having a glass transition temperature within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 and
120,000;
a cosolvent;
an emulsifier;
water, wherein
the pH value of the water-based acrylate adhesive composition is below 6.
Alternatively, a weight ratio of the cosolvent to the polyacrylate is within a range of 0.1 : 100 and 15: 100.
Alternatively, the weight ratio of the cosolvent to the polyacrylate is within a range of 5 : 100 and 10: 100.
Alternatively, when the amount of the polyacrylate is 40 to 80 parts by weight, the amount of the emulsifier is 0.5 to 2 parts by weight, and the amount of the water is 20 to 60 parts by weight.
Alternatively, polymerizable monomers for the polyacrylate comprise methacrylic acid, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, or a combination thereof.
Alternatively, polymerizable monomers for the polyacrylate comprise styrene, ethylene acetate, or a combination thereof.
Alternatively, the cosolvent is selected from the group consisting of cyclohexane, n-heptane, ethyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate and a combination thereof.
Alternatively, the glass transition temperature of the polyacrylate is above -30°C, preferably above -20°C.
Alternatively, the glass transition temperature of the polyacrylate is below 10°C.
Alternatively, the pH value of the water-based acrylate adhesive composition is below 5, preferably below 4.5.
DETAILED DESCRIPTION
The present invention provides a water-based acrylate adhesive composition that has excellent room -temperature fast-bonding performance.
The water-based acrylate adhesive composition provided by the present invention comprises: polyacrylate, the polyacrylate having a glass transition temperature within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 and 120,000;
a cosolvent; an emulsifier;
water, wherein
the pH value of the water-based acrylate adhesive composition is below 6.
The adhesive composition provided by the present invention is based on polyacrylate rather than chloroprene rubber. Polyacrylate is more environmentally friendly than chloroprene rubber.
The adhesive composition provided by the present invention is water-based, which does not contain a high amount of volatile solvents, thereby improving the environmental friendliness of the adhesive composition as compared with that of solvent-based fast-bonding adhesive compositions.
In the adhesive composition provided by the present invention, polyacrylate refers to a polymer which is mainly polymerized by (meth)acrylic acid and (meth)acrylate monomers. For example, the monomers may be acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, etc. More preferably, the monomers are methacrylic acid, acrylic acid, 2-ethylhexyl acrylate, and a combination thereof.
In addition to (meth)acrylic acid and (meth)acrylate monomers, other polymerization monomers may also be added. For example, styrene or vinyl acetate monomers may be added. These monomers can adjust the glass transition temperature and hydrophilicity of the obtained polymers. Acrylamide monomers such as methacrylamide and acryloyl morpholine may also be used.
In the adhesive composition provided by the present invention, polyacrylate, in the form of an emulsion, exists in water. Therefore, the composition comprises an emulsifier. Emulsifiers that can be used are non- cationic emulsifiers (i.e., anionic emulsifiers and non-ionic emulsifiers or a combination thereof), such as DS-10 (alkylbenzene sulfonate, purchased from Rhodia), SR- 10 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), SR-20 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), ER-10 (Reactive nonylphenol free type anionic emulsifier purchased from ADEKA), ER-20 (Reactive nonylphenol free type anionic emulsifier, purchased from ADEKA), FES- 32 (Aliphatic alcohol ether sulfate, purchased from BASF), OP- 10 (Polyoxyethylene octyl phenol ether, purchased from DOW), and TO-8 (Iso-tridecanol polyoxyethylene ether, purchased from BASF). The adhesive composition will lost its fast bonding property when employing a cationic emulsifier. The inventor of the invention discovered that when a proper amount of cosolvent was added to the composition, the emulsion composition has excellent fast-bonding performance. The cosolvent in the present invention is a solvent with good compatibility with polyacrylate; that is, the solubility of the polymer and the solubility of the solvent are similar. That the solubility of the polymer and the solubility of the solvent being similar refers to that the difference between the solubility parameter of the solvent and that of the polymers is not greater than 1.5. For example, in example 1 , according to the combination of the monomers, the solubility parameter of the obtained emulsion polymer is 9.30, so the solubility parameter of the selected cosolvent should be about 9.30, such as cyclohexane (8.59), isobutyl acetate (9.10), and hexyl acetate (9.15). The added cosolvent may be well dispersed in polymer emulsion particles and serves as a plasticizer, so that the adhesive composition has excellent fast-bonding performance. Cosolvents that can be used include cyclohexane, n-heptane, ethyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate, etc. Based on the weight of the polyacrylate in the composition, the amount of the used cosolvent is preferably in a range of 0.1- 15%, i.e., the weight ratio of the cosolvent to the polyacrylate is 0.1: 100-15: 100. More preferably, the weight ratio is within a range of 5% and 10%. In a non-theoretical sense, it is considered that, when the amount of the cosolvent is too small, the effect of improving the fast-bonding performance is not obvious; and when the amount of the cosolvent is too high, the stability of the emulsion will be decreased, and too much VOC will be introduced in.
The properties of the polyacrylate itself also have an important influence on fast-bonding performance. In order for the composition to function at a normal temperature (including room temperature and a temperature slightly lower than room temperature, such as below 10°C), the glass transition temperature Tg of the polyacrylate is specifically selected to be within a range of -40°C and 15°C. In a non-theoretical sense, it is considered that when the glass transition temperature is too high, the fast-bonding performance is poor; and when the glass transition temperature is too low, the final strength is insufficient. Further, the glass transition temperature of the polyacrylate is preferably above -30°C, more preferably above -20°C. The glass transition temperature of the polyacrylate is preferably below 10°C. When the glass transition temperature is within the preferred range, the composition exhibits better fast-bonding performance at low temperature.
In addition, the number-average molecular weight of the polyacrylate is selected to be within a range of 30,000 and 120,000. In a non-theoretical sense, it is considered that, when the number- average molecular weight is too high, the fast-bonding performance is poor; and when the number- average molecular weight is too low, the final strength is insufficient.
For the present invention, the most important thing is the pH value of the emulsion. As discovered by the inventor, when the pH value is too high, specifically for example higher than 6, the emulsion composition loses fast-bonding performance. The pH value of the emulsion may be tested by pH meter. When the pH value of the emulsion is below 5, more preferably below 4.5, the fast-bonding performance of the emulsion composition is further improved. The weight proportions of the polyacrylate, water and emulsifier may be selected appropriately. Preferably, when the amount of the polyacrylate is 40 to 80 parts by weight, the amount of the emulsifier is 0.5 to 2 parts by weight, and the amount of the water is 20 to 60 parts by weight. The emulsion obtained accordingly has suitable fluidity and viscosity, and thus ensuring the fast-bonding performance.
Technical solutions in the examples of the present disclosure will be described clearly and completely below in combination with the specific implementation solutions of the present disclosure. The described implementation solutions and/or examples are only a part, rather than all, of the implementation solutions and/or examples of the present disclosure. All other examples obtained by a person skilled in the art based on the implementation solutions and/or examples of the present disclosure, without contributing any inventive labor, shall belong to the protection scope of the present disclosure.
Embodiments
A person skilled in the art may obviously make changes and variations to the embodiments of the present disclosure without departing from the spirit and scope of the present disclosure. Thus, when these modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalent technologies, the present disclosure is also intended to include these modifications and variations.
In the following examples and comparative examples, the abbreviation 2-EHA denotes 2-ethylhexyl acrylate, MAA denotes methacrylic acid, AA denotes acrylic acid, VAc denotes vinyl acetate, ST denotes styrene, IOTG denotes isooctyl thioglycolate, KPS denotes potassium persulfate, TBHP denotes tetrabutyl diphosphate.
The commodities mentioned in the examples and comparative examples include SIPONATE DS- 10, which is an emulsifier purchased from RHODIA; ER-20, which is an emulsifier purchased from ADEKA CHEMICAL; and T1651, which is a reducing agent purchased from BRIJGGEMANN CHEMICAL.
The following analysis is performed in various examples and comparative examples.
1) Glass transition temperature (Tg)
The glass transition temperature of the poly acrylate obtained through polymerization is measured by adopting a DSC thermal analysis method.
2) pH value
The pH value of the obtained emulsion is measured by adopting a pH meter.
3) Number-average molecular weight (Mn) and polymer dispersion index (PDI) The number-average molecular weight of the polyacrylate obtained through polymerization and the polymer dispersion index are measured by adopting gel permeation chromatography.
4) Fast-bonding performance measurement
A piece of 10 cm c 10 cm c 5 cm cuboid thick PU foam sheet (polyurethane, with density of 19 kg/m3) and a piece of 10 cm c 10 cm c 1.5 cm cuboid thin PU foam sheet (with density of 19 kg/m3) are used for performing a 90-degree bonding test to evaluate the fast-bonding performance. Five grams of the adhesive composition to be tested are sprayed evenly on two adjacent surfaces of the thick PU foam sheet (10 cm c 1.5 cm surface and 10 cm c 10 cm surface). The thin PU foam sheet is immediately bent for 90 degrees and then attached to the two surfaces of the thick PU foam sheet just sprayed with adhesive, and the thin PU foam sheet is then pressed with just the right force for fitting. After a period of time, the hand lets go of the PU foam sheet. If the PU foam sheets seperate, the hand continue to press on the PU foam sheet until the thin PU foam sheet does not seperate with the thick PU foam sheet, and the time needed to complete the bonding is recorded. After that, the bonded foam is let stand, and the duration to the time at which the thin PU foam sheet is warped from the thick PU foam sheet is recorded. If no warping occurs within 24h, it is evaluated as "non-debonded".
Example 1
An anionic emulsifier SIPONATE DS-10 (1.37 g) and ER-20 (0.27 g) were added to deionized water (160.67 g), stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump, after the emulsifier was completely dissolved, a mixture of 2-EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (37.68 g) and IOTG (0.27 g) was added, nitrogen was fed into reaction solution to remove oxygen, stirring was performed for emulsification for 20 min, then the temperature was increased to 45°C, then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization, the reaction solution was stirred to emit heat for 30 min, the temperature was set to 70° C, and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1. Example 2
NH3Ή2O was added to the emulsion obtained in example 1 to regulate the pH value to 3.52.
The glass transition temperature, the number-average molecular weight and the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 3
NH3Ή2O was added to the emulsion obtained in example 1 to regulate the pH value to 5.02.
The glass transition temperature, the number-average molecular weight and the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 4
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g), stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump, after the emulsifier was completely dissolved, a mixture of 2- EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (37.68 g) and IOTG (0.13 g) was added, nitrogen was fed into reaction solution to remove oxygen, stirring was performed for emulsification for 20 min, then the temperature was increased to 45°C, then KPS (0.27 g), NazSzOs (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization, the reaction solution was stirred to emit heat for 30 min, the temperature was set to 70° C, and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 5
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g), stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump, after the emulsifier was completely dissolved, a mixture of 2-EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (37.68 g) and IOTG (0.54 g) was added, nitrogen was fed into reaction solution to remove oxygen, stirring was performed for emulsification for 20 min, then the temperature was increased to 45 °C, then KPS (0.27 g), Na2S2C>5 (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization, the reaction solution was stirred to emit heat for 30 min, the temperature was set to 70°C, and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion. The pH value of the obtained emulsion was 3.42.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 6
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g), stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump, after the emulsifier was completely dissolved, a mixture of 2- EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (37.68 g) and IOTG (0.27 g) was added, nitrogen was fed into reaction solution to remove oxygen, stirring was performed for emulsification for 20 min, then the temperature was increased to 45°C, then KPS (0.27 g), Na2S205 (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization, the reaction solution was stirred to emit heat for 30 min, the temperature was set to 70° C, and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 7
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g), stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump, after the emulsifier was completely dissolved, a mixture of 2- EHA (82.20 g), MA (16.44 g), AA (6.85 g), ST (24.70 g), VAc (6.85 g) and IOTG (0.27 g) was added, nitrogen was fed into reaction solution to remove oxygen, stirring was performed for emulsification for 20 min, then the temperature was increased to 45°C, then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization, the reaction solution was stirred to emit heat for 30 min, the temperature was set to 70° C, and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization, then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped, the dropping was completed after lh, the temperature was decreased to room temperature, cyclohexane (6.87 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 8
The polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, cyclohexane (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Example 9
The polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, hexyl acetate (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1. Example 10
The polymerization of the emulsion was the same as that in example 1, the difference only lied in that, after polymerization was finished and the temperature was decreased to room temperature, isobutyl acetate (13.74 g) was added, stirring was performed for half an hour, and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 1
An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (68.7 g), MA (16.44 g), AA (4.12 g), ST (41.22 g), VAc (6.85 g) and IOTG (0.27 g) was added, nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 2
An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (79.46 g), MA (16.44 g), AA (6.85 g), ST (27.4 g), VAc (6.85 g) and IOTG (0.14 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na S O (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 3
An anionic emulsifier SIPONATE DS-10 (1.37 g) was added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (79.46 g), MA (16.44 g), AA (6.85 g), ST (27.4 g), VAc (6.85 g) and IOTG (0.54 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na2S20> (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 4
NH3Ή2O was added to the emulsion obtained in example 1 to regulate the pH value to 6.52.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, and the fast-bonding performance of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 5
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g) and ST (37.68 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na2S20s (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60°C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 6
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and NaaHPCE (0.27 g) were added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (69.19 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (37.68 g) and IOTG (0.80 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na2S20> (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 7
An anionic emulsifier SIPONATE DS-10 (1.37 g), ER-20 (0.27 g) and Na2HP04 (0.27 g) were added to deionized water (160.67 g); stirring was performed in a five-neck bottle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (62.34 g), MA (16.44 g), AA (6.87 g), VAc (6.85 g), ST (44.53 g) and IOTG (0.27 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na2S20s (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1.
Comparative example 8
An anionic emulsifier SIPONATE™ DS-10 (1.37 g), ER-20 (0.27 g) and NaaHPCE (0.27 g) were added to deionized water (160.67 g); stirring was performed in a five-neck botle containing a reflux condenser, a thermometer, a stirrer and a feeding pump; after the emulsifier was completely dissolved, a mixture of 2-EHA (93.16 g), MA (16.44 g), AA (6.85 g), ST (13.70 g), VAc (6.85 g) and IOTG (0.27 g) was added; nitrogen was fed into reaction solution to remove oxygen; stirring was performed for emulsification for 20 min; then the temperature was increased to 45°C; then KPS (0.27 g), Na2S20> (0.07 g) and 0.22% ferrous sulfate heptahydrate aqueous solution (0.6 g) were sequentially added to initiate polymerization; the reaction solution was stirred to emit heat for 30 min; the temperature was set to 70°C; and polymerization was continuously performed for 90 min. In order to increase the monomer conversion rate, the temperature was set to 60° C at the end of polymerization; then 10% TBHP aqueous solution (1.58 g) and 10% T1651 aqueous solution (1.32 g) were dropped; the dropping was completed after lh; the temperature was decreased to room temperature; cyclohexane (6.87 g) was added; stirring was performed for half an hour; and filtration was performed to obtain an emulsion.
The glass transition temperature, the number-average molecular weight, the polymer dispersion index of the polyacrylate, the fast-bonding performance of the emulsion, and the pH value of the emulsion were measured according to the above methods. The results were as shown in Table 1. Table 1
Figure imgf000015_0001
Table 1 shows that the various parameters of the water-based emulsion compositions in Examples 1-10 meet the requirements of the present invention. The bonding can be finished within 5s; debonding does not occur within 24h. It can be seen that the composition can form bonds fast.
In contrast, since the emulsion in comparative examples 1-3 do not contain any cosolvent, the emulsion fails to create a bond, or debonding occurs very quickly after bonding. In comparative examples 4-8, even though cosolvents are used, the following parameters do not meet the requirements of the present invention: the pH value of the emulsion in comparative example 4 is higher than pH 6; the number-average molecular weight of the polyacrylate in comparative example 5 is greater than 120,000; the number-average molecular weight of the polyacrylate in comparative example 6 is less than 30,000; the glass transition temperature of the polyacrylate in comparative example 7 is above 15°C; and the glass transition temperature of the polyacrylate in comparative example 8 is below -40°C. As a result, the emulsions in these comparative examples have poor fast bonding performance.
Even though all bonds were finished within 5s, the time required for bonding is shorter in examples 1 and 2 than example 3, which indicates that the fast-bonding performance of the emulsion composition can be further improved when the pH value is below 5, and more preferably below 4.5.
Obviously, a person skilled in the art may make various changes and variations to the examples of the present disclosure without departing from the spirit and scope of the present disclosure. Thus, if these modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalent technologies, the present disclosure is also intended to include these modifications and variations.

Claims

1. A water-based acrylate adhesive composition, the water-based acrylate adhesive composition comprising: polyacrylate, the polyacrylate being formed by copolymerization of raw materials containing at least two polymerizable monomers, the polyacrylate having a glass transition temperature of within a range of -40°C and 15°C, and a number-average molecular weight within a range of 30,000 to 120,000;
a cosolvent;
an emulsifier; and
water, wherein
a pH value of the water-based acrylate adhesive composition is less than 6.
2. The water-based acrylate adhesive composition according to claim 1, wherein a weight ratio of the cosolvent to the polyacrylate is within a range of 0.1 : 100 and 15: 100.
3. The water-based acrylate adhesive composition according to claim 2, wherein the weight ratio of the cosolvent to the polyacrylate is within a range of 5: 100 and 10: 100.
4. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein when an amount of the polyacrylate is from 40 to 80 parts by weight, an amount of the emulsifier is from 0.5 to 2 parts by weight, and an amount of the water is from 20 to 60 parts by weight.
5. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the polymerizable monomers for the polyacrylate comprises methacrylic acid, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, or a combination thereof.
6. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the polymerizable monomers for the polyacrylate comprises styrene, ethylene acetate, or a combination thereof.
7. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the cosolvent is selected from the group consisting of cyclohexane, n-heptane, ethyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate and a combination thereof.
8. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the glass transition temperature of the polyacrylate is above -30°C, preferably above -20°C.
9. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the glass transition temperature of the polyacrylate is below 10°C.
10. The water-based acrylate adhesive composition according to any one of claims 1 to 3, wherein the pH value of the water-based acrylate adhesive composition is less than 5, preferably less than 4.5.
PCT/IB2020/054845 2019-06-03 2020-05-21 Water-based acrylate adhesive composition WO2020245690A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112680143A (en) * 2020-12-21 2021-04-20 四川开物华包装材料有限公司 Glue for Japanese paper adhesive tape and production process thereof
CN115340625A (en) * 2022-09-29 2022-11-15 惠州市赛力达化工有限公司 Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216005A (en) * 1994-01-27 1995-08-15 Daicel Chem Ind Ltd Aqueous emulsion composition and its production
JPH10158615A (en) * 1996-11-30 1998-06-16 Chuo Rika Kogyo Kk Adhesive composition and information carrier sheet produced by using the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3640921B2 (en) * 2001-12-28 2005-04-20 クラリアントポリマー株式会社 Synthetic resin emulsion, easily water-swellable pressure-sensitive adhesive composition comprising the same, and method for producing synthetic resin emulsion
CN101481437B (en) * 2009-01-23 2011-04-27 华南理工大学 Preparation of high closeness polyacrylacid ester dispersion
JP6537171B2 (en) * 2014-06-04 2019-07-03 昭和電工株式会社 Polymer emulsion, aqueous pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
CN105837757B (en) * 2016-04-06 2021-11-12 北京金汇利应用化工制品有限公司 Microgel aqueous acrylic acid shell-core resin emulsion and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216005A (en) * 1994-01-27 1995-08-15 Daicel Chem Ind Ltd Aqueous emulsion composition and its production
JPH10158615A (en) * 1996-11-30 1998-06-16 Chuo Rika Kogyo Kk Adhesive composition and information carrier sheet produced by using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112680143A (en) * 2020-12-21 2021-04-20 四川开物华包装材料有限公司 Glue for Japanese paper adhesive tape and production process thereof
CN112680143B (en) * 2020-12-21 2022-05-06 四川开物华包装材料有限公司 Glue for Japanese paper adhesive tape and production process thereof
CN115340625A (en) * 2022-09-29 2022-11-15 惠州市赛力达化工有限公司 Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof

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