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WO2022074925A1 - Procédé de production d'une composition d'émulsion - Google Patents

Procédé de production d'une composition d'émulsion Download PDF

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Publication number
WO2022074925A1
WO2022074925A1 PCT/JP2021/028743 JP2021028743W WO2022074925A1 WO 2022074925 A1 WO2022074925 A1 WO 2022074925A1 JP 2021028743 W JP2021028743 W JP 2021028743W WO 2022074925 A1 WO2022074925 A1 WO 2022074925A1
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WIPO (PCT)
Prior art keywords
emulsion composition
emulsion
paraffin wax
melting point
producing
Prior art date
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Ceased
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PCT/JP2021/028743
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English (en)
Japanese (ja)
Inventor
康史 藤原
美佳 真継
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Seiko PMC Corp
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Seiko PMC Corp
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Publication date
Application filed by Seiko PMC Corp filed Critical Seiko PMC Corp
Priority to JP2022538907A priority Critical patent/JP7303993B2/ja
Priority to CN202180068746.4A priority patent/CN116323721A/zh
Publication of WO2022074925A1 publication Critical patent/WO2022074925A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined

Definitions

  • the present invention relates to a method for producing an emulsion composition having an excellent water vapor barrier property and an excellent storage stability on a substrate such as paper or a film.
  • the function required for paper and film represented by food packaging materials has a water vapor barrier property, and it is considered to be an important property for suppressing deterioration and discoloration of the contents, growth of bacteria and mold growth.
  • a method for imparting water vapor barrier properties to paper and film a method of coating an inorganic compound such as mica, an organic compound such as wax, a polymer such as polyvinylidene chloride, and a product combining these is widely used. ing.
  • the present invention is an emulsion composition that forms a coating film having excellent water vapor barrier properties on a substrate such as paper or film, can be used as a single liquid from the viewpoint of operability, and has excellent storage stability.
  • the purpose is to provide a manufacturing method.
  • the present invention ⁇ 1> Emulsion polymerization of a vinyl group-containing monomer mixture (D) in the presence of water (A), a surfactant (B), and a paraffin wax (C) having a melting point in the range of 57 to 71 ° C.
  • A water
  • B surfactant
  • C paraffin wax
  • the surfactant (B) contains a low molecular weight emulsifier (B1) having a sodium sulfonate group (2) It contains glycidyl methacrylate (E) at the time of emulsion polymerization ⁇ 2> Water (A) and A method for producing an emulsion composition obtained by emulsion polymerization of a vinyl group-containing monomer mixture (D) in the presence of a surfactant (B) and a paraffin wax (C) having a melting point in the range of 57 to 71 ° C.
  • the temperature at which emulsion polymerization is carried out is equal to or higher than the melting point of the paraffin wax (C) present at the time of emulsion polymerization, and the surfactant (B) contains a low molecular weight emulsifier (B1) having a sodium sulfonate group.
  • Method for producing emulsion composition ⁇ 3> Emulsion polymerization of a vinyl group-containing monomer mixture (D) in the presence of water (A), a surfactant (B), and a paraffin wax (C) having a melting point in the range of 57 to 71 ° C.
  • ⁇ 8> The above-mentioned ⁇ 1>, wherein the viscosity change rate (%) of the emulsion composition at 25 ° C. after 28 days of standing at 40 ° C. with respect to 1 day after standing at 40 ° C. is ⁇ 10 to 10%.
  • the emulsion obtained in the present invention it is possible to enhance the water vapor barrier property of the paper or film substrate, and this emulsion has excellent storage stability and the desired performance can be obtained with one liquid.
  • the sex can be improved.
  • the raw materials used in the method for producing an emulsion composition of the present invention are at least water (A), a surfactant (B), paraffin wax (C) having a melting point in the range of 57 to 71 ° C., and a vinyl group. It is a mixture of contained monomers (D).
  • the surfactant (B) used in the present invention is appropriately selected according to the conditions (1) and (2) described later as long as the effect of the invention is not impaired, and is ionic, its chemical species, molecular weight, and amount used. It can be used without any particular restrictions.
  • both the low molecular weight emulsifier and the high molecular weight emulsifier mean a surfactant that can be used for emulsion polymerization, and the high molecular weight emulsifier consists of a polymer synthesized by radical polymerization and a naturally occurring polymer.
  • low molecular weight emulsifiers refer to other emulsifiers.
  • paraffin wax (C) having a melting point in the range of 57 to 71 ° C is not particularly limited as long as the melting point is in the range specified in the present invention.
  • the paraffin wax refers to a mixture of normal paraffin having 20 or more carbon atoms, which is solid (wax-like) and insoluble in water at room temperature.
  • paraffin wax having a melting point in the range of 57 to 71 ° C. for example, the trade name "Paraffin WAX” series (135 (melting point 59 ° C.), 140 (61 ° C.), 145) manufactured by Nippon Seiro Co., Ltd. (63 ° C.), 150 (66 ° C.), 155 (69 ° C.)) and the like.
  • the ratio of the paraffin wax (C) to the polymer component contained in the emulsion composition is 2 to 10 mass by mass from the viewpoint of water vapor barrier property. % Is preferable.
  • the polymer component contained in the emulsion composition refers to a copolymer obtained by emulsion polymerization of a vinyl group-containing monomer mixture (D) described later and a carboxy group-containing vinyl polymer (B2) which is a polymer emulsifier.
  • the vinyl group-containing monomer refers to a vinyl group-containing monomer excluding glycidyl methacrylate (E) described later.
  • a hydrophobic monomer having a solubility in water at 20 ° C. of less than 2% by mass is preferable as long as the effect of the present invention is not impaired.
  • Styrenes and (meth) acrylic acid alkyl esters having 1 to 8 carbon atoms of an alkyl group are preferable.
  • Styrenes include styrene, ⁇ -methylstyrene, and (meth) acrylates having an alkyl group having 1 to 8 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate. Examples thereof include butyl and 2-ethylhexyl (meth) acrylate, and one or a mixture of two or more of these vinyl group-containing monomers is used. More preferably, it is one or more selected from styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • an anionic monomer such as acrylic acid and methacrylic acid, and a nonionic monomer such as acrylamide and diacetoneacrylamide can be used.
  • a vinyl group-containing monomer is present in the presence of water (A), a surfactant (B), and a paraffin wax (C) having a melting point in the range of 57 to 71 ° C.
  • the temperature at which the emulsion polymerization is carried out needs to be equal to or higher than the melting point of the paraffin wax (C) present at the time of emulsion polymerization. If the polymer is polymerized below the melting point of the paraffin wax, it is difficult to incorporate it into the polymer particles because the state of the paraffin wax is not a liquid. Therefore, the obtained emulsion composition may cause separation over time.
  • the surfactant (B) contains a low molecular weight emulsifier (B1) having a sodium sulfonate group (2) It contains glycidyl methacrylate (E) at the time of emulsion polymerization. If none of the conditions are satisfied, the storage stability of the obtained emulsion composition is inferior, and therefore, thickening or separation over time may occur at high temperatures.
  • a low molecular weight emulsifier (B1) having a sodium sulfonate group (2) It contains glycidyl methacrylate (E) at the time of emulsion polymerization.
  • the surfactant (B) needs to contain a small molecule emulsifier (B1) having a sodium sulfonate group.
  • a small molecule emulsifier (B1) having a sodium sulfonate group examples include sodium alkylbenzene sulfonate, sodium dialkyl sulfosuccinate, sodium alkylallyl sulfosuccinate, and formalin condensates of sodium naphthalene sulfonate.
  • a low molecular weight emulsifier having a sodium sulfonate group having no polyoxyalkylene (polyoxyethylene, polyoxypropylene, etc.) alkyl (or alkenyl) ether structure is preferable from the viewpoint of water resistance of the coating film, and more preferably.
  • the ratio of the low molecular weight emulsifier (B1) having a sodium sulfonate group to the vinyl group-containing monomer mixture (D) is preferably 0.5 to 5% by mass.
  • the surfactant (B) preferably contains a carboxy group-containing vinyl polymer (B2) as a polymer emulsifier.
  • the coating film coated with the emulsion composition obtained in the present invention on the substrate can be obtained. , It becomes more excellent in water vapor barrier property.
  • the carboxy group-containing vinyl polymer (B2) which is a polymer emulsifier, a styrene acrylic resin, an acrylic resin, or a styrene maleine in which a vinyl monomer having a carboxy group such as (meth) acrylic acid or maleic acid is used as a copolymerization component.
  • Acrylic resin and the like can be mentioned.
  • the carboxy group-containing vinyl polymer (B2) is neutralized with a basic substance such as ammonia, an organic amine and sodium hydroxide to be solubilized and used.
  • the concentration of the obtained emulsion, and handling is preferably in the range of 5000 to 30,000, the acid value is preferably in the range of 100 to 300, and from the viewpoint of water resistance, ammonia and organic amines are preferable. It is preferable to neutralize with.
  • the vinyl group-containing monomer mixture (D) is used from the viewpoint of water resistance of the coating film regardless of the conditions (1) and (2).
  • a carboxy group-containing vinyl polymer (B2) 60 to 80/20 to 40 (% by mass).
  • a conventionally known method of emulsion polymerization can be applied.
  • water (A), a surfactant (B), and a paraffin wax (C) are charged in a reaction vessel equipped with a stirrer and a nitrogen gas introduction tube, and ammonium persulfate, potassium persulfate, and hydrogen peroxide are used as polymerization initiators.
  • a vinyl group-containing monomer mixture using any redox initiator consisting of a peroxide such as, or a combination of these peroxides with a reducing agent such as iron sulfate, sodium bisulfite, ascorbic acid, sodium ascorbate, etc.
  • the emulsion composition can be obtained by dropping (D) over 60 to 180 minutes and reacting for 60 to 480 minutes after the completion of the dropping.
  • a known chain transfer agent such as alkyl mercaptan may be used in combination with the reaction of the vinyl group-containing monomer mixture (D).
  • the reaction temperature of the emulsion polymerization is set to a temperature equal to or higher than the melting point of the paraffin wax (C).
  • the emulsion composition obtained by the method for producing an emulsion composition of the present invention is an emulsion obtained after 28 days of standing at 40 ° C. as an index thereof from the viewpoint of storage stability, which is a subject of the present invention.
  • the viscosity change rate (%) of the composition at 25 ° C. is preferably ⁇ 10 to 10%.
  • the emulsion composition obtained by the present invention is useful as an aqueous coating agent, and if necessary, a general-purpose organic solvent such as isopropyl alcohol (IPA) or butyl cell solution, a filler, a wax, a film-forming aid, and a leveling agent. , Antifoaming agent, preservative can be added.
  • IPA isopropyl alcohol
  • the target base material is not only an absorbent base material such as paper but also a non-absorbent base material such as PET, polyethylene and polypropylene. It can also be used.
  • Acid value Amount of dropped 0.5N potassium hydroxide ethanol solution (mL) x 0.5 x 56.11 / sample (g) ⁇ Measurement of viscosity> Measured at 25 ° C. using B-type viscosity.
  • Example 1 ⁇ Preparation of emulsion composition> (Example 1) In a separable flask equipped with a thermometer, a condenser, and a stirrer, 500 g of ion-exchanged water, 121 g of carboxy group-containing vinyl polymer (B2a), and 25.6 g of 28% ammonia water are charged and heated at 90 ° C. for 120 minutes to carboxy. An aqueous solution of a group-containing vinyl polymer was used.
  • neogen S20 sodium dodecylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., effective content 20%
  • B1 low molecular weight emulsifier
  • C paraffin wax
  • paraffin WAX155 Paraffin WAX155
  • a diluted solution prepared by dissolving 1.7 g of ammonium persulfate in 17 g of ion-exchanged water as a polymerization initiator was added, and after 5 minutes, 120 g of styrene and 142 g of 2-ethylhexyl acrylate as a vinyl group-containing monomer mixture (D) were added.
  • Emulsion polymerization was carried out by dropping over a minute. 60 minutes after the completion of the dropping, a diluted solution prepared by dissolving 0.3 g of ammonium persulfate in 3 g of ion-exchanged water was added. After 120 minutes from the completion of the dropping, the mixture was cooled and diluted with ion-exchanged water to a concentration of 41% to obtain an emulsion composition (1).
  • Example 2 Emulsion composition (same as in Example 1) except that 8.1 g of Jamaicasurf P-10 (sodium dioctylsulfosuccinate, manufactured by Shin Nihon Rika Co., Ltd., effective content 70%) was used as the small molecule emulsifier (B1). 2) was obtained.
  • Jamaicasurf P-10 sodium dioctylsulfosuccinate, manufactured by Shin Nihon Rika Co., Ltd., effective content 70%
  • Example 3 Emulsion in the same manner as in Example 1 except that 14.3 g of Cellflow 110 (formalin condensate of sodium naphthalene sulfonate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., effective content 40%) was used as the low molecular weight emulsifier (B1). The composition (3) was obtained.
  • Cellflow 110 formalin condensate of sodium naphthalene sulfonate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., effective content 40%
  • Example 4 During the emulsion polymerization of the vinyl group-containing monomer mixture (D), 5.7 g of glycidyl methacrylate (E), which is 2% by mass based on the vinyl group-containing monomer mixture (D), was added without using the low molecular weight emulsifier (B1).
  • the emulsion composition (4) was obtained in the same manner as in Example 1 except for the above.
  • Example 5 123 g of vinyl polymer (B2a) containing a carboxy group, 26.0 g of 28% aqueous ammonia, 28.7 g of Neogen S20, and 8.4 g of paraffin wax having a melting point of 69 ° C. (2 mass with respect to the polymer component contained in the emulsion composition). %), 143 g of styrene, 143 g of 2-ethylhexyl acrylate, and 5.7 g of glycidyl methacrylate (E), which is 2% by mass based on the vinyl group-containing monomer mixture (D), as in Example 1. Similarly, the emulsion composition (5) was obtained.
  • Example 6 120 g of carboxy group-containing vinyl polymer (B2a), 25.3 g of 28% aqueous ammonia, 27.9 g of Neogen S20, 20.3 g of paraffin wax having a melting point of 69 ° C., 140 g of styrene, and 140 g of 2-ethylhexyl acrylate.
  • the emulsion composition (6) was obtained in the same manner as in Example 1 except that 5.6 g of glycidyl methacrylate (E), which was 5% by mass based on the vinyl group-containing monomer mixture (D), was added.
  • Example 7 114 g of vinyl polymer (B2a) containing a carboxy group, 24.0 g of 28% aqueous ammonia, 26.6 g of Neogen S20, and 38.8 g of paraffin wax having a melting point of 69 ° C. (10 mass with respect to the polymer component contained in the emulsion composition). %), 133 g of styrene, 133 g of 2-ethylhexyl acrylate, 5.3 g of glycidyl methacrylate (E) which is 10% by mass with respect to the vinyl group-containing monomer mixture (D), and 1.6 g of ammonium persulfate is ionized.
  • the emulsion composition (7) was obtained in the same manner as in Example 1 except that the emulsion polymerization was started with a diluted solution dissolved in 16 g of exchanged water.
  • Example 8 The emulsion composition (8) was obtained in the same manner as in Example 6 except that 20.3 g of paraffin wax (manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin WAX135) having a melting point of 59 ° C. was used as the paraffin wax (C). rice field.
  • paraffin wax manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin WAX1305 having a melting point of 59 ° C.
  • Example 9 122 g of carboxy group-containing vinyl polymer (B2a), 25.7 g of 28% aqueous ammonia, 7.1 g of Neogen S20 (0.5% by mass with respect to the vinyl group-containing monomer mixture (D)), paraffin having a melting point of 69 ° C.
  • the emulsion composition (9) was obtained in the same manner as in Example 1 except that the amount of wax was 20.4 g, the amount of styrene was 143 g, and the amount of 2-ethylhexyl acrylate was 143 g.
  • Example 10 450 g of ion-exchanged water, 119 g of carboxy group-containing vinyl polymer (B2a), 25.1 g of 28% ammonia water, 69.4 g of Neogen S20 (5% by mass with respect to the vinyl group-containing monomer mixture (D)), melting point.
  • the emulsion composition (10) was obtained in the same manner as in Example 1 except that 19.8 g of paraffin wax at 69 ° C., 139 g of styrene and 139 g of 2-ethylhexyl acrylate were used.
  • Example 11 During the emulsion polymerization of the vinyl group-containing monomer mixture (D), 122 g of the carboxy group-containing vinyl polymer (B2a), 25.7 g of 28% aqueous ammonia, and a paraffin wax having a melting point of 69 ° C. were used without using the low molecular weight emulsifier (B1). It was carried out except that 20.5 g, 143 g of styrene, 143 g of 2-ethylhexyl acrylate, and 1.4 g of glycidyl methacrylate (E), which was 0.5% by mass based on the vinyl group-containing monomer mixture (D), were added.
  • the emulsion composition (11) was obtained in the same manner as in Example 1.
  • Example 12 During the emulsion polymerization of the vinyl group-containing monomer mixture (D), 115 g of the carboxy group-containing vinyl polymer (B2a), 24.3 g of 28% aqueous ammonia, and a paraffin wax having a melting point of 69 ° C. were used without using the low molecular weight emulsifier (B1). 21.0 g, 134 g of styrene, 134 g of 2-ethylhexyl acrylate, 26.8 g of glycidyl methacrylate (E), which is 10% by mass based on the vinyl group-containing monomer mixture (D), are added, and 1.6 g of ammonium persulfate is added.
  • the emulsion composition (12) was obtained in the same manner as in Example 1 except that the emulsion polymerization was started with a diluted solution dissolved in 16 g of ion-exchanged water.
  • Example 13 An emulsion composition (13) was obtained in the same manner as in Example 6 except that the carboxy group-containing vinyl polymer (B2) was used as the carboxy group-containing vinyl polymer (B2b).
  • Example 14 An emulsion composition (14) was obtained in the same manner as in Example 6 except that 95 g of methyl methacrylate, 92 g of butyl acrylate and 92 g of 2-ethylhexyl acrylate were used as the vinyl group-containing monomer mixture (D).
  • Example 15 In a separable flask equipped with a thermometer, a cooling tube, and a stirrer, 440 g of ion-exchanged water under nitrogen substitution, 39.4 g of Neogen S20 as a low molecular weight emulsifier (B1), and paraffin wax having a melting point of 69 ° C. as paraffin wax (C). was added in an amount of 20.1 g, and the temperature was maintained at 80 ° C.
  • Neogen S20 as a low molecular weight emulsifier
  • C paraffin wax
  • a diluted solution prepared by dissolving 2.4 g of ammonium persulfate in 24 g of ion-exchanged water was added, and after 5 minutes, 173 g of methyl methacrylate, 150 g of butyl acrylate, 55 g of 2-ethylhexyl acrylate, and acrylic as a vinyl group-containing monomer mixture (D).
  • a diluted solution prepared by dissolving 0.4 g of ammonium persulfate in 4 g of ion-exchanged water was added.
  • 13.2 g of a 28% aqueous ammonia solution was added, cooled, and diluted with ion-exchanged water to a concentration of 39% to obtain an emulsion composition (15).
  • Example 16 The emulsion composition (16) was obtained in the same manner as in Example 15 except that acrylic acid was methacrylic acid and a 28% aqueous ammonia solution was 11.1 g.
  • Example 17 124 g of carboxy group-containing vinyl polymer (B2a), 26.2 g of 28% aqueous ammonia, 29.0 g of monomeric acid S20, 4.2 g of paraffin wax having a melting point of 69 ° C. (1 mass with respect to the polymer component contained in the emulsion composition). %), 145 g of styrene, 145 g of 2-ethylhexyl acrylate, and 5.8 g of glycidyl methacrylate (E), which is 2% by mass based on the vinyl group-containing monomer mixture (D), as in Example 1. Similarly, the emulsion composition (17) was obtained.
  • Example 18 112 g of carboxy group-containing vinyl polymer (B2a), 23.6 g of 28% aqueous ammonia, 26.2 g of Neogen S20, 45.8 g of paraffin wax having a melting point of 69 ° C. (12 mass with respect to the polymer component contained in the emulsion composition). %), 131 g of styrene, 131 g of 2-ethylhexyl acrylate, 5.2 g of glycidyl methacrylate (E) which is 2% by mass with respect to the vinyl group-containing monomer mixture (D), and 1.6 g of ammonium persulfate is ionized.
  • the emulsion composition (18) was obtained in the same manner as in Example 1 except that the emulsion polymerization was started with a diluted solution dissolved in 16 g of exchanged water.
  • Example 19 123 g of carboxy group-containing vinyl polymer (B2a), 26.0 g of 28% aqueous ammonia, 1.4 g of Neogen S20 (0.1% by mass with respect to the vinyl group-containing monomer mixture (D)), and paraffin having a melting point of 69 ° C.
  • the emulsion composition (19) was obtained in the same manner as in Example 1 except that the amount of wax was 20.5 g, the amount of styrene was 143 g, and the amount of 2-ethylhexyl acrylate was 143 g.
  • Example 20 390 g of ion-exchanged water, 115 g of carboxy group-containing vinyl polymer (B2a), 24.3 g of 28% ammonia water, 134.4 g of Neogen S20 (10% by mass with respect to the vinyl group-containing monomer mixture (D)), melting point.
  • Example 1 except that emulsion polymerization was started with a diluted solution containing 19.2 g of paraffin wax at 69 ° C., 134 g of styrene, 134 g of 2-ethylhexyl acrylate, and 1.6 g of ammonium persulfate dissolved in 16 g of ion-exchanged water. In the same manner as above, the emulsion composition (20) was obtained.
  • Example 21 During the emulsion polymerization of the vinyl group-containing monomer mixture (D), 123 g of the carboxy group-containing vinyl polymer (B2a), 26.0 g of 28% aqueous ammonia, and a paraffin wax having a melting point of 69 ° C. were used without using the low molecular weight emulsifier (B1). It was carried out except that 20.5 g, 143 g of styrene, 143 g of 2-ethylhexyl acrylate, and 0.3 g of glycidyl methacrylate (E), which was 0.1% by mass based on the vinyl group-containing monomer mixture (D), were added.
  • the emulsion composition (21) was obtained in the same manner as in Example 1.
  • Example 22 During the emulsion polymerization of the vinyl group-containing monomer mixture (D), 123 g of the carboxy group-containing vinyl polymer (B2a), 23.4 g of 28% aqueous ammonia, and a paraffin wax having a melting point of 69 ° C. were used without using the low molecular weight emulsifier (B1). 21.3 g, 129 g of styrene, 129 g of 2-ethylhexyl acrylate, 38.8 g of glycidyl methacrylate (E), which is 15% by mass based on the vinyl group-containing monomer mixture (D), are added, and 1.6 g of ammonium persulfate is added.
  • the emulsion composition (22) was obtained in the same manner as in Example 1 except that the emulsion polymerization was started with a diluted solution dissolved in 16 g of ion-exchanged water.
  • Example 1 The emulsion composition (23) was obtained in the same manner as in Example 6 except that 20.3 g of paraffin wax (manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin WAX115) having a melting point of 48 ° C. was used as the paraffin wax (C). rice field.
  • paraffin wax manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin WAX115
  • the emulsion composition (24) was prepared in the same manner as in Example 6 except that 20.3 g of paraffin wax (manufactured by Nippon Seiro Co., Ltd., trade name: HNP-51) having a melting point of 77 ° C. was used as the paraffin wax (C). Obtained.
  • Example 3 The emulsion composition (25) was obtained in the same manner as in Example 6 except that the emulsion polymerization was carried out at 65 ° C. (less than the melting point of the paraffin wax (C)).
  • a diluted solution prepared by dissolving 1.7 g of ammonium persulfate in 17 g of ion-exchanged water was added, and after 5 minutes, 140 g of styrene, 140 g of 2-ethylhexyl acrylate and a vinyl group-containing monomer mixture (D) were added as a vinyl group-containing monomer mixture (D). ), A mixed solution of 5.6 g of glycidyl methacrylate (E), which is 2% by mass, was added dropwise over 120 minutes. 60 minutes after the completion of the dropping, a diluted solution prepared by dissolving 0.3 g of ammonium persulfate in 3 g of ion-exchanged water was added.
  • paraffin wax emulsion EMUSTER1155 manufactured by Nippon Seiro Co., Ltd., effective content 40%
  • C paraffin wax
  • ion-exchanged water was added. Dilute to a concentration of 41% with the emulsion composition (28).
  • Table 1 shows the compositions and physical properties of the emulsion compositions (1) to (28) obtained in Examples 1 to 22 and Comparative Examples 1 to 6.
  • B1a Sodium dodecylbenzene sulfonate
  • B1b Sodium dioctyl sulfosuccinate
  • B1c Formalin condensate of sodium naphthalene sulfonate
  • Db Methyl methacrylate / butyl acrylate /
  • Table 2 shows the storage stability and water vapor barrier properties of the emulsion compositions (1) to (28) obtained in Examples 1 to 22 and Comparative Examples 1 to 6.
  • ⁇ Storage stability> The emulsion composition was evaluated by confirming the change in viscosity at 25 ° C. after standing at 40 ° C. and the presence or absence of separation in appearance observation. In the present invention, it is a necessary level that separation does not occur. Therefore, the moisture permeability of the emulsion compositions (25) to (28) of Comparative Examples 3 to 6 separated after 1 day of standing at 40 ° C. for storage stability was not evaluated.
  • the viscosity change rate (%) is preferably within -10 to 10%.
  • Emulsion compositions (1) to (24) were applied to one side of a neutral woodfree paper (basis weight 65 g / m 2 ) and a PET (polyester) film using a wire bar # 5.
  • the coating amount of the coating liquid was 9 g / m 2 .
  • the moisture permeability was measured as an index of water vapor barrier property. The results are shown in Table 2.
  • Moisture permeability can be improved by increasing the amount of coating, but under the evaluation conditions of the present invention, it is preferable to have both storage stability and water vapor barrier properties in a well-balanced manner, and the viscosity change rate ( %) Is more preferably -7 to 7% or less, and the moisture permeability is 50 or less for neutral woodfree paper and 10 or less for PET film.
  • Examples 1 to 22 satisfying all the constituent requirements of the present invention include Comparative Examples 1 and 2 in which the melting point of the paraffin wax (C) is out of the range, Comparative Example 3 in which the temperature for emulsion polymerization is out of the range, and conditions ( Compared with Comparative Examples 4 and 5 that do not satisfy both 1) and (2) and Comparative Example 6 that does not perform emulsion polymerization in the presence of paraffin wax (C), which does not satisfy even one of the constituent requirements of the present invention. Therefore, it can be seen that the emulsion is stable without separation and has excellent water vapor barrier properties.
  • the ratio of the low molecular weight emulsifier (B1) having a sodium sulfonate group to the vinyl group-containing monomer mixture (D) is in the range of 0.5 to 5% by mass. It can be seen that the water vapor barrier property is excellent and the rate of change in viscosity is small.

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Abstract

Le but de la présente invention est de fournir un procédé de production d'une composition d'émulsion qui est capable de former un film de revêtement, qui présente d'excellentes propriétés de barrière à la vapeur d'eau, sur un matériau de base tel qu'une feuille de papier et un film, ladite composition d'émulsion pouvant être utilisée dans un seul bloc du point de vue de l'opérabilité, tout en présentant une excellente stabilité au stockage. La solution selon l'invention porte sur un procédé de production d'une composition d'émulsion qui est obtenue par émulsification et polymérisation d'un mélange de monomères contenant un groupe vinyle (D) en présence d'eau (A), d'un tensioactif (B) et d'une cire de paraffine (C) qui a un point de fusion dans la plage allant de 57 °C à 71 °C, ledit procédé étant caractérisé en ce que : la température à laquelle la polymérisation en émulsion est réalisée n'est pas inférieure au point de fusion de la cire de paraffine (C) qui est présente pendant la polymérisation en émulsion ; et la condition (1) ou la condition (2) décrite ci-dessous est satisfaite. Condition (1) : le tensioactif (B) contient un agent émulsifiant de faible poids moléculaire (B1) qui a un groupe sulfonate de sodium. Condition (2) : le méthacrylate de glycidyle (E) est contenu pendant la polymérisation en émulsion.
PCT/JP2021/028743 2020-10-09 2021-08-03 Procédé de production d'une composition d'émulsion Ceased WO2022074925A1 (fr)

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JP2022538907A JP7303993B2 (ja) 2020-10-09 2021-08-03 エマルション組成物の製造方法
CN202180068746.4A CN116323721A (zh) 2020-10-09 2021-08-03 乳液组合物的制造方法

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