Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09D133/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

• the present invention relates to an emulsion composition capable of forming a coating film having excellent water resistance and oil resistance on a substrate, an aqueous coating agent containing the emulsion composition, and a method for producing the emulsion composition.
• Laminated films using plastics such as polyethylene represented by food packaging are widely used because they have excellent water resistance and oil resistance.
• plastics such as polyethylene represented by food packaging
• it is difficult to recycle these laminated wrapping papers, and in recent years, there has been an increasing demand for deplasticization as an environmentally friendly effort.
• An object of the present invention is to provide an emulsion composition having both excellent water resistance and oil resistance, an aqueous coating agent containing the emulsion composition, and a method for producing the emulsion composition.
• the present inventors use methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, which are general-purpose monomers that can be used in radical polymerization, in a specific ratio without using a fluororesin or an ethylene (meth) acrylate polymer.
• methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate which are general-purpose monomers that can be used in radical polymerization, in a specific ratio without using a fluororesin or an ethylene (meth) acrylate polymer.
• the present invention (1) An emulsion composition containing water (A) and a copolymer (B) of a monomer containing at least methyl methacrylate (b1), butyl acrylate (b2), and 2-ethylhexyl acrylate (b3).
• the ratio of the copolymer (B) contained in the emulsion composition is 1 to 60% by mass, and it is calculated from the ratios of (b1), (b2), and (b3) constituting the copolymer (B).
• the glass transition temperature (Tg) to be formed is ⁇ 10 to ⁇ 45 ° C., and the proportion of (b1), (b2), and (b3) in the total polymer components contained in the emulsion composition is 70 to 100% by mass.
• An emulsion composition characterized by being present.
• Emulsion composition (3) The emulsion composition according to (1) or (2) above, wherein the copolymer (B) has a weight average molecular weight of 50,000 to 3,000,000.
• Emulsion composition containing a copolymer (B) obtained by emulsion polymerization of a monomer containing at least methyl methacrylate (b1), butyl acrylate (b2), and diethylhexyl acrylate (b3) in water.
• Tg glass transition temperature
• a method for producing an emulsion composition wherein the ratio of (b1), (b2), and (b3) to the total amount of monomers subjected to emulsion polymerization is 70 to 100% by mass.
• Tg glass transition temperature
• the total mass of b1), (b2), and (b3) is 70 to 100% by mass of the total mass of the monomer subjected to the polymerization of the polymer emulsifier (C) and the monomer subjected to the emulsion polymerization.
• both water resistance and oil resistance can be obtained at a high level, and deplasticization can be realized by substituting a laminated film.
• the emulsion composition of the present invention contains at least water (A) and a copolymer (B) of a monomer containing at least methyl methacrylate (b1), butyl acrylate (b2), and diethylhexyl acrylate (b3).
• A water
• B copolymer of a monomer containing at least methyl methacrylate (b1), butyl acrylate (b2), and diethylhexyl acrylate (b3).
• the water used in the present invention is preferably ion-exchanged water or soft water, and water that adversely affects radical polymerization cannot be used.
• the copolymer (B) of the present invention is a copolymer of a monomer containing at least methyl methacrylate (b1), butyl acrylate (b2), and 2-ethylhexyl acrylate (b3) as essential components.
• the skeleton derived from the component (b1), the component (b2), and the component (b3) constituting the copolymer (B) plays an important role in controlling the surface physical properties and the film forming property from the viewpoint of water resistance and oil resistance.
• the glass transition temperature (Tg) calculated from the ratio of the component (b1), the component (b2), and the component (b3) constituting the copolymer (B) needs to be ⁇ 10 to ⁇ 45 ° C.
• Tg in the formula is the glass transition temperature (K: Kelvin)
• W1, W2, W3 constitute the copolymer (B)
• vinyl group-containing monomers can be used up to 30% by mass of the total amount of the monomers used for the copolymer. ..
• examples of other vinyl group-containing monomers include nonionic monomers and ionic monomers.
• nonionic monomer examples include styrenes, (meth) acrylic acid alkyl esters other than (b1) to (b3), (meth) acrylamide, and the like.
• ionic monomer examples include (meth) acrylic acid and maleic acid.
• an emulsifying agent higher molecular weight emulsifying agent (C) or small molecule described later
• the weight average molecular weight of the copolymer (B) is preferably 50,000 to 3,000,000 from the viewpoint of water resistance, handling, and printability. Specifically, the weight average molecular weight is preferably 50,000 or more because the water resistance deteriorates as the molecular weight of the produced polymer decreases. On the other hand, since the emulsion viscosity increases as the molecular weight increases, the weight average molecular weight is preferably 3,000,000 or less from the viewpoint of handling and print coating suitability. In the present invention, the weight average molecular weight is 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
• the emulsion composition of the present invention may contain a copolymer other than the copolymer (B) such as the polymer emulsifier (C) described later, but accounts for all the polymer components contained in the emulsion composition (b1). ), (B2), and (b3) need to be 70 to 100% by mass because they have a great influence on the surface physical properties and film forming properties of the emulsion coating film as described in the copolymer (B). There is. If it is less than 70% by mass, both water resistance and oil resistance are significantly deteriorated.
• a copolymer other than the copolymer (B) such as the polymer emulsifier (C) described later
• the glass transition temperature (Tg (total)) of all the polymer components contained in the emulsion composition is less likely to cause the problem of blocking due to the adhesiveness of the coating film, and the emulsion is sufficiently formed only by the drying heat by the coating device.
• the range of ⁇ 45 ° C. to 40 ° C. is preferable because it can be used.
• Tg (total) in the formula is the glass transition temperature (K: Kelvin) of all polymer components contained in the emulsion composition.
• W1, W2 ... Wn is the mass fraction of each monomer constituting all the polymer components contained in the emulsion composition
• Tg1, Tg2 ... Tgn is the glass transition temperature of the homopolymer of each monomer. Represents.
• a polymer emulsifier (C) can be used, if necessary, for the purpose of stably emulsifying and dispersing the copolymer (B) in the emulsion composition.
• the polymer emulsifier anionic styrene acrylic resin or acrylic resin having a weight average molecular weight of 5,000 to 30,000 is neutralized with a basic compound such as ammonia, an organic amine, or sodium hydroxide to be water-soluble. Examples thereof include water-soluble resins such as polyacrylamide and starch.
• an anionic styrene acrylic resin having a weight average molecular weight of 5,000 to 30,000 or an ammonia neutralized product of an acrylic resin, which is generally used for emulsifying an acrylic emulsion, is preferable.
• the ratio of the copolymer (B) to the polymer emulsifier (C) does not reduce the water resistance due to the hydrophilicity of the polymer emulsifier and is emulsified.
• Copolymer (B): polymer emulsifier (C) 95: 5 to 50:50 is preferable, and 90: 10 to 60 is particularly preferable, because side reactions such as micellar external polymerization and emulsion aggregation are unlikely to occur in the polymerization. : 40 is preferable.
• both the copolymer (B) and the polymer emulsifier (C) were used at the time of each polymerization.
• the total ratio of only the monomer components constituting each is used without including the agent, the chain transfer agent and the basic compound used for neutralization.
• the emulsion composition of the present invention may contain a low molecular weight emulsifier as long as the effects of the present invention are not impaired.
• a commercially available nonionic emulsifier or anionic emulsifier described later can be used.
• the nonionic emulsifier include polyethylene oxide and polypropylene oxide compounds.
• the anionic emulsifier include sodium dodecylbenzene sulfonate, sodium polyoxyethylene styrenated phenol sulfate, and formalin condensates of sodium naphthalene sulfonate. These can be used up to 0.1 to 10% by mass with respect to the polymer contained in the emulsion composition.
• the copolymer (B) contains at least methyl methacrylate (b1), butyl acrylate (b2), and diethylhexyl acrylate (b3) in water (A). Obtained by emulsion polymerization of the monomer.
• the ratio of the component (b1), the component (b2), and the component (b3) in the monomer used for the emulsion polymerization needs to be 70 to 100% by mass because it greatly affects the surface physical properties and the film forming property of the emulsion coating film. There is.
• the copolymer (B) contains methyl methacrylate (b1), butyl acrylate (b2), and acrylic in water in the presence of the polymer emulsifier (C). It may be obtained by emulsion polymerization of a monomer containing at least 2 ethylhexyl acid (b3). (B1), (b2), and (b3) contained in the monomer subjected to the polymerization of the polymer emulsifier (C) and (b1), (b1), (b1) contained in the monomer subjected to the emulsion polymerization of the copolymer (B).
• the total masses of b2) and (b3) have a great influence on the surface physical properties and film forming properties of the emulsion coating film
• the total of the monomers used for the polymerization of the polymer emulsifier (C) and the monomers used for the emulsion polymerization It needs to be 70 to 100% by mass of the mass.
• a conventionally known method of emulsion polymerization can be applied.
• water (A) a high molecular weight emulsifier (C) or a low molecular weight emulsifier, if necessary, is charged in a reaction vessel equipped with a stirrer and a nitrogen gas introduction tube, and ammonium persulfate, potassium persulfate, and excess are used as polymerization initiators.
• any redox initiator consisting of peroxides such as hydrogen oxide or a combination of these peroxides with reducing agents such as iron sulfate, sodium bicarbonate, ascorbic acid, sodium ascorbate, etc. to control the reaction temperature.
• a mixture containing a monomer containing the components (b1) to (b3) and, if necessary, a known chain transfer agent such as alkyl mercaptan is added dropwise over 60 to 180 minutes, and 60 after completion of the addition.
• the emulsion composition can be obtained by reacting for about 480 minutes.
• the emulsion composition of the present invention is useful as a component of 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 coating base material is paper or paperboard, and specific examples thereof include cup base paper, food wrapping paper, kraft paper, liner paper, and high-quality paper.
• Examples of the coating conditions for the water-based coating agent include a method using a printing machine such as flexographic printing and gravure printing, and a method using a coating machine such as a roll coater, a size press, a blade coater, and a curtain coater.
• the amount of coating may be about 0.5 to 30 g / m 2 on one side of the base material with a solid content of the water-based coating agent, depending on the required level of water resistance and oil resistance.
• the drying method after coating is not particularly limited, and examples thereof include non-contact infrared drying, hot air drying, and contact cylinder drying.
• water-based coating agent is not particularly limited, but any application that requires water resistance and / or oil resistance is suitable for use, and in particular, applications in which water resistance and oil resistance have been obtained by conventional polyethylene laminating. It is suitable as an alternative to polyethylene laminate in.
• Example 1 Ion-exchanged water (563 g) was charged in a separable flask having a thermometer, a cooling tube and a stirrer, and the temperature was raised to 80 ° C. under nitrogen substitution. Then, a diluted solution prepared by dissolving ammonium persulfate (3.5 g) in ion-exchanged water (35 g) was added, and after 5 minutes, methyl methacrylate (154 g), butyl acrylate (133 g), and 2-ethylhexyl acrylate (49 g) were added. , Acrylic acid (14 g) mixed solution was added dropwise over 120 minutes.
• emulsion composition (1) having a viscosity of 350 mPa ⁇ s and a pH of 7.9.
• Example 2 An emulsion composition (2) having a viscosity of 950 mPa ⁇ s and a pH of 7.8 was obtained in the same manner as in Example 1 except that methacrylic acid (14 g) was used instead of acrylic acid (14 g).
• Example 3 In the same manner as in Example 1, except that ion-exchanged water (546 g) and Neogen S20 (17.5 g, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were used as the low molecular weight emulsifier instead of the ion-exchanged water (563 g).
• Example 4 Viscosity in the same manner as in Example 1 except that ion-exchanged water (560 g) was used instead of ion-exchanged water (563 g) and Neucol N2360 (3.5 g, manufactured by Nippon Emulsifier Co., Ltd.) was used as a low molecular weight emulsifier.
• Example 5 Methyl methacrylate (133 g), butyl acrylate (150.5 g), acrylic instead of methyl methacrylate (154 g), butyl acrylate (133 g), acrylic acid (14 g), 28% aqueous ammonia solution (10.6 g).
• An emulsion composition (5) having a viscosity of 260 mPa ⁇ s and a pH of 7.9 was obtained in the same manner as in Example 1 except that an acid (17.5 g) and a 28% aqueous ammonia solution (13.3 g) were used.
• Example 6 Methyl methacrylate (66.5 g), butyl acrylate (182 g), 2 ethyl hexyl acrylate (84 g) instead of methyl methacrylate (133 g), butyl acrylate (150.5 g), 2 ethyl hexyl acrylate (49 g).
• an emulsion composition (6) having a viscosity of 220 mPa ⁇ s and a pH of 7.9 was obtained in the same manner as in Example 5.
• Example 7 An emulsion composition (7) having a viscosity of 210 mPa ⁇ s and a pH of 7.9 was obtained in the same manner as in Example 5 except that Tashalead decylmercaptan (3.5 g) was further added to the monomer mixed solution as a chain transfer agent. ..
• Example 8 The emulsion composition (8) having a viscosity of 1650 mPa ⁇ s and a pH of 8.1 was prepared in the same manner as in Example 5 except that glycidyl methacrylate (3.5 g) was further added to the monomer mixed solution as another vinyl group-containing monomer. Obtained.
• Example 9 An emulsion composition (9) having a viscosity of 90 mPa ⁇ s and a pH of 7.9 was obtained in the same manner as in Example 5 except that Tashalead decylmercaptan (7.0 g) was further added to the monomer mixed solution as a chain transfer agent. ..
• Example 10 Ion-exchanged water (410 g), polymer emulsifier (1) (135 g), and 28% aqueous ammonia solution (25.6 g) were placed in a separable flask equipped with a thermometer, a condenser, and a stirrer, and 90% under nitrogen substitution. The temperature was raised to ° C. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (2.5 g) in ion-exchanged water (25 g) was added, and after 5 minutes, methyl methacrylate (157.5 g), butyl acrylate (75.6 g), and acrylate 2
• methyl methacrylate (157.5 g), butyl acrylate (75.6 g), and acrylate 2 A mixed solution of ethylhexyl (81.9 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.3 g) in ion-exchanged water (3 g) was added.
• an emulsion composition (10) having a viscosity of 380 mPa ⁇ s and a pH of 8.2.
• Example 11 Methyl methacrylate (63 g), butyl acrylate (163.8 g), 2 acrylate instead of methyl methacrylate (157.5 g), butyl acrylate (75.6 g), 2 ethylhexyl acrylate (81.9 g)
• An emulsion composition (11) having a viscosity of 360 mPa ⁇ s and a pH of 8.2 was obtained in the same manner as in Example 10 except that ethylhexyl (88.2 g) was used.
• Example 12 Ion-exchanged water (405 g), polymer emulsifier (1) (112.5 g), and 28% aqueous ammonia solution (21.4 g) were placed in a separable flask equipped with a thermometer, a condenser, and a stirrer under nitrogen substitution. , The temperature was raised to 90 ° C. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (2.7 g) in ion-exchanged water (27 g) was added, and after 5 minutes, methyl methacrylate (114.8 g), butyl acrylate (111.4 g), and acrylate 2
• a mixed solution of ethylhexyl (111.4 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.3 g) in ion-exchanged water (3 g) was added.
• an emulsion composition (12) having a viscosity of 310 mPa ⁇ s and a pH of 8.0.
• Example 13 An emulsion composition (13) having a viscosity of 610 mPa ⁇ s and a pH of 8.0 was obtained in the same manner as in Example 12 except that the polymer emulsifier (2) was used instead of the polymer emulsifier (1).
• Example 14 Ion-exchanged water (330 g), polymer emulsifier (3) (180 g), and 28% aqueous ammonia solution (34.2 g) were placed in a separable flask equipped with a thermometer, a condenser, and a stirrer, and 90% under nitrogen substitution. The temperature was raised to ° C. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (2.2 g) in ion-exchanged water (22 g) was added, and after 5 minutes, methyl methacrylate (91.8 g), butyl acrylate (89.1 g), and acrylate 2 were added.
• a mixed solution of ethylhexyl (89.1 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.3 g) in ion-exchanged water (3 g) was added.
• an emulsion composition (14) having a viscosity of 1420 mPa ⁇ s and a pH of 7.9.
• Example 15 Ion-exchanged water (410 g), polymer emulsifier (1) (45 g), and 28% aqueous ammonia solution (8.6 g) were charged in a separable flask equipped with a thermometer, a cooling tube, and a stirrer, and 90% under nitrogen substitution. The temperature was raised to ° C. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (3.2 g) in ion-exchanged water (32 g) was added, and after 5 minutes, methyl methacrylate (137.7 g), butyl acrylate (133.7 g), and acrylate 2
• a mixed solution of ethylhexyl (133.7 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.4 g) in ion-exchanged water (4 g) was added.
• Example 16 In a separable flask equipped with a thermometer, a cooling tube and a stirrer, ion-exchanged water (412 g), high molecular weight emulsifier (1) (22.5 g), and Neogen S20 (21.5 g) as a low molecular weight emulsifier, Dai-ichi Kogyo Seiyaku Co., Ltd. A 28% aqueous aqueous solution of ammonia (4.3 g) was charged (manufactured by the company), and the temperature was raised to 90 ° C. under nitrogen substitution. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (3.4 g) in ion-exchanged water (34 g) was added, and after 5 minutes, methyl methacrylate (145.4 g), butyl acrylate (141.1 g), and acrylate 2
• a mixed solution of ethylhexyl (141.1 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.4 g) in ion-exchanged water (4 g) was added.
• Example 17 Ion-exchanged water (398 g), polymer emulsifier (4) (225 g), and 28% aqueous ammonia solution (42.7 g) were placed in a separable flask equipped with a thermometer, a condenser, and a stirrer, and 90% under nitrogen substitution. The temperature was raised to ° C. After holding at 90 ° C. for 180 minutes, the mixture was cooled to 80 ° C.
• a diluted solution prepared by dissolving ammonium persulfate (1.8 g) in ion-exchanged water (18 g) was added, and after 5 minutes, methyl methacrylate (103.5 g), butyl acrylate (78.8 g), and acrylate 2
• methyl methacrylate (103.5 g), butyl acrylate (78.8 g), and acrylate 2 A mixed solution of ethylhexyl (42.8 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.2 g) in ion-exchanged water (2 g) was added.
• a diluted solution prepared by dissolving ammonium persulfate (2.3 g) in ion-exchanged water (23 g) was added, and after 5 minutes, methyl methacrylate (58.5 g), butyl acrylate (152.1 g), and acrylate 2
• methyl methacrylate (58.5 g), butyl acrylate (152.1 g), and acrylate 2 A mixed solution of ethylhexyl (81.9 g) was added dropwise over 120 minutes.
• a diluted solution prepared by dissolving ammonium persulfate (0.3 g) in ion-exchanged water (3 g) was added.
• an emulsion composition (21) having a viscosity of 860 mPa ⁇ s and a pH of 8.0.
• Table 1 shows the compositions and physical properties of the emulsion compositions (1) to (24) obtained in Examples 1 to 17 and Comparative Examples 1 to 7.
• Water repellency Evaluation was performed in accordance with JAPAN TAPPI No68. The evaluation of the water repellency (R0 to R10) shows the cases where the states shown below are obtained.
• R0 Continuous traces showing a uniform width
• R2 Continuous traces showing a width slightly narrower than water droplets
• R4 Continuous traces but broken in places, clearly more than water droplets
• Narrow width R6: Half of the trace is wet
• R7 1/4 of the trace is wet with long stretched water droplets
• R9 Small spherical water droplets scattered in places
• R10 Completely rolling down
• the water repellency is at a practical level of R6 to R10.
• Kit value Evaluation was performed in accordance with JAPAN TAPPI No41.
• the Kit value is in the range of 6 to 12 at a practical level.

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