Classifications

• • 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
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
  • C09D5/028—Pigments; Filters
• • 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
  • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated 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
• • 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
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C09D7/66—Additives characterised by particle size
  • C09D7/69—Particle size larger than 1000 nm
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/40—Glass

Definitions

• the present invention is used in the civil engineering / architecture field, where a glass filler is combined with a water-based synthetic resin emulsion to exhibit excellent drying properties, and a film excellent in water resistance, acid resistance and alkali resistance can be formed.
• Concrete structures are subject to deterioration under various environmental conditions, and various surface treatment materials are used for the purpose of improving durability.
• various surface treatment materials are used for the purpose of improving durability.
• the shift from solvent-based resins to water-based resins has been promoted in the trend of strengthening VOC regulations and the rapid increase in social environmental protection awareness.
• waterproofing and anticorrosion materials for concrete structures in the civil engineering and construction fields various problems such as regulations on odors and volatile components and regulations on raw materials used have been addressed due to environmental problems. Development as a waterproofing material and anticorrosion material of resin is required.
• composition for reinforced mortar characterized by containing glass fiber, cement, sand and the like in a vinyl acetate-ethylenic copolymer emulsion (see, for example, Patent Document 2).
• the mortar composition has a non-volatile content that is too high, the viscosity rapidly increases, and there is a problem in workability.
• an aqueous resin composition in which an organic filler is added to a synthetic resin emulsion for example, an adhesive containing at least one of a styrene-butadiene copolymer resin latex and a chloroprene rubber latex, and an acrylic resin powder (organic filler)
• the composition is disclosed (for example, refer patent document 3). This is for the purpose of being used as an adhesive, and is not for the purpose of forming a thick film unlike the waterproof / corrosive material of concrete structures.
• a vibration-damping composition characterized by containing an organic filler in a base emulsion using a core-shell emulsion has been disclosed (see, for example, Patent Document 4). Cracks may occur during formation.
• the present invention is capable of thick film construction on a surface to be treated such as a concrete structure and can be dried within 12 hours after coating, and the coated film has excellent durability, for example, water resistance,
• An object is to provide an aqueous resin composition for thick film construction having acid resistance and alkali resistance, and a surface treatment method using the same.
• the present invention relates to an aqueous resin composition for pressure membrane construction, which contains an aqueous synthetic resin emulsion (A) and a glass filler (B) and has a nonvolatile content of 65 to 80% by mass.
• the viscosity of the water-based resin composition for pressure membrane construction is preferably 8,000 mPa ⁇ s or more.
• a glass filler (B) is 25 mass% or more with respect to the non volatile matter of the water based resin composition for thick film construction.
• the solid content ratio of the water-based synthetic resin emulsion (A) and the glass filler (B) is preferably 7/3 to 3/7.
• the average particle size of the glass filler (B) is preferably 0.3 mm or less.
• the aqueous synthetic resin emulsion (A) is preferably a styrene-acrylic resin emulsion or an acrylic resin emulsion.
• the present invention provides a surface treatment to be treated, characterized in that a coating film having a film thickness of 0.1 to 2.0 mm is formed by applying an aqueous resin composition for thick film construction to the surface to be treated and drying it. Regarding the method.
• the present invention relates to a concrete structure surface treatment method characterized in that a water-based resin composition for thick film construction is applied to a concrete structure and dried.
• an aqueous resin composition for thick film construction that does not generate odor during work, is environmentally friendly, and has excellent water resistance, acid resistance, and alkali resistance.
• the aqueous synthetic resin emulsion (A) used in the present invention is an emulsion polymer that can be obtained by radical polymerization of an ethylenically unsaturated monomer composition using a water-soluble polymer or a surfactant. Or latex polymer.
• emulsion polymers include styrene-acrylic resin emulsions, acrylic resin emulsions, ethylene-vinyl acetate emulsions, vinyl acetate emulsions, urethane emulsions, and latex polymers include styrene-butadiene resin latexes.
• a suspension obtained by emulsifying and dispersing an organic resin in water can also be used in combination.
• styrene-acrylic resin emulsions and acrylic resin emulsions are preferred from the viewpoints of adjusting properties such as nonvolatile content of the water-based synthetic resin emulsion (A), Tg design of the resin, miscibility and physical properties.
• a styrene-acrylic resin emulsion is preferable because of excellent acid resistance and alkali resistance.
• the aqueous synthetic resin emulsion (A) used in the present invention is styrene that can be obtained by radical polymerization of an ethylenically unsaturated monomer composition in the presence of water-soluble or water-dispersible polyester.
• -Acrylic resin emulsion or acrylic resin emulsion are preferred because of its excellent acid resistance and alkali resistance.
• the amount of water-soluble or water-dispersible polyester is preferably 10% by mass to 30% by mass in terms of solid content in a synthetic resin emulsion obtained by polymerizing an ethylenically unsaturated monomer. More preferably, it is ⁇ 20% by mass.
• the water-soluble or water-dispersible polyester is less than 10% by mass, the polymerization stability may be lowered. On the other hand, when it exceeds 30% by mass, the water resistance may be lowered.
• the component derived from the styrene monomer is preferably 10 to 80% by mass, and more preferably 40 to 60% by mass.
• the content is less than 10% by mass, a decrease in toughness is observed as a film physical property.
• the content is more than 80% by mass, an increase in the amount of film forming auxiliary agent is required due to the problem of film forming property, causing a decrease in film physical properties. There is a tendency.
• the glass filler (B) used in the present invention means glass powder, and examples thereof include glass fiber, glass frit, glass flake, and glass beads. These may be used alone or in combination of two or more. Among these, glass frit and glass flake are preferable from the viewpoints of miscibility and durability.
• the shape of the cross section of the glass filler (B) includes, in addition to a general spherical shape, an irregular cross-sectional shape and a scale-like shape represented by glass flakes. Among them, a spherical shape is preferable from the viewpoint of miscibility and durability.
• the glass filler (B) used in the present invention is preferably used in an amount of 25% by mass or more, more preferably 30% by mass or more, and more preferably 45% by mass with respect to the nonvolatile content of the thick film construction aqueous resin composition. % Or more is particularly preferable, and 50% by mass or more is more preferable.
• the ratio of the glass filler (B) to the non-volatile content of the thick film construction water-based resin composition is less than 25% by mass, the thick film dryness tends to deteriorate and the water-stopping property, acid resistance, and alkali resistance tend to decrease.
• the average particle size of the glass filler (B) used in the present invention is preferably 0.3 mm or less, more preferably 1 ⁇ m to 100 ⁇ m from the viewpoint of dispersibility. If the average particle size is larger than 0.3 mm, a uniform dispersion in the resin cannot be obtained, a tendency to separate is observed, it becomes difficult to form a uniform film during film formation, and a decrease in film properties (strength and durability) is observed. It is done.
• an inorganic filler may be added in order to improve the viscosity within the range not impairing the object of the present invention.
• an inorganic filler known and conventional ones may be used.
• aluminum oxide and silica may be used alone or in combination of two or more.
• the organic filler means a powder of an organic polymer that is hardly soluble in water, and preferably has a solubility in 100 g of water at 23 ° C. and 1 atm of 0.1 g or less.
• the organic filler include polyethylene, polypropylene, polystyrene, polymethyl methacrylate and copolymers thereof, vinyl acetate and copolymers thereof, saturated polyester (aliphatic ester type / aromatic ester type), cellulose acetate butyrate, Examples thereof include ⁇ -caprolactone polymer, polybutadiene, and polyvinyl chloride.
• elastomeric polymers such as styrene-butadiene-styrene (SBS) block polymers, starch powder, cellulose powder and the like can be mentioned. These may be used alone or in combination of two or more. Among these, polystyrene, polyethylene, and polypropylene are preferable from the viewpoints of miscibility and durability.
• SBS styrene-butadiene-styrene
• the average particle size of the organic filler is preferably several ⁇ m to 300 ⁇ m from the viewpoint of dispersibility.
• the solid content ratio of the aqueous synthetic resin emulsion (A) and the glass filler (B) is preferably 7/3 to 3/7, and 6/4 to 4 / 6 is more preferable. If the solid content ratio of the water-based synthetic resin emulsion (A) and the glass filler (B) is larger than 7/3, that is, if the water-based synthetic resin emulsion (A) component is large, the expected drying property cannot be obtained, and the physical properties of the film Even in (strength etc.), good results cannot be obtained.
• the solid content ratio of the water-based synthetic resin emulsion (A) and the glass filler (B) is less than 3/7, that is, when the glass filler component is large, stability cannot be maintained, and uniform film formation is difficult. Therefore, it is difficult to obtain a sufficient effect in the durability of the film such as water resistance, acid resistance, and alkali resistance.
• a plasticizer e.g., ethylene glycol dimethacrylate copolymer (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate
• the minimum film formation temperature of the aqueous resin composition for thick film construction of the present invention is preferably 0 to 5 ° C., particularly preferably 0 ° C. If the temperature is higher than 5 ° C., the film tends to be affected by the drying temperature condition, so that the film formability is likely to be deteriorated, and sufficient film durability tends not to be obtained. Adjustment of the minimum film-forming temperature of the water-based resin composition for thick film construction can be achieved by adding a film-forming auxiliary or by synthesizing an aqueous synthetic resin emulsion (A) having a high minimum film-forming temperature with a low minimum film-forming temperature. It can be carried out by a method such as adding the resin emulsion (A).
• the water-based resin composition for thick film construction of the present invention preferably has a nonvolatile content of 65 to 80% by mass, and more preferably 65 to 70% by mass.
• a nonvolatile content of 65 to 80% by mass, and more preferably 65 to 70% by mass.
• the aqueous resin composition for thick film construction of the present invention preferably has a viscosity of 8,000 mPa ⁇ s or more, more preferably 9,000 to 60,000 mPa ⁇ s.
• a viscosity 8,000 mPa ⁇ s or more, more preferably 9,000 to 60,000 mPa ⁇ s.
• the aqueous resin composition for thick film construction of the present invention preferably has a film thickness of 0.1 to 2.0 mm, more preferably 0.3 to 1.5 mm after being applied to the surface to be treated and dried. . If the film thickness is less than 0.1 mm, there is an influence of the base, but the continuity of the film becomes insufficient due to the occurrence of pinholes, etc., and if it is more than 2.0 mm, it causes a drying delay, and sufficient performance cannot be exhibited. There is a tendency.
• the water-based resin composition for thick film construction of the present invention does not contain a solvent or the like, or contains only a small amount of a solvent or the like, and therefore does not generate odor during work, is environmentally friendly, and has excellent drying properties.
• a protective film having excellent physical properties such as water resistance, acid resistance and alkali resistance is formed. Therefore, it is thought that the durability of the surface to be treated is improved.
• the concrete structure is a concept including a structure made of ordinary concrete, mortar, or the like.
• Examples of the application method of the thick film construction aqueous resin composition of the present invention include spray coating, roller coating, and iron coating.
• the coating amount (solid content) may be determined as appropriate according to the purpose of protection, preferably 0.2kg / m 2 ⁇ 2.0kg / m 2, more preferably 0.3kg / m 2 ⁇ 1. 2 kg / m 2 .
• the coating amount can not form a sufficient film continuous layer is less than 0.2 kg / m 2, the occurrence of pinholes are concerned, also be a factor of drying retardant is more than 2.0 kg / m 2, sufficient Tend to cease to perform well.
• undercoat paint When applying the water-based resin composition for thick film construction of the present invention to a surface to be treated such as a concrete structure, it is also possible to use an undercoat paint.
• the undercoat paint include acrylic emulsion type undercoat paint (primer, sealer), epoxy type undercoat paint, urethane type, undercoat paint and the like. It can also be used as a cement-based primer.
• examples of the admixture include cement base preparation such as acrylic emulsion, ethylene-vinyl acetate emulsion, and epoxy emulsion.
• Non-volatile content About 1 g of the resin emulsion or aqueous resin composition was weighed on an aluminum dish having a diameter of 5 cm, dried at 105 ° C. for 1 hour, and the remainder was weighed.
• MFT Minimum deposition temperature
• a frame is created on a glass plate, and the water-based resin composition is poured into the glass plate so that the film thickness after drying is 2 mm.
• the surface is dried in an environment of 20 ° C. ⁇ 50% RH. The time until no trace was made was measured.
• Example 1 As an aqueous synthetic resin emulsion, emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50% by mass, styrene-derived component 50% by mass of resin component, acrylic acid ester-derived component 50% by mass, viscosity 4 , 500 mPa ⁇ s, minimum film forming temperature 0 ° C.), and glass frit CF0007-05B (manufactured by Nippon Frit Co., Ltd .: average particle size 5 ⁇ m) was used as the glass filler.
• emulsion (1) styrene-acrylic acid ester copolymer, nonvolatile content 50% by mass, styrene-derived component 50% by mass of resin component, acrylic acid ester-derived component 50% by mass, viscosity 4 , 500 mPa ⁇ s, minimum film forming temperature 0 ° C.
• glass frit CF0007-05B manufactured by Nippon Fri
• CF0007-05B 50 parts by mass of CF0007-05B was added to 100 parts by mass of the emulsion (1), and the mixture was stirred with a disper at 3,000 rpm for 20 minutes.
• 0.05 part by mass of an antifoaming agent Nopco 8034L: manufactured by San Nopco Co., Ltd.
• the obtained aqueous resin composition was filtered with an 80th filter cloth, and it was confirmed that there was no generation of coarse particles and aggregates.
• the aqueous resin composition of Example 1 was obtained by such a production method.
• the properties of the obtained aqueous resin composition were a non-volatile content of 66.7% by mass and a viscosity of 12,000 mPa ⁇ s.
• emulsion (2) poly(polyester-styrene-acrylic acid ester copolymer, nonvolatile content 51% by mass, polyester-derived component 10% by mass, styrene-derived component 40% by mass, acrylic acid Ester-derived component 50 mass%, viscosity 500 mPa ⁇ s, minimum film forming temperature 40 ° C.
• emulsion (3) styrene-acrylate copolymer, nonvolatile content 58 mass%, styrene-derived component in resin component 10% by mass, 90% by mass of an acrylate-derived component, a viscosity of 3,000 mPa ⁇ s, and a minimum film-forming temperature of 0 ° C.
• An aqueous resin composition was obtained in the same manner as in Example 1 except that 50 parts by mass of CF0007-05B was added to 50 parts by mass of emulsion (2) and 50 parts by mass of emulsion (3). MFT was adjusted by mixing emulsion (2) and emulsion (3).
• the properties of the obtained water-based resin composition were a non-volatile content of 69.3% by mass and a viscosity of 11,000 mPa ⁇ s.
• Example 3 As an aqueous synthetic resin emulsion, 100 parts by mass of emulsion (4) (acrylic ester polymer, nonvolatile content 50% by mass, viscosity 2,500 mPa ⁇ s, minimum filming temperature 2 ° C.) is used, and CF0007- Aqueous resin composition was prepared in the same manner as in Example 1 except that 50 parts by mass of 05B (manufactured by Nippon Frit Co., Ltd .: average particle size: 5 ⁇ m) and 2 parts by mass of Texanol CS-12 as a film forming aid were added. I got a thing. The properties of the obtained water-based resin composition were a non-volatile content of 66.7% by mass and a viscosity of 13,000 mPa ⁇ s.
• emulsion (4) acrylic ester polymer, nonvolatile content 50% by mass, viscosity 2,500 mPa ⁇ s, minimum filming temperature 2 ° C.
• Example 4 As an aqueous synthetic resin emulsion, 100 parts by mass of emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50% by mass, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.) is used as a glass filler. An aqueous resin composition was obtained in the same manner as in Example 1 except that 50 parts by mass of CF0002-30A (manufactured by Nippon Frit Co., Ltd .: average particle size 30 ⁇ m) was used. The properties of the obtained water-based resin composition were a non-volatile content of 66.7% by mass and a viscosity of 9,000 mPa ⁇ s.
• emulsion (1) styrene-acrylic acid ester copolymer, nonvolatile content 50% by mass, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.
• Example 5 As an aqueous synthetic resin emulsion, 100 parts by mass of emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50% by mass, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.) is used as a glass filler.
• a water-based resin composition was obtained in the same manner as in Example 1 except that 50 parts by mass of microglass glass flake RCF-150 (manufactured by Nippon Sheet Glass Co., Ltd .: average particle size 150 ⁇ m) was used.
• the properties of the obtained water-based resin composition were a non-volatile content of 66.7% by mass and a viscosity of 13,000 mPa ⁇ s.
• Comparative Example 1 Emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50 mass%, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.) without adding glass filler, aqueous resin composition of Comparative Example 1 Used as a product.
• Emulsion (1) styrene-acrylic acid ester copolymer, nonvolatile content 50 mass%, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.
• Comparative Example 2 Emulsion (4) (acrylic ester polymer, non-volatile content 50 mass%, viscosity 2,500 mPa ⁇ s, minimum film forming temperature 2 ° C.) without adding glass filler is used as the aqueous resin composition of Comparative Example 2. It was.
• Emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50 mass%, viscosity 4,500 mPa ⁇ s, minimum filming temperature 0 ° C.) is used as the water-based synthetic resin emulsion, and CF0007— 05B (manufactured by Nippon Frit Co., Ltd .: average particle size 5 ⁇ m) was used. 12.5 parts by mass of CF0007-05B was added to 100 parts by mass of the emulsion (1), and the mixture was stirred with a disper at 3,000 rpm for 20 minutes.
• 0.05 part by mass of an antifoaming agent Nopco 8034L: manufactured by San Nopco Co., Ltd.
• the obtained aqueous resin composition was filtered with an 80th filter cloth, and it was confirmed that there was no generation of coarse particles and aggregates.
• the aqueous resin composition of Comparative Example 3 was obtained by such a production method.
• the properties of the obtained water-based resin composition were a non-volatile content of 55.6% by mass and a viscosity of 6,500 mPa ⁇ s.
• Emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50 mass%, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.) is used as the water-based synthetic resin emulsion, and microglass is used as the glass filler.
• Flakes RCF-150 (manufactured by Nippon Sheet Glass Co., Ltd .: average particle size 150 ⁇ m) was used. 12.5 parts by mass of RCF-150 was added to 100 parts by mass of the emulsion (1), and the mixture was stirred with a disper at 3,000 rpm for 20 minutes.
• 0.05 part by mass of an antifoaming agent (Nopco 8034L: manufactured by San Nopco Co., Ltd.) was added for defoaming to adjust the aqueous resin composition.
• the aqueous resin composition of Comparative Example 4 was obtained by such a production method.
• the properties of the obtained water-based resin composition were a non-volatile content of 55.6% by mass and a viscosity of 7,500 mPa ⁇ s.
• Emulsion (1) (styrene-acrylic acid ester copolymer, nonvolatile content 50 mass%, viscosity 4,500 mPa ⁇ s, minimum film forming temperature 0 ° C.) is used as the water-based synthetic resin emulsion, and CF007— 05B (Nippon Frit Co., Ltd .: average particle size 5 ⁇ m) and CF0002-30A (Nippon Frit Co., Ltd .: average particle size 30 ⁇ m) were used.
• CF-007-05B and 100 parts by mass of CF0002-30A were added to 100 parts by mass of the emulsion (1), and the mixture was stirred with a disper at 3,000 rpm for 20 minutes.
• 0.1 part by mass of an antifoaming agent Nopco 8034L: manufactured by San Nopco Co., Ltd.
• the obtained aqueous resin composition was filtered with an 80th filter cloth, and it was confirmed that there was no generation of coarse particles and aggregates.
• the aqueous resin composition of Comparative Example 5 was obtained by such a production method.
• the properties of the obtained water-based resin composition were a non-volatile content of 83.3 mass% and a viscosity of 100,000 mPa ⁇ s or more.
• the swelling rate and elution rate in the acid resistance evaluation were obtained by cutting the prepared film into 40 mm ⁇ 40 mm, measuring the mass, and then dipping in a 10% sulfuric acid aqueous solution at 40 ° C. for 7 days.
• the immersed film was taken out, the mass was measured, and the swelling ratio was calculated by dividing the increase from the mass before immersion by the mass before immersion.
• the dissolution rate was calculated by measuring the mass after drying the immersed film at 40 ° C. for 12 hours, and dividing the decrease from the mass before immersion by the mass before immersion.
• the film strength retention rate and the film elongation retention rate in the acid resistance evaluation were performed by the following methods.
• the created film was cut out to 10 mm ⁇ 30 mm, a tensile test was performed at a tensile speed of 100 mm / min, and the strength and elongation of the film before being immersed in a 10% sulfuric acid aqueous solution were measured from the maximum strength and the elongation of a marked line of 10 mm. .
• the prepared film was cut into 10 mm ⁇ 30 mm separately, immersed in a 10% sulfuric acid aqueous solution at 40 ° C. for 7 days, and dried at 40 ° C. for 12 hours. Then, the strength and elongation of the immersed film were measured.
• the film strength retention is calculated by dividing the strength of the film after immersion by the strength of the film before immersion, and the film elongation retention is the elongation of the film after immersion as the elongation of the film before immersion. Calculated by

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