WO2022074925A1 - Method for producing emulsion composition - Google Patents

Method for producing emulsion composition 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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Prior art keywords
emulsion composition
emulsion
paraffin wax
melting point
producing
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PCT/JP2021/028743
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French (fr)
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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Priority to CN202180068746.4A priority Critical patent/CN116323721B/en
Priority to JP2022538907A priority patent/JP7303993B2/en
Publication of WO2022074925A1 publication Critical patent/WO2022074925A1/en
Anticipated expiration legal-status Critical
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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

[Problem] The purpose of the present invention is to provide a method for producing an emulsion composition that is capable of forming a coating film, which exhibits excellent water vapor barrier properties, on a base material such as a paper sheet and a film, said emulsion composition being able to be used in a single pack from the viewpoint of operability, while exhibiting excellent storage stability. [Solution] A method for producing an emulsion composition that is obtained by emulsifying and polymerizing a vinyl group-containing monomer mixture (D) in the presence of water (A), a surfactant (B) and a paraffin wax (C) that has a melting point within the range of from 57°C to 71°C, said method being characterized in that: the temperature at which the emulsion polymerization is performed is not less than the melting point of the paraffin wax (C) that is present during the emulsion polymerization; and the condition (1) or the condition (2) described below is satisfied. Condition (1): The surfactant (B) contains a low-molecular-weight emulsifying agent (B1) that has a sodium sulfonate group. Condition (2): Glycidyl methacrylate (E) is contained during the emulsion polymerization.

Description

エマルション組成物の製造方法Method for producing emulsion composition

　本発明は、紙やフィルムなどの基材上に水蒸気バリア性に優れた塗膜を形成し、かつ保存安定性に優れるエマルション組成物の製造方法に関する。 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.

　食品包装材料に代表される紙やフィルムに求められる機能に水蒸気バリア性があり、内容物の劣化や変色、菌の増殖やカビの発生を抑制するために重要な特性とされている。紙やフィルムに水蒸気バリア性を付与するための方法として、マイカ等の無機化合物やワックス等の有機化合物、ポリ塩化ビニリデン等のポリマー、さらにはこれらを組み合わせた製品を塗工する方法が広く使用されている。 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. As 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.

　その中でも、安価で安全性の高いパラフィンワックスを用いた水蒸気バリア剤の検討が古くから行われている。例えば、パラフィンワックスと高分子乳化剤存在下でビニル基含有モノマーを乳化重合して得る、スチレンアクリル系エマルションからなる水蒸気バリア性エマルションがあるが、この技術では水蒸気バリア性は得られるものの、高温下ではパラフィンワックスの分離が経時で起こり、水蒸気バリア性エマルションの保存安定性に課題があった（特許文献１）。 Among them, studies on water vapor barrier agents using paraffin wax, which is inexpensive and highly safe, have been conducted for a long time. For example, there is a steam barrier emulsion composed of a styrene acrylic emulsion obtained by emulsion polymerization of a vinyl group-containing monomer in the presence of paraffin wax and a polymer emulsifier. Although this technique can obtain a steam barrier property, it can be obtained at high temperature. Separation of the paraffin wax occurs over time, and there is a problem in the storage stability of the water vapor barrier emulsion (Patent Document 1).

　また、ワックスによるブリード現象の問題を解決することを目的として、ワックスエマルションと低分子乳化剤の存在下で、ビニル基含有モノマーを乳化重合して得る、紙塗工用の水蒸気バリア性エマルションがあるが、得られる水蒸気バリア性は不十分なものであった（特許文献２）。 Further, for the purpose of solving the problem of bleeding phenomenon due to wax, there is a steam barrier emulsion for paper coating obtained by emulsion polymerization of a vinyl group-containing monomer in the presence of a wax emulsion and a low molecular weight emulsifier. The obtained steam barrier property was insufficient (Patent Document 2).

　この保存安定性の課題を解決する方法として、ワックスエマルションとポリマーエマルションをブレンドすることで水蒸気バリア性を発現する発明も行われてきたが、ブレンド後の水蒸気バリア性エマルションの保存安定性が悪いため、使用する直前にブレンドする２液処方となるため、操業性の観点において煩雑であることが課題であった（特許文献３）。 As a method for solving this problem of storage stability, an invention has been made in which a water vapor barrier property is exhibited by blending a wax emulsion and a polymer emulsion, but the storage stability of the water vapor barrier emulsion after blending is poor. Since it is a two-component formulation that is blended immediately before use, it has been a problem that it is complicated from the viewpoint of operability (Patent Document 3).

　水蒸気バリア性エマルションの開発に関して、性能面においては優れた水蒸気バリア性を発現し、操業性の観点からは１液で使用可能であり、かつ保存安定性に優れる製品が要求されている。 Regarding the development of water vapor barrier emulsions, there is a demand for products that exhibit excellent water vapor barrier properties in terms of performance, can be used as a single solution from the viewpoint of operability, and have excellent storage stability.

特開２０００－１１９５２８JP 2000-119528 特開２００２－１３８３９４JP-A-2002-138394 特開平８－１７６９９２Japanese Patent Application Laid-Open No. 8-176992

　本発明は、紙やフィルムなどの基材上に水蒸気バリア性に優れた塗膜を形成し、操業性の観点からは１液で使用可能であり、かつ保存安定性に優れる、エマルション組成物の製造方法を提供することを目的とする。 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.

　本発明者らは、前記課題について鋭意検討した結果、水蒸気バリア性を発現し、かつ保存安定性に優れるエマルション組成物の製造方法を見出した。 As a result of diligent studies on the above-mentioned problems, the present inventors have found a method for producing an emulsion composition which exhibits a water vapor barrier property and is excellent in storage stability.

　すなわち、本発明は、
＜１＞水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、下記（１）または（２）の条件を満足することを特徴とするエマルション組成物の製造方法、
（１）界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含むこと
（２）乳化重合時に、グリシジルメタクリレート（Ｅ）を含むこと
＜２＞水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含むことを特徴とするエマルション組成物の製造方法、
＜３＞水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、乳化重合時に、グリシジルメタクリレート（Ｅ）を含むことを特徴とするエマルション組成物の製造方法、
＜４＞エマルション組成物に含まれるポリマー成分に対するパラフィンワックス（Ｃ）の比率が２～１０質量％であることを特徴とする、前記＜１＞～＜３＞いずれか一項に記載のエマルション組成物の製造方法、
＜５＞ビニル基含有モノマー混合物（Ｄ）に対するスルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）の比率が０．５～５質量％であることを特徴とする、前記＜１＞または＜２＞に記載のエマルション組成物の製造方法、
＜６＞ビニル基含有モノマー混合物（Ｄ）に対するグリシジルメタクリレート（Ｅ）の比率が０．５～１０質量％であることを特徴とする、前記＜１＞または＜３＞に記載のエマルション組成物の製造方法、
＜７＞界面活性剤（Ｂ）が、カルボキシ基含有ビニルポリマー（Ｂ２）を含み、ビニル基含有モノマー混合物（Ｄ）／カルボキシ基含有ビニルポリマー（Ｂ２）＝６０～８０／２０～４０（質量％）であることを特徴とする、前記＜１＞～＜３＞いずれか一項に記載のエマルション組成物の製造方法、
＜８＞４０℃静置１日後に対する４０℃静置２８日後の、エマルション組成物の２５℃における粘度変化率（％）が、－１０～１０％であることを特徴とする、前記＜１＞～＜７＞いずれか一項に記載のエマルション組成物の製造方法、
である。 That is, 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. Is a method for producing an emulsion composition obtained by
A method for producing an emulsion composition, wherein 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 condition of (1) or (2) below is satisfied.
(1) 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. And,
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. Is a method for producing an emulsion composition obtained by
A method for producing an emulsion composition, wherein 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 glycidyl methacrylate (E) is contained at the time of emulsion polymerization.
<4> The emulsion composition according to any one of <1> to <3>, wherein the ratio of the paraffin wax (C) to the polymer component contained in the emulsion composition is 2 to 10% by mass. Manufacturing method of things,
<5> The above <1> or <2>, wherein the ratio of the low molecular weight emulsifier (B1) having a sodium sulfonate group to the vinyl group-containing monomer mixture (D) is 0.5 to 5% by mass. The method for producing an emulsion composition according to the above,
<6> The emulsion composition according to <1> or <3>, wherein the ratio of glycidyl methacrylate (E) to the vinyl group-containing monomer mixture (D) is 0.5 to 10% by mass. Production method,
<7> The surfactant (B) contains a carboxy group-containing vinyl polymer (B2), and the vinyl group-containing monomer mixture (D) / carboxy group-containing vinyl polymer (B2) = 60 to 80/20 to 40 (mass%). ), The method for producing an emulsion composition according to any one of <1> to <3>.
<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%. <7> The method for producing an emulsion composition according to any one of the above.
Is.

　本発明で得られるエマルションを用いることにより、紙やフィルム基材の水蒸気バリア性を高めることが可能であり、このエマルションは保存安定性に優れ、１液で目的の性能を得られることから、操業性を改善することが出来る。 By using 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.

　以下に本発明のエマルション組成物の製造方法について、具体的に説明する。 The method for producing the emulsion composition of the present invention will be specifically described below.

　本発明のエマルション組成物の製造方法で用いられる原料は、少なくとも、水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）と、ビニル基含有モノマー混合物（Ｄ）である。 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).

＜水（Ａ）＞
　本発明で使用する水（Ａ）は、ビニル基含有モノマー混合物（Ｄ）の乳化重合時に使用することから、ラジカル重合を阻害しない、イオン交換水、軟水が好ましい。 <Water (A)>
Since the water (A) used in the present invention is used during the emulsion polymerization of the vinyl group-containing monomer mixture (D), ion-exchanged water and soft water that do not inhibit radical polymerization are preferable.

＜界面活性剤（Ｂ）＞
　本発明で使用する界面活性剤（Ｂ）は、発明の効果を損なわない限り、後述する（１）、（２）の条件に応じて適宜選択され、イオン性やその化学種、分子量、使用量など特に制限なく使用することができる。なお、本発明において、低分子乳化剤、高分子乳化剤はいずれも乳化重合に用いることのできる界面活性剤を意味し、高分子乳化剤はラジカル重合により合成するポリマーと天然に存在する高分子からなるものを指し、低分子乳化剤はそれ以外の乳化剤を指す。 <Surfactant (B)>
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. In the present invention, 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. And low molecular weight emulsifiers refer to other emulsifiers.

＜融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）＞
　本発明で使用する融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）は、その融点が本発明で規定する範囲にあれば特に限定されない。なお、本発明でパラフィンワックスとは、常温において固体（蝋状）で水に不溶な炭素数２０以上のノルマルパラフィンの混合物を指す。入手可能な融点が５７～７１℃の範囲であるパラフィンワックスとしては、例えば、日本精蝋株式会社製の商品名「Ｐａｒａｆｆｉｎ　ＷＡＸ」シリーズ（１３５（融点５９℃）、１４０（同６１℃）、１４５（同６３℃）、１５０（同６６℃）、１５５（同６９℃））などが挙げられる。 <Paraffin wax (C) having a melting point in the range of 57 to 71 ° C>
The paraffin wax (C) having a melting point in the range of 57 to 71 ° C. used in the present invention is not particularly limited as long as the melting point is in the range specified in the present invention. 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. As 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.

　本発明で使用する融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）は、水蒸気バリア性の観点から、エマルション組成物に含まれるポリマー成分に対するパラフィンワックス（Ｃ）の比率が２～１０質量％であることが好ましい。なお、本発明でエマルション組成物に含まれるポリマー成分とは、後述するビニル基含有モノマー混合物（Ｄ）を乳化重合した共重合物および高分子乳化剤であるカルボキシ基含有ビニルポリマー（Ｂ２）を指す。 In the paraffin wax (C) having a melting point in the range of 57 to 71 ° C. used in the present invention, 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. In the present invention, 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.

　＜ビニル基含有モノマー混合物（Ｄ）＞
　本発明でビニル基含有モノマーとは、後述するグリシジルメタクリレート（Ｅ）を除くビニル基含有モノマーを指す。本発明の効果を損なわない限り、特に限定はされないが、２０℃での水への溶解度が２質量％未満である疎水性モノマーが好ましい。スチレン類やアルキル基の炭素数が１～８である（メタ）アクリル酸アルキルエステル類が好ましい。スチレン類としてはスチレン、αメチルスチレン、アルキル基の炭素数が１～８である（メタ）アクリル酸エステル類としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシルが挙げられ、これらビニル基含有モノマーを１種または２種以上混合して用いる。より好ましくは、スチレン、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシルから選ばれる１種または２種以上である。また、疎水性モノマー以外のモノマーとして、アクリル酸、メタクリル酸等のアニオン性モノマー、アクリルアミド、ダイアセトンアクリルアミド等のノニオン性モノマーが使用できる。 <Vinyl group-containing monomer mixture (D)>
In the present invention, 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, α-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. Further, as the monomer other than the hydrophobic monomer, an anionic monomer such as acrylic acid and methacrylic acid, and a nonionic monomer such as acrylamide and diacetoneacrylamide can be used.

　本発明のエマルション組成物の製造方法においては、水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合する際に、乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上である必要がある。パラフィンワックスの融点未満で重合するとパラフィンワックスの状態が液体で無いために、ポリマー粒子に組み込まれ難くなる。このため、得られるエマルション組成物は経時で分離を起こすおそれがある。 In the method for producing an emulsion composition of the present invention, 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. When the mixture (D) is emulsion-polymerized, 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.

　また、本発明のエマルション組成物の製造方法においては、更に、保存安定性の観点から少なくとも下記（１）または（２）の条件を満足する必要がある。
（１）界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含むこと
（２）乳化重合時に、グリシジルメタクリレート（Ｅ）を含むこと
前記（１）、（２）の条件をいずれも満足しない場合、得られるエマルション組成物の保存安定性に劣るため、高温下では経時での増粘や分離を起こすおそれがある。以下、前記（１）、（２）の条件それぞれに対応する本発明の製造方法の態様について説明する。 Further, in the method for producing an emulsion composition of the present invention, it is necessary to further satisfy at least the following conditions (1) or (2) from the viewpoint of storage stability.
(1) 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. Hereinafter, embodiments of the manufacturing method of the present invention corresponding to each of the above conditions (1) and (2) will be described.

＜（１）の条件における態様＞
　前記（１）の条件においては、界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含む必要がある。スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ1）としては、アルキルベンゼンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、アルキルアリルスルホコハク酸ナトリウム、ナフタレンスルホン酸ナトリウムのホルマリン縮合物等が挙げられる。好ましくは、塗膜の耐水性の観点から、ポリオキシアルキレン（ポリオキシエチレン、ポリオキシプロピレンなど）アルキル（またはアルケニル）エーテル構造を有しないスルホン酸ナトリウム基を有する低分子乳化剤であり、より好ましくは、アルキル基の炭素数が１０～１４であるアルキルベンゼンスルホン酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ナフタレンスルホン酸ナトリウムのホルマリン縮合物である。ビニル基含有モノマー混合物（Ｄ）に対するスルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）の比率は０．５～５質量％であることが好ましい。 <Aspect in the condition of (1)>
Under the condition (1), the surfactant (B) needs to contain a small molecule emulsifier (B1) having a sodium sulfonate group. Examples of the low molecular weight emulsifier (B1) having a sodium sulfonate group 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. , A formalin condensate of sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, and sodium naphthalene sulfonate having an alkyl group having 10 to 14 carbon atoms. 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.

＜（２）の条件における態様＞
　前記（２）の条件においては、乳化重合時に、グリシジルメタクリレート（Ｅ）を含む必要がある。ビニル基含有モノマー混合物（Ｄ）に対するグリシジルメタクリレート（Ｅ）の比率は、０．５～１０質量％であることが好ましい。 <Aspect in the condition of (2)>
Under the condition (2) above, it is necessary to include glycidyl methacrylate (E) at the time of emulsion polymerization. The ratio of glycidyl methacrylate (E) to the vinyl group-containing monomer mixture (D) is preferably 0.5 to 10% by mass.

　前記（１）、（２）の条件とも、塗膜の耐水性の観点から、界面活性剤（Ｂ）は、高分子乳化剤としてカルボキシ基含有ビニルポリマー（Ｂ２）を含むことが好ましい。とりわけ、前記（１）、（２）の条件を共に満足した場合において、更にカルボキシ基含有ビニルポリマー（Ｂ２）を含むと、本発明で得られるエマルション組成物を基材に塗工した塗膜は、より水蒸気バリア性に優れるものとなる。 In both of the above conditions (1) and (2), from the viewpoint of water resistance of the coating film, the surfactant (B) preferably contains a carboxy group-containing vinyl polymer (B2) as a polymer emulsifier. In particular, when both the conditions (1) and (2) are satisfied, and further containing the carboxy group-containing vinyl polymer (B2), 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.

　高分子乳化剤であるカルボキシ基含有ビニルポリマー（Ｂ２）としては、（メタ）アクリル酸やマレイン酸などのカルボキシ基を有するビニルモノマーが共重合成分として用いられているスチレンアクリル樹脂やアクリル樹脂、スチレンマレイン酸樹脂などが挙げられる。本発明のエマルションの製造方法においては、カルボキシ基含有ビニルポリマー（Ｂ２）をアンモニア、有機アミン、水酸化ナトリウム等の塩基性物質で中和することにより水溶化して用いる。乳化重合安定性や、得られるエマルションの濃度、ハンドリングの観点から、重量平均分子量が５０００～３００００の範囲が好ましく、酸価は１００～３００の範囲が好ましく、耐水性の観点から、アンモニアや有機アミンで中和することが好ましい。 As 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. In the method for producing an emulsion of the present invention, 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. From the viewpoint of emulsion polymerization stability, the concentration of the obtained emulsion, and handling, the weight average molecular weight 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.

　界面活性剤（Ｂ）にカルボキシ基含有ビニルポリマー（Ｂ２）を用いる場合は、前記（１）、（２）の条件に関わらず、塗膜の耐水性の観点から、ビニル基含有モノマー混合物（Ｄ）／カルボキシ基含有ビニルポリマー（Ｂ２）＝６０～８０／２０～４０（質量％）であることが好ましい。 When a carboxy group-containing vinyl polymer (B2) is used as the surfactant (B), 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). ) / Carboxy group-containing vinyl polymer (B2) = 60 to 80/20 to 40 (% by mass).

　本発明のエマルション組成物の製造方法においては、従来公知の乳化重合の方法を適用することが出来る。例えば、攪拌機、および窒素ガス導入管を備えた反応容器に、水（Ａ）、界面活性剤（Ｂ）、パラフィンワックス（Ｃ）を仕込み、重合開始剤として過硫酸アンモニウム、過硫酸カリウム、過酸化水素等の過酸化物、あるいはこれらの過酸化物と硫酸亜鉄、重亜硫酸ソーダ、アスコルビン酸、アスコルビン酸ナトリウム等の還元剤との組み合わせからなる任意のレドックス開始剤を使用し、ビニル基含有モノマー混合物（Ｄ）を６０～１８０分間かけて滴下し、滴下終了後６０～４８０分間反応させることで、エマルション組成物を得ることが出来る。必要に応じて、ビニル基含有モノマー混合物（Ｄ）の反応時に、アルキルメルカプタンなどの公知の連鎖移動剤を併用してもよい。ただし、乳化重合の反応温度をパラフィンワックス（Ｃ）の融点以上の温度で行うことを必須とする。 In the method for producing an emulsion composition of the present invention, a conventionally known method of emulsion polymerization can be applied. For example, 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. If necessary, 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). However, it is essential that 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).

　本発明のエマルション組成物の製造方法で得られるエマルション組成物は、本発明の課題である保存安定性の観点から、その指標として、４０℃静置１日後に対する４０℃静置２８日後の、エマルション組成物の２５℃における粘度変化率（％）が、－１０～１０％であることが好ましい。 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%.

　本発明で得られるエマルション組成物は、水性コート剤として有用であり、必要に応じてイソプロピルアルコール（ＩＰＡ）やブチルセルソルブなどの汎用の有機溶剤や、フィラー、ワックス、造膜助剤、レベリング剤、消泡剤、防腐剤を添加することが出来る。 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.

　本発明で得られるエマルション組成物を水性コート剤の原料として使用する際、対象となる基材は紙の様な吸収性基材に加えて、ＰＥＴ、ポリエチレン、ポリプロピレン等の非吸収性基材に対しても使用することが出来る。 When the emulsion composition obtained in the present invention is used as a raw material for an aqueous coating agent, 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.

　以下、実施例および比較例により、本発明を詳細に説明する。なお、％は特に記載がない限り、質量％である。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. Unless otherwise specified,% is mass%.

＜パラフィンワックス（Ｃ）の融点の測定＞
　融点については示差走査熱量測定計を使用し以下の条件で測定した。
　装置：ティー・エイ・インスツルメントジャパン製　ＤＩＳＣＯＶＥＲＹ　ＤＳＣ２５
　昇温速度：１０℃／分
　測定温度範囲：０～２００℃
＜分子量の測定＞
　重量平均分子量については以下の条件によりＧＰＣ法で測定した。
装置：ＨＬＣ－８３２０ＧＰＣ
カラム：東ソー製　ＴＳＫ－ｇｅｌ　ＳＵＰＥＲ　ＭＵＬＴＩＰＯＲＥ　ＨＺ－ＨとＳＵＰＥＲ　ＭＵＬＴＩＰＯＲＥ　ＨＺ－Ｍを連結して使用
溶離液：テトラヒドロフラン、０．３５ｍＬ／分
＜酸価の測定＞
　酸価については、試料を０．１ｇ採取し、５０ｍＬのテトラヒドロフランに溶解した後、指示薬としてフェノールフタレインを数滴加え、撹拌下、０．５Ｎ水酸化カリウムエタノール溶液を、淡赤色に呈色するまで滴下した。
酸価　＝　
滴下した０．５Ｎ水酸化カリウムエタノール溶液の量（ｍＬ）×０．５×５６．１１／試料（ｇ）
＜粘度の測定＞
Ｂ型粘度を用いて２５℃で測定した。 <Measurement of melting point of paraffin wax (C)>
The melting point was measured under the following conditions using a differential scanning calorimeter.
Equipment: DISCOVERY DSC25 made by TA Instruments Japan
Temperature rise rate: 10 ° C / min Measurement temperature range: 0 to 200 ° C
<Measurement of molecular weight>
The weight average molecular weight was measured by the GPC method under the following conditions.
Equipment: HLC-8320GPC
Column: Used by connecting TSK-gel SUPER MULTIPORE HZ-H and SUPER MULTIPORE HZ-M manufactured by Tosoh Eluent: Tetrahydrofuran, 0.35 mL / min <Measurement of acid value>
Regarding the acid value, 0.1 g of the sample is collected, dissolved in 50 mL of tetrahydrofuran, a few drops of phenolphthalein are added as an indicator, and the 0.5N potassium hydroxide ethanol solution is colored pale red with stirring. Dropped up to.
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.

＜カルボキシ基含有ビニルポリマー（Ｂ２）の合成＞
（合成例１）
　温度計、冷却管、撹拌機を有するセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート５００ｇを仕込み、窒素置換下で、１４５℃まで昇温した。次いで、スチレン１７５ｇ、αメチルスチレン２００ｇ、アクリル酸１２５ｇ、ジターシャリーブチルパーオキサイド７．５ｇの混合液を１２０分間かけて滴下した。滴下終了から６０分後、常圧蒸留および減圧蒸留を行い、プロピレングリコールモノメチルエーテルアセテートを留去して、重量平均分子量１００００、酸価１９５ｍｇＫＯＨ／ｇのカルボキシ基含有ビニルポリマー（Ｂ２ａ）を得た。 <Synthesis of carboxy group-containing vinyl polymer (B2)>
(Synthesis Example 1)
500 g of propylene glycol monomethyl ether acetate was placed in a separable flask having a thermometer, a cooling tube and a stirrer, and the temperature was raised to 145 ° C. under nitrogen substitution. Then, a mixed solution of 175 g of styrene, 200 g of α-methylstyrene, 125 g of acrylic acid, and 7.5 g of jittery butyl peroxide was added dropwise over 120 minutes. After 60 minutes from the completion of the dropping, atmospheric distillation and vacuum distillation were carried out to distill off propylene glycol monomethyl ether acetate to obtain a carboxy group-containing vinyl polymer (B2a) having a weight average molecular weight of 10,000 and an acid value of 195 mgKOH / g.

（合成例２）
　温度計、冷却管、撹拌機を有するセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート５００ｇを仕込み、窒素置換下で、１４５℃まで昇温した。次いで、スチレン２５０ｇ、アクリル酸２－エチルヘキシル１２５ｇ、アクリル酸１２５ｇ、ジターシャリーブチルパーオキサイド７．５ｇの混合液を１２０分間かけて滴下した。滴下終了から６０分後、常圧蒸留および減圧蒸留を行い、プロピレングリコールモノメチルエーテルアセテートを留去して、重量平均分子量１４５００、酸価１９６ｍｇＫＯＨ／ｇのカルボキシ基含有ビニルポリマー（Ｂ２ｂ）を得た。 (Synthesis Example 2)
500 g of propylene glycol monomethyl ether acetate was placed in a separable flask having a thermometer, a cooling tube and a stirrer, and the temperature was raised to 145 ° C. under nitrogen substitution. Then, a mixed solution of 250 g of styrene, 125 g of 2-ethylhexyl acrylate, 125 g of acrylic acid, and 7.5 g of jittery butyl peroxide was added dropwise over 120 minutes. After 60 minutes from the completion of the dropping, atmospheric distillation and vacuum distillation were carried out to distill off propylene glycol monomethyl ether acetate to obtain a carboxy group-containing vinyl polymer (B2b) having a weight average molecular weight of 14500 and an acid value of 196 mgKOH / g.

＜エマルション組成物の調製＞
（実施例１）
　温度計、冷却管、撹拌機を有するセパラブルフラスコに、イオン交換水５００ｇ、カルボキシ基含有ビニルポリマー（Ｂ２ａ）１２１ｇ、２８％アンモニア水２５．６ｇを仕込み、９０℃で１２０分間かけて加熱しカルボキシ基含有ビニルポリマーの水溶液とした。次いで、窒素置換下で、低分子乳化剤（Ｂ１）としてネオゲンＳ２０（ドデシルベンゼンスルホン酸ナトリウム、第一工業製薬株式会社製、有効分２０％）２８．３ｇ、パラフィンワックス（Ｃ）として融点６９℃のパラフィンワックス（日本精蝋株式会社製、商品名Ｐａｒａｆｆｉｎ　ＷＡＸ１５５）２０．２ｇ（エマルション組成物に含まれるポリマー成分に対し５質量％）を加え、８０℃に保持した。重合開始剤として過硫酸アンモニウム１．７ｇをイオン交換水１７ｇに溶解した希釈液を添加し、５分後、ビニル基含有モノマー混合物（Ｄ）としてスチレン１４２ｇ、アクリル酸２－エチルヘキシル１４２ｇの混合液を１２０分間かけて滴下し乳化重合を行った。滴下終了から６０分後、過硫酸アンモニウム０．３ｇをイオン交換水３ｇに溶解した希釈液を添加した。滴下終了から１２０分後、冷却し、イオン交換水で４１％濃度に希釈して、エマルション組成物（１）を得た。 <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. Then, under nitrogen substitution, 28.3 g of neogen S20 (sodium dodecylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., effective content 20%) as a low molecular weight emulsifier (B1), and a paraffin wax (C) having a melting point of 69 ° C. 20.2 g of paraffin wax (manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin WAX155) (5% by mass based on the polymer component contained in the emulsion composition) was added and kept at 80 ° C. 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).

（実施例２）
　低分子乳化剤（Ｂ１）としてリカサーフＰ－１０（ジオクチルスルホコハク酸ナトリウム、新日本理化株式会社製、有効分７０％）８．１ｇを用いた以外は、実施例１と同様にして、エマルション組成物（２）を得た。 (Example 2)
Emulsion composition (same as in Example 1) except that 8.1 g of Ricasurf 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.

（実施例３）
　低分子乳化剤（Ｂ１）としてセルフロー１１０（ナフタレンスルホン酸ナトリウムのホルマリン縮合物、第一工業製薬株式会社製、有効分４０％）１４．３ｇを用いた以外は、実施例１と同様にして、エマルション組成物（３）を得た。 (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.

（実施例４）
　ビニル基含有モノマー混合物（Ｄ）の乳化重合時に、低分子乳化剤（Ｂ１）を用いず、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）５．７ｇを加えた以外は、実施例１と同様にして、エマルション組成物（４）を得た。 (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.

（実施例５）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２３ｇ、２８％アンモニア水を２６．０ｇ、ネオゲンＳ２０を２８．７ｇ、融点６９℃のパラフィンワックスを８．４ｇ（エマルション組成物に含まれるポリマー成分に対し２質量％）、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）５．７ｇを加えた以外は、実施例１と同様にして、エマルション組成物（５）を得た。 (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.

（実施例６）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２０ｇ、２８％アンモニア水を２５．３ｇ、ネオゲンＳ２０を２７．９ｇ、融点６９℃のパラフィンワックスを２０．３ｇ、スチレンを１４０ｇ、アクリル酸２－エチルヘキシルを１４０ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して５質量％となるグリシジルメタクリレート（Ｅ）５．６ｇを加えた以外は、実施例１と同様にして、エマルション組成物（６）を得た。 (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.

（実施例７）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１１４ｇ、２８％アンモニア水を２４．０ｇ、ネオゲンＳ２０を２６．６ｇ、融点６９℃のパラフィンワックスを３８．８ｇ（エマルション組成物に含まれるポリマー成分に対し１０質量％）、スチレンを１３３ｇ、アクリル酸２－エチルヘキシルを１３３ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して１０質量％となるグリシジルメタクリレート（Ｅ）５．３ｇを加え、過硫酸アンモニウム１．６ｇをイオン交換水１６ｇに溶解した希釈液で乳化重合を開始した以外は、実施例１と同様にして、エマルション組成物（７）を得た。 (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.

（実施例８）
　パラフィンワックス（Ｃ）として融点５９℃のパラフィンワックス（日本精蝋株式会社製、商品名Ｐａｒａｆｆｉｎ　ＷＡＸ１３５）２０．３ｇを用いた以外は、実施例６と同様にして、エマルション組成物（８）を得た。 (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.

（実施例９）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２２ｇ、２８％アンモニア水を２５．７ｇ、ネオゲンＳ２０を７．１ｇ（ビニル基含有モノマー混合物（Ｄ）に対して０．５質量％）、融点６９℃のパラフィンワックスを２０．４ｇ、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとした以外は、実施例１と同様にして、エマルション組成物（９）を得た。 (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.

（実施例１０）
　イオン交換水を４５０ｇ、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１１９ｇ、２８％アンモニア水を２５．１ｇ、ネオゲンＳ２０を６９．４ｇ（ビニル基含有モノマー混合物（Ｄ）に対して５質量％）、融点６９℃のパラフィンワックスを１９．８ｇ、スチレンを１３９ｇ、アクリル酸２－エチルヘキシルを１３９ｇとした以外は、実施例１と同様にして、エマルション組成物（１０）を得た。 (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.

（実施例１１）
　ビニル基含有モノマー混合物（Ｄ）の乳化重合時に、低分子乳化剤（Ｂ１）を用いず、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２２ｇ、２８％アンモニア水を２５．７ｇ、融点６９℃のパラフィンワックスを２０．５ｇ、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して０．５質量％となるグリシジルメタクリレート（Ｅ）１．４ｇを加えた以外は、実施例１と同様にして、エマルション組成物（１１）を得た。 (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.

（実施例１２）
　ビニル基含有モノマー混合物（Ｄ）の乳化重合時に、低分子乳化剤（Ｂ１）を用いず、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１１５ｇ、２８％アンモニア水を２４．３ｇ、融点６９℃のパラフィンワックスを２１．０ｇ、スチレンを１３４ｇ、アクリル酸２－エチルヘキシルを１３４ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して１０質量％となるグリシジルメタクリレート（Ｅ）２６．８ｇを加え、過硫酸アンモニウム１．６ｇをイオン交換水１６ｇに溶解した希釈液で乳化重合を開始した以外は、実施例１と同様にして、エマルション組成物（１２）を得た。 (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.

（実施例１３）
　カルボキシ基含有ビニルポリマー（Ｂ２）として、カルボキシ基含有ビニルポリマー（Ｂ２ｂ）を用いた以外は、実施例６と同様にして、エマルション組成物（１３）を得た。 (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).

（実施例１４）
　ビニル基含有モノマー混合物（Ｄ）として、メタクリル酸メチル９５ｇ、アクリル酸ブチル９２ｇ、アクリル酸２－エチルヘキシル９２ｇを用いた以外は、実施例６と同様にして、エマルション組成物（１４）を得た。 (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).

（実施例１５）
　温度計、冷却管、撹拌機を有するセパラブルフラスコに、窒素置換下でイオン交換水４４０ｇ、低分子乳化剤（Ｂ１）としてネオゲンＳ２０を３９．４ｇ、パラフィンワックス（Ｃ）として融点６９℃のパラフィンワックスを２０．１ｇ加え、８０℃に保持した。過硫酸アンモニウム２．４ｇをイオン交換水２４ｇに溶解した希釈液を添加し、５分後、ビニル基含有モノマー混合物（Ｄ）としてメタクリル酸メチル１７３ｇ、アクリル酸ブチル１５０ｇ、アクリル酸２－エチルヘキシル５５ｇ、アクリル酸１６ｇと、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）７．９ｇの混合液を１２０分間かけて滴下した。滴下終了から６０分後、過硫酸アンモニウム０．４ｇをイオン交換水４ｇに溶解した希釈液を添加した。滴下終了から１２０分後、２８％アンモニア水溶液１３．２ｇを添加した後、冷却し、イオン交換水で３９％濃度に希釈して、エマルション組成物（１５）を得た。 (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. 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 mixed solution of 16 g of acid and 7.9 g of glycidyl methacrylate (E), which was 2% by mass based on the vinyl group-containing monomer mixture (D), was added dropwise over 120 minutes. 60 minutes after the completion of the dropping, a diluted solution prepared by dissolving 0.4 g of ammonium persulfate in 4 g of ion-exchanged water was added. 120 minutes after the completion of the dropping, 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).

（実施例１６）
　アクリル酸をメタクリル酸に、２８％アンモニア水溶液を１１．１ｇとした以外は、実施例１５と同様にして、エマルション組成物（１６）を得た。 (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.

（実施例１７）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２４ｇ、２８％アンモニア水を２６．２ｇ、ネオゲンＳ２０を２９．０ｇ、融点６９℃のパラフィンワックスを４．２ｇ（エマルション組成物に含まれるポリマー成分に対し１質量％）、スチレンを１４５ｇ、アクリル酸２－エチルヘキシルを１４５ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）５．８ｇを加えた以外は、実施例１と同様にして、エマルション組成物（１７）を得た。 (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.

（実施例１８）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１１２ｇ、２８％アンモニア水を２３．６ｇ、ネオゲンＳ２０を２６．２ｇ、融点６９℃のパラフィンワックスを４５．８ｇ（エマルション組成物に含まれるポリマー成分に対し１２質量％）、スチレンを１３１ｇ、アクリル酸２－エチルヘキシルを１３１ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）５．２ｇを加え、過硫酸アンモニウム１．６ｇをイオン交換水１６ｇに溶解した希釈液で乳化重合を開始した以外は、実施例１と同様にして、エマルション組成物（１８）を得た。 (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.

（実施例１９）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２３ｇ、２８％アンモニア水を２６．０ｇ、ネオゲンＳ２０を１．４ｇ（ビニル基含有モノマー混合物（Ｄ）に対して０．１質量％）、融点６９℃のパラフィンワックスを２０．５ｇ、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとした以外は、実施例１と同様にして、エマルション組成物（１９）を得た。 (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.

　（実施例２０）
　イオン交換水を３９０ｇ、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１１５ｇ、２８％アンモニア水を２４．３ｇ、ネオゲンＳ２０を１３４．４ｇ（ビニル基含有モノマー混合物（Ｄ）に対して１０質量％）、融点６９℃のパラフィンワックスを１９．２ｇ、スチレンを１３４ｇ、アクリル酸２－エチルヘキシルを１３４ｇとし、過硫酸アンモニウム１．６ｇをイオン交換水１６ｇに溶解した希釈液で乳化重合を開始した以外は、実施例１と同様にして、エマルション組成物（２０）を得た。 (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.

（実施例２１）
　ビニル基含有モノマー混合物（Ｄ）の乳化重合時に、低分子乳化剤（Ｂ１）を用いず、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２３ｇ、２８％アンモニア水を２６．０ｇ、融点６９℃のパラフィンワックスを２０．５ｇ、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して０．１質量％となるグリシジルメタクリレート（Ｅ）０．３ｇを加えた以外は、実施例１と同様にして、エマルション組成物（２１）を得た。 (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.

（実施例２２）
　ビニル基含有モノマー混合物（Ｄ）の乳化重合時に、低分子乳化剤（Ｂ１）を用いず、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２３ｇ、２８％アンモニア水を２３．４ｇ、融点６９℃のパラフィンワックスを２１．３ｇ、スチレンを１２９ｇ、アクリル酸２－エチルヘキシルを１２９ｇとし、ビニル基含有モノマー混合物（Ｄ）に対して１５質量％となるグリシジルメタクリレート（Ｅ）３８．８ｇを加え、過硫酸アンモニウム１．６ｇをイオン交換水１６ｇに溶解した希釈液で乳化重合を開始した以外は、実施例１と同様にして、エマルション組成物（２２）を得た。 (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.

（比較例１）
　パラフィンワックス（Ｃ）として融点４８℃のパラフィンワックス（日本精蝋株式会社製、商品名Ｐａｒａｆｆｉｎ　ＷＡＸ１１５）２０．３ｇを用いた以外は、実施例６と同様にして、エマルション組成物（２３）を得た。 (Comparative 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.

　パラフィンワックス（Ｃ）として融点７７℃のパラフィンワックス（日本精蝋株式会社製、商品名ＨＮＰ－５１）２０．３ｇを用いた以外は、実施例６と同様にして、エマルション組成物（２４）を得た。 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.

（比較例３）
　乳化重合を６５℃（パラフィンワックス（Ｃ）の融点未満）で行った以外は、実施例６と同様にして、エマルション組成物（２５）を得た。 (Comparative 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)).

（比較例４）
　低分子乳化剤（Ｂ１）を使用せず、カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２３ｇ、２８％アンモニア水を２６．０ｇ、融点６９℃のパラフィンワックスを２０．５ｇ、スチレンを１４３ｇ、アクリル酸２－エチルヘキシルを１４３ｇとした以外は、実施例１と同様にして、エマルション組成物（２６）を得た。 (Comparative Example 4)
Without using a small molecule emulsifier (B1), 123 g of carboxy group-containing vinyl polymer (B2a), 26.0 g of 28% aqueous ammonia, 20.5 g of paraffin wax having a melting point of 69 ° C., 143 g of styrene, 2-acrylic acid The emulsion composition (26) was obtained in the same manner as in Example 1 except that the amount of ethylhexyl was 143 g.

（比較例５）
　カルボキシ基含有ビニルポリマー（Ｂ２ａ）を１２０ｇ、２８％アンモニア水を２５．３ｇ、低分子乳化剤（Ｂ１）に代えてスルホン酸ナトリウム基を含まない低分子乳化剤であるプルロニック（登録商標）Ｌ－３１（ＥＯＰＯブロック共重合物、ＡＤＥＫＡ株式会社製、有効分１００％）を５．６ｇ（ビニル基含有モノマー混合物（Ｄ）に対して２質量％）、融点６９℃のパラフィンワックスを２０．３ｇ、スチレンを１４０ｇ、アクリル酸２－エチルヘキシルを１４０ｇとした以外は、実施例１と同様にして、エマルション組成物（２７）を得た。 (Comparative Example 5)
120 g of carboxy group-containing vinyl polymer (B2a), 25.3 g of 28% aqueous ammonia, and Pluronic® L-31 (registered trademark), which is a low molecular weight emulsifier containing no sodium sulfonate group instead of the low molecular weight emulsifier (B1). EOPO block copolymer, manufactured by ADEKA Co., Ltd., effective content 100%) 5.6 g (2% by mass with respect to the vinyl group-containing monomer mixture (D)), paraffin wax having a melting point of 69 ° C., 20.3 g, and styrene. The emulsion composition (27) was obtained in the same manner as in Example 1 except that 140 g and 140 g of 2-ethylhexyl acrylate were used.

（比較例６）
　温度計、冷却管、撹拌機を有するセパラブルフラスコに、イオン交換水５００ｇ、カルボキシ基含有ビニルポリマー（Ｂ２ａ）１２０ｇ、２８％アンモニア水２５．３ｇを仕込み、９０℃で１２０分間かけて加熱した。次いで、窒素置換下で、低分子乳化剤（Ｂ１）としてネオゲンＳ２０を２７．９ｇ加え、８０℃に保持した。過硫酸アンモニウム１．７ｇをイオン交換水１７ｇに溶解した希釈液を添加し、５分後、ビニル基含有モノマー混合物（Ｄ）としてスチレン１４０ｇ、アクリル酸２－エチルヘキシル１４０ｇと、ビニル基含有モノマー混合物（Ｄ）に対して２質量％となるグリシジルメタクリレート（Ｅ）５．６ｇの混合液を１２０分間かけて滴下した。滴下終了から６０分後、過硫酸アンモニウム０．３ｇをイオン交換水３ｇに溶解した希釈液を添加した。滴下終了から１２０分後、３０℃まで冷却を行った後、パラフィンワックス（Ｃ）として融点６９℃のパラフィンワックスエマルションＥＭＵＳＴＥＲ１１５５（日本精蝋株式会社製、有効分４０％）５１ｇを加え、イオン交換水で４１％濃度に希釈して、エマルション組成物（２８）を得た。 (Comparative Example 6)
In a separable flask equipped with a thermometer, a cooling tube and a stirrer, 500 g of ion-exchanged water, 120 g of carboxy group-containing vinyl polymer (B2a) and 25.3 g of 28% ammonia water were charged and heated at 90 ° C. for 120 minutes. Then, under nitrogen substitution, 27.9 g of Neogen S20 as a small molecule emulsifier (B1) was added and kept at 80 ° 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. 120 minutes after the completion of dropping, after cooling to 30 ° C., 51 g of paraffin wax emulsion EMUSTER1155 (manufactured by Nippon Seiro Co., Ltd., effective content 40%) having a melting point of 69 ° C. was added as paraffin wax (C), and ion-exchanged water was added. Dilute to a concentration of 41% with the emulsion composition (28).

　　実施例１～２２、および比較例１～６で得られた各エマルション組成物（１）～（２８）の組成および物性を表１に示す。 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.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

　表中の略号：
＜界面活性剤（Ｂ）＞
　Ｂ１ａ：ドデシルベンゼンスルホン酸ナトリウム
　Ｂ１ｂ：ジオクチルスルホコハク酸ナトリウム
　Ｂ１ｃ：ナフタレンスルホン酸ナトリウムのホルマリン縮合物
　Ｂ２ａ：スチレン／αメチルスチレン／アクリル酸＝３５／４０／２５（質量％）の共重合体
　Ｂ２ｂ：スチレン／アクリル酸２－エチルヘキシル／アクリル酸＝５０／２５／２５（質量％）の共重合体
　ｂ１ｄ：エチレンオキサイドプロピレンオキサイドブロック共重合物
＜ビニル基含有モノマー混合物（Ｄ）のモノマー組成＞
　Ｄａ：スチレン／アクリル酸2-エチルヘキシル＝５０／５０（質量％）
　Ｄｂ：メタクリル酸メチル／アクリル酸ブチル／アクリル酸２－エチルヘキシル＝３４／３３／３３（質量％）
　Ｄｃ：メタクリル酸メチル／アクリル酸ブチル／アクリル酸２－エチルヘキシル／アクリル酸＝４４／３８／１４／４（質量％）
　Ｄｄ：メタクリル酸メチル／アクリル酸ブチル／アクリル酸２－エチルヘキシル／メタクリル酸＝４４／３８／１４／４（質量％） Abbreviations in the table:
<Surfactant (B)>
B1a: Sodium dodecylbenzene sulfonate B1b: Sodium dioctyl sulfosuccinate B1c: Formalin condensate of sodium naphthalene sulfonate B2a: Copolymer of styrene / α-methylstyrene / acrylic acid = 35/40/25 (% by mass) B2b: Styrene / 2-Ethylhexyl acrylate / Acrylic acid = 50/25/25 (% by mass) copolymer b1d: Ethylene oxide styrene oxide block copolymer <Monomer composition of vinyl group-containing monomer mixture (D)>
Da: Styrene / 2-ethylhexyl acrylate = 50/50 (% by mass)
Db: Methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate = 34/33/33 (% by mass)
Dc: Methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate / acrylic acid = 44/38/4/4 (mass%)
Dd: Methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid = 44/38/4/4 (mass%)

　実施例１～２２、および比較例１～６で得られた各エマルション組成物（１）～（２８）の保存安定性、水蒸気バリア性を表２に示す。 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.

＜保存安定性＞
　エマルション組成物を４０℃で静置した１日後および２８日後の２５℃における粘度の変化および、外観観察における分離の有無を確認することで評価した。なお、本発明においては、分離が発生しないことが必要レベルである。このため、保存安定性が４０℃静置１日後で分離した比較例３～６のエマルション組成物（２５）～（２８）については透湿度の評価を行わなかった。４０℃静置１日後に対する２８日後の粘度変化率（％）は、以下の式で求めた。
粘度変化率（％）＝（４０℃静置２８日後の粘度－４０℃静置１日後の粘度）／（４０℃静置１日後の粘度）×１００
粘度変化率（％）は－１０～１０％以内であることが好ましい。 <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 (%) after 28 days with respect to 1 day after standing at 40 ° C. was calculated by the following formula.
Viscosity change rate (%) = (Viscosity after 28 days of standing at 40 ° C. Viscosity after 1 day of standing at 40 ° C.) / (Viscosity after 1 day of standing at 40 ° C.) × 100
The viscosity change rate (%) is preferably within -10 to 10%.

＜塗工評価＞
　ワイヤーバー♯５を用いて、中性上質紙（坪量６５ｇ／ｍ２)、ＰＥＴ（ポリエステル）フィルムの片面にエマルション組成物（１）～（２４）を塗工した。塗工液の塗布量は９ｇ／ｍ２であった。塗工後、水蒸気バリア性の指標として透湿度を測定した。その結果を表２に示す。 <Coating evaluation>
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 . After coating, the moisture permeability was measured as an index of water vapor barrier property. The results are shown in Table 2.

＜透湿度＞
　ＪＩＳ　Ｚ０２０８（カップ法、４０℃、湿度９０％ＲＨ、２４時間）に準拠し評価を行った。透湿度の値が小さいほど、水蒸気バリア性に優れることを示す。なお、本発明において透湿度は、中性上質紙では１００以下、ＰＥＴフィルムでは１５以下が実用レベルである。 <Humidity permeability>
Evaluation was performed in accordance with JIS Z0208 (cup method, 40 ° C., humidity 90% RH, 24 hours). The smaller the moisture permeability value, the better the water vapor barrier property. In the present invention, the moisture permeability is 100 or less for neutral woodfree paper and 15 or less for PET film, which is a practical level.

　透湿度は塗工量を増やすことで向上させることもできるが、本発明の評価条件において、保存安定性と水蒸気バリア性の両方の性能をバランスよく有していることが好ましく、粘度変化率（％）が－７～７％以内、かつ透湿度が中性上質紙では５０以下、ＰＥＴフィルムでは１０以下であることがより好ましい。 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.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

　本発明の構成要件を全て満足する実施例１～２２は、パラフィンワックス（Ｃ）の融点が範囲外である比較例１、２、乳化重合を行う温度が範囲外である比較例３、条件（１）、（２）ともに満足しない比較例４、５、パラフィンワックス（Ｃ）存在下で乳化重合を行わない比較例６のように、本発明の構成要件を一つでも満足しない比較例に比べて、エマルションが分離することなく安定で、かつ水蒸気バリア性に優れていることがわかる。 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.

　実施例５、７と実施例１７、１８より、エマルション組成物に含まれるポリマー成分に対するパラフィンワックス（Ｃ）の比率が２～１０質量％の範囲にあると、水蒸気バリア性により優れ、粘度変化率も小さいことが分かる。 From Examples 5 and 7 and Examples 17 and 18, when the ratio of the paraffin wax (C) to the polymer component contained in the emulsion composition is in the range of 2 to 10% by mass, the water vapor barrier property is excellent and the viscosity change rate is excellent. It turns out that is also small.

　実施例９、１０と実施例１９、２０より、ビニル基含有モノマー混合物（Ｄ）に対するスルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）の比率が０．５～５質量％の範囲にあると、水蒸気バリア性により優れ、粘度変化率も小さいことが分かる。 From Examples 9 and 10 and Examples 19 and 20, 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.

　実施例１１、１２と実施例２１、２２より、ビニル基含有モノマー混合物（Ｄ）に対するグリシジルメタクリレート（Ｅ）の量が０．５～５質量％の範囲にあると、粘度変化率が小さく、より好ましい。 From Examples 11 and 12 and Examples 21 and 22, when the amount of glycidyl methacrylate (E) with respect to the vinyl group-containing monomer mixture (D) is in the range of 0.5 to 5% by mass, the viscosity change rate is smaller and more. preferable.

Claims (8)

水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、下記（１）または（２）の条件を満足することを特徴とするエマルション組成物の製造方法。
（１）界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含むこと
（２）乳化重合時に、グリシジルメタクリレート（Ｅ）を含むこと Obtained by 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 method for producing an emulsion composition.
A method for producing an emulsion composition, wherein 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 conditions (1) or (2) below are satisfied.
(1) The surfactant (B) contains a low molecular weight emulsifier (B1) having a sodium sulfonate group (2) contains glycidyl methacrylate (E) at the time of emulsion polymerization. 水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、界面活性剤（Ｂ）が、スルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）を含むことを特徴とするエマルション組成物の製造方法。 Obtained by 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 method for producing an emulsion composition.
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. A method for producing an emulsion composition. 水（Ａ）と、界面活性剤（Ｂ）と、融点が５７～７１℃の範囲であるパラフィンワックス（Ｃ）の存在下に、ビニル基含有モノマー混合物（Ｄ）を乳化重合することにより得られるエマルション組成物の製造方法であって、
乳化重合を行う温度が乳化重合時に存在するパラフィンワックス（Ｃ）の融点以上であり、かつ、乳化重合時に、グリシジルメタクリレート（Ｅ）を含むことを特徴とするエマルション組成物の製造方法。 Obtained by 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 method for producing an emulsion composition.
A method for producing an emulsion composition, wherein 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 glycidyl methacrylate (E) is contained at the time of emulsion polymerization. エマルション組成物に含まれるポリマー成分に対するパラフィンワックス（Ｃ）の比率が２～１０質量％であることを特徴とする、請求項１～３いずれか一項に記載のエマルション組成物の製造方法。 The method for producing an emulsion composition according to any one of claims 1 to 3, wherein the ratio of the paraffin wax (C) to the polymer component contained in the emulsion composition is 2 to 10% by mass. ビニル基含有モノマー混合物（Ｄ）に対するスルホン酸ナトリウム基を有する低分子乳化剤（Ｂ１）の比率が０．５～５質量％であることを特徴とする、請求項１または２に記載のエマルション組成物の製造方法。 The emulsion composition according to claim 1 or 2, wherein the ratio of the low molecular weight emulsifier (B1) having a sodium sulfonate group to the vinyl group-containing monomer mixture (D) is 0.5 to 5% by mass. Manufacturing method. ビニル基含有モノマー混合物（Ｄ）に対するグリシジルメタクリレート（Ｅ）の比率が０．５～１０質量％であることを特徴とする、請求項１または３に記載のエマルション組成物の製造方法。 The method for producing an emulsion composition according to claim 1 or 3, wherein the ratio of glycidyl methacrylate (E) to the vinyl group-containing monomer mixture (D) is 0.5 to 10% by mass. 界面活性剤（Ｂ）が、カルボキシ基含有ビニルポリマー（Ｂ２）を含み、ビニル基含有モノマー混合物（Ｄ）／カルボキシ基含有ビニルポリマー（Ｂ２）＝６０～８０／２０～４０（質量％）であることを特徴とする、請求項１～３いずれか一項に記載のエマルション組成物の製造方法。 The surfactant (B) contains a carboxy group-containing vinyl polymer (B2), and is a vinyl group-containing monomer mixture (D) / carboxy group-containing vinyl polymer (B2) = 60 to 80/20 to 40 (% by mass). The method for producing an emulsion composition according to any one of claims 1 to 3, wherein the emulsion composition is produced. ４０℃静置１日後に対する４０℃静置２８日後の、エマルション組成物の２５℃における粘度変化率（％）が、－１０～１０％であることを特徴とする、請求項１～７いずれか一項に記載のエマルション組成物の製造方法。 Any of claims 1 to 7, wherein the viscosity change rate (%) of the emulsion composition at 25 ° C. after 28 days of standing at 40 ° C. for 1 day after standing at 40 ° C. is −10 to 10%. The method for producing an emulsion composition according to item 1.
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