WO2020196433A1 - Composition de résine type dispersion aqueuse et film de revêtement - Google Patents

Composition de résine type dispersion aqueuse et film de revêtement Download PDF

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Publication number
WO2020196433A1
WO2020196433A1 PCT/JP2020/012797 JP2020012797W WO2020196433A1 WO 2020196433 A1 WO2020196433 A1 WO 2020196433A1 JP 2020012797 W JP2020012797 W JP 2020012797W WO 2020196433 A1 WO2020196433 A1 WO 2020196433A1
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coating film
resin composition
water
resin
film
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PCT/JP2020/012797
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English (en)
Japanese (ja)
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雄太 竹ノ内
暁恵 池永
和也 藤岡
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日東電工株式会社
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    • 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
    • C08K5/00—Use of organic ingredients
    • 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
    • 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
    • C09D121/00—Coating compositions based on unspecified rubbers
    • 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
    • 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • 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
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an aqueous dispersion type resin composition and a coating film.
  • Patent Document 1 a water-based acrylic resin is applied to the surface of a cured coating film coated on an automobile outer panel. , And a method of forming a coating film on an automobile outer panel with a peelable water-based coating composition containing an ultraviolet absorber to temporarily protect it. Further, Patent Document 2 describes a coating film that can be easily peeled off, which is formed by a peelable coating film forming paint composed of an acrylic resin-based emulsion and a urethane resin-based emulsion.
  • the coating film formed by the composition containing an organic solvent has excellent water resistance, there is a concern that the volatilized organic solvent may affect the human body. For example, it is used for articles and structures related to foods and medical supplies. And there are restrictions on its use in buildings.
  • the coating films described in Patent Documents 1 and 2 use an aqueous solvent, there is a problem that they are difficult to remove when dirt adheres to them. Therefore, as a result of focusing on the swelling property of the coating film, the present inventors have found that if the swelling property is high, the stains are difficult to remove, and in particular, the antifouling property against proteins is lowered. Then, they have found that the above-mentioned problems can be solved by setting the water content and the peelability index when the coating film is formed in a specific range, and have completed the present invention.
  • the present invention has been completed in view of the above, and is capable of forming a sheet-peelable coating film having excellent antifouling property, particularly antifouling property against protein, excellent peelability, and less burden on the environment. It is an object of the present invention to provide a water-dispersible resin composition and a coating film formed from the water-dispersible resin composition.
  • a water-dispersible resin composition When the aqueous dispersion type resin composition is dried at 25 ° C. for 12 hours to form a film, and further dried at 35 ° C. for 4 hours to form a coating film having a thickness of 230 ⁇ 170 ⁇ m, the coating film is as follows (1). And (2), an aqueous dispersion type resin composition. (1) The water content of the coating film after being immersed in a 5% ethanol aqueous solution at 25 ° C. for 2 hours is 110% or less. (2) The coating film is peeled off represented by the following formula (2a).
  • the sex index is more than 2.5 and the adhesive strength is 0.5 N / 20 mm or more.
  • Peelability index (tensile breaking strength (MPa)) / ⁇ adhesive strength (N) / (thickness (mm) x width ( mm)) ⁇ ... Equation (2a)
  • [2] The water-dispersible resin composition according to [1], which contains at least one resin selected from an acrylic resin, a styrene resin, a rubber resin, and a urethane resin.
  • the water-dispersible resin composition according to [1] which contains an acrylic resin as a resin and further contains a release agent or a film forming aid.
  • the water-dispersible resin composition according to [1] which contains a urethane-based resin as a resin and further contains a film-forming auxiliary or a cross-linking agent.
  • a coating film comprising the water-dispersible resin composition according to any one of [1] to [6].
  • the water-dispersible resin composition of the present invention has a small impact on the environment, and is excellent in antifouling property, particularly antifouling property against protein, and can form a sheet peelable coating film having excellent peelability.
  • FIG. 1 is a diagram showing the relationship between the swelling property of the coating film and the antifouling effect (residual amount of BSA).
  • FIG. 2 is a diagram showing the relationship between the swellability and the peelability of the coating film.
  • the aqueous dispersion type resin composition of the present embodiment is an aqueous dispersion type resin composition containing an aqueous solvent, and the aqueous dispersion type resin composition is dried at 25 ° C. for 12 hours to form a film, and further at 35 ° C. 4
  • a coating film having a thickness of 230 ⁇ 170 ⁇ m is dried for an hour, the following (1) and (2) are satisfied.
  • the water content of the coating film after being immersed in a 5% ethanol aqueous solution at 25 ° C. for 2 hours is 110% or less.
  • the coating film has a peelability represented by the following formula (2a).
  • Peelability index (tensile breaking strength (MPa)) / ⁇ adhesive strength (N) / (thickness (mm) x width (mm) )) ⁇ ... Equation (2a)
  • the water-dispersible resin composition of the present embodiment is excellent in handleability because it can be formed into a film at room temperature (25 ° C.). Further, since the coating film formed by the water-dispersible resin composition of the present embodiment does not easily swell, it prevents the stains from penetrating into the coating film even when the stains adhere, and exhibits an excellent antifouling effect. To do. It is also possible to wash the surface of the coating film with water or the like.
  • the coating film formed by the water-dispersible resin composition of the present embodiment is a coating film having excellent peelability, and is preferably a peelable coating film.
  • the peelable coating film means a coating film that can be peeled off into a sheet without cracking.
  • the peelable coating film can be formed by applying and drying the water-dispersible resin composition, and since the sheet can be peeled off, the removal work can be facilitated.
  • the water content in (1) above can be used as an index of the swelling property of the coating film, and there is a correlation between the swelling property of the coating film and the antifouling effect.
  • the water content in (1) above needs to be 110% or less, preferably 107% or less, and more preferably 105% or less.
  • the lower limit of the water content in (1) above is not particularly limited. The closer the water content is to 100%, the lower the swelling property.
  • the water content indicates the mass change rate when the initial stage (the mass of the coating film before immersion) is 100%.
  • the water content of the coating film is determined by immersing the coating film formed under the above conditions with the water-dispersible resin composition in a 5% ethanol aqueous solution at 25 ° C. for 2 hours, and measuring the mass before and after the immersion. It can be calculated by the following formula (1a).
  • Formula (1a): Moisture content (%) 100 + [(mass after immersion-mass before immersion) / mass before immersion] ⁇ 100
  • the antifouling effect can be measured, for example, by measuring the amount of protein adhering to the coating film.
  • Examples of the method for measuring the amount of protein adsorbed include the bicinchoninic acid method (BCA method).
  • BCA method is a highly sensitive protein colorimetric quantification method and is suitable for quantification of protein solutions solubilized with a surfactant. Specifically, II-valent copper ions are reduced to I-valent copper by peptide binding in the protein, and the produced I-valent copper is chelated by bicinconic acid to form a complex having a specific absorption of 562 nm. To do. The amount of protein is determined from this absorption intensity.
  • the coating film formed by the aqueous dispersion type resin composition of the present embodiment is dried at 25 ° C. for 12 hours to form a film, and further dried at 35 ° C. for 4 hours to obtain a coating film having a thickness of 230 ⁇ 170 ⁇ m.
  • the peelability index is preferably 3.0 or more, more preferably 5.0 or more, and further preferably 10 or more from the viewpoint of ease of peeling work.
  • the tensile breaking strength is the tensile breaking strength of the coating film at a tensile speed of 300 mm / min.
  • the adhesive force is the adhesive force of the coating film to SUS.
  • Adhesive strength to the SUS304 2B shirring (hereinafter referred to as SUS) finish can be used as an index indicating the difficulty of peeling from the adherend when the coating film is used.
  • the coating film formed by the water-dispersible resin composition of the present embodiment under the above conditions preferably has a tensile breaking strength of 2.0 MPa or more, preferably 2.5 MPa or more at a tensile speed of 300 mm / min. Is more preferable, and 3.0 MPa or more is further preferable. When the tensile breaking strength of the coating film is 2.0 MPa or more, the strength of the coating film is sufficiently high, a peelable coating film can be obtained, and deformation of the coating film due to an external force is prevented.
  • the coating film formed under the above conditions by the water-dispersible resin composition of the present embodiment is SUS using a tensile tester (AUTOGRAPH AGS-X, manufactured by Shimadzu Corporation) from the viewpoint of adhesion.
  • the adhesive force when peeled from the substrate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min needs to be 0.5 N / 20 mm or more, and preferably 1.0 N / 20 mm or more. Further, from the viewpoint of workability at the time of peeling, it is preferably 15 N / 20 mm or less, more preferably 10 N / 20 mm or less, and further preferably 5 N / 20 mm or less.
  • the adhesive strength of the coating film can be measured by the method described in Examples.
  • the water content in the above (1) and the peelability in the above (2) of the coating film formed by the water-dispersible resin composition of the present embodiment can be contained in the composition of the water-dispersible resin composition, for example. It can be adjusted by the type and content of the resin, the type and content of the release agent or the film forming aid that can be used in combination with the resin, and the like.
  • the water-dispersible resin composition is an aqueous dispersion in which at least the resin is dispersed and contained in water.
  • a solution in which the resin is dispersed in the presence of a surfactant is usually used, but if the resin is dispersed and contained in water, the self-dispersible resin is self-dispersed. It is possible to use a solution which is an aqueous dispersion.
  • resins can be used in the water-dispersible resin composition, for example, rubber-based resin, acrylic-based resin, silicone-based resin, polyurethane resin (urethane-based resin), vinyl alkyl ether-based resin, polyvinyl alcohol-based resin. , Polypolypyrrolidone resin, polyacrylamide resin, cellulose resin, polyester resin, polystyrene resin, fluorine resin, etc., but at least one selected from acrylic resin, styrene resin, rubber resin, etc. Is preferable, and acrylic resin is more preferable.
  • the rubber-based resin for example, acrylic rubber, diene-based rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, fluororubber, silicone rubber, ethylenepropylene rubber, chloroprene rubber, urethane rubber, and epichlorohydrin rubber can be used.
  • Acrylic rubber, diene rubber, urethane rubber are preferably used.
  • diene rubber natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, and acrylonitrile butadiene rubber can be used, and styrene butadiene rubber is preferably used.
  • the acrylic resin is preferably obtained by, for example, emulsifying and polymerizing a monomer component containing an alkyl (meth) acrylate.
  • the alkyl (meth) acrylate refers to an alkyl acrylate and / or an alkyl methacrylate, and has the same meaning as the (meth) of the present invention.
  • Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • the ratio of alkyl (meth) acrylate to all monomer components used in the synthesis of acrylic resin is preferably 70% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more.
  • the upper limit of the ratio of the alkyl (meth) acrylate is not particularly limited, but it is usually preferably 99.5% by mass or less (for example, 99% by mass or less).
  • the acrylic resin may be substantially polymerized only with an alkyl (meth) acrylate.
  • styrene resin examples include SBS (styrene / butadiene / styrene block copolymer), SIS (styrene / isoprene / styrene block copolymer), SEBS (styrene / ethylene / butylene / styrene block copolymer), and SEPS.
  • SBS styrene / butadiene / styrene block copolymer
  • SIS styrene / isoprene / styrene block copolymer
  • SEBS styrene / ethylene / butylene / styrene block copolymer
  • SEPS styrene / ethylene / propylene / styrene block copolymer
  • SEEPS styrene / ethylene / ethylene / propylene / styren
  • the urethane-based resin examples include a urethane-based resin formed from a composition containing a polyol and a polyfunctional isocyanate compound, or a urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound.
  • a urethane-based resin formed from a composition containing a polyol and a polyfunctional isocyanate compound or a urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound.
  • polycarbonate-based polyurethane, polyester-based polyurethane, polyether-based polyurethane and the like can be used.
  • Polyurethane-based resin is typically a reaction product of polyol and polyisocyanate.
  • a polymer polyol such as a polyacrylic polyol, a polyester polyol, or a polyether polyol is preferably used.
  • the polyacrylic polyol is typically obtained by polymerization of a (meth) acrylic acid ester and a hydroxyl group-containing monomer.
  • the (meth) acrylic acid ester include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and the like.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth).
  • Hydroxyalkyl esters of (meth) acrylic acids such as 4-hydroxybutyl acrylate and 2-hydroxypentyl (meth) acrylate; (meth) acrylic acid monoesters of polyhydric alcohols such as glycerin and trimethylpropane; N-methylol (Meta) acrylamide and the like can be mentioned.
  • the polyester polyol is typically obtained by the reaction of a polybasic acid with a polyol.
  • the polybasic acid include aromatics such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid.
  • Dicarboxylic acids oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, dodecanecarboxylic acid, octadecanedicarboxylic acid, tartaric acid, alkylsuccinic acid, linoleic acid , Maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid and other aliphatic dicarboxylic acids; hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like Formula dicarboxylic acid; or reactive derivatives such as these acid anhydrides, alkyl esters, acid halides and the like can be mentioned.
  • Polyether polyols are typically obtained by ring-opening polymerization of alkylene oxides on polyhydric alcohols and adding them.
  • the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, and trimethylolpropane.
  • the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran and the like.
  • polyisocyanate examples include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate, 2.
  • Aliphatic diisocyanates such as -methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexamethylene diisocyanate, 1,4-cyclohexanediisocyanate , Methylcyclohexamethylene diisocyanate, alicyclic diisocyanates such as 1,3-bis (isocyanatemethyl) cyclohexane; tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate , 4,4'-Diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, 1,5-naphthylene
  • the water-dispersible resin composition may contain a compound containing a polar group.
  • a compound containing a polar group examples include a resin containing a polar group, a silane coupling agent, a cross-linking agent, a silicone oil, and the like.
  • the resin containing a polar group examples include ionomer, rosin resin, silicone resin and the like.
  • the content of these compounds with respect to the resin component in the water-dispersible resin composition is preferably 0.1 to 95% by mass, preferably 0.5 to 60% by mass, based on the total mass of the resin component. It is more preferably 0.5 to 40% by mass, particularly preferably 0.5 to 20% by mass, and most preferably 1 to 20% by mass.
  • the content ratio of the resin component in the water-dispersible resin composition is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and further preferably 15% by mass to 80% by mass. It is particularly preferably 20% by mass to 70% by mass, and most preferably 25% by mass to 60% by mass.
  • the water-dispersed resin composition may be an emulsion, and is preferably an emulsion-type resin composition using a polymer emulsion obtained by emulsification polymerization.
  • the emulsion-type resin composition include emulsions containing the above-mentioned resin components, and urethane-based emulsions containing urethane rubber or acrylic-based emulsions containing acrylic resins are preferable.
  • Emulsion polymerization is carried out by emulsifying the monomer component in water and then emulsifying and polymerizing by a conventional method. As a result, an aqueous dispersion (polymer emulsion) is prepared.
  • a surfactant embroidery
  • a radical polymerization initiator e.g., a chain transfer agent
  • chain transfer agent e.g., a chain transfer agent
  • known emulsification polymerization methods such as a batch charging method (batch polymerization method), a monomer dropping method, and a monomer emulsion dropping method can be adopted.
  • the monomer dropping method and the monomer emulsion dropping method continuous dropping or divided dropping is appropriately selected. These methods can be combined as appropriate.
  • the reaction conditions and the like are appropriately selected, but the polymerization temperature is preferably about 40 to 95 ° C., and the polymerization time is preferably about 30 minutes to 24 hours.
  • the initiator used for emulsion polymerization can be appropriately selected from conventionally known polymerization initiators.
  • an azo-based polymerization initiator such as 2,2'-azobisisobutyronitrile can be preferably used.
  • Other examples of polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds. ; Etc. can be mentioned.
  • Yet another example of a polymerization initiator is a redox-based initiator in which a peroxide and a reducing agent are combined.
  • Such a polymerization initiator can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be a normal amount, and is selected from the range of about 0.005 to 1 part by mass (typically 0.01 to 1 part by mass) with respect to 100 parts by mass of the monomer raw material. can do.
  • any of anionic, nonionic, and cationic types can be used. These can be used alone or in combination of two or more. Usually, it is preferable to use an anionic or nonionic emulsifier.
  • the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like.
  • nonionic emulsifier examples include polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether.
  • a radically polymerizable emulsifier (reactive emulsifier) having a structure in which a radically polymerizable group such as a propenyl group is introduced into the anionic or nonionic emulsifier as described above may be used.
  • an embodiment in which only an emulsifier having no radically polymerizable group is used can be preferably adopted from the viewpoint of polymerization stability at the time of resin synthesis, storage stability of the pressure-sensitive adhesive composition, and the like.
  • chain transfer agents which can also be grasped as a molecular weight adjusting agent or a degree of polymerization adjusting agent
  • a chain transfer agent may be one or more selected from mercaptans such as n-lauryl mercaptan, tert-lauryl mercaptan, glycidyl mercaptan, 2-mercaptoethanol and the like.
  • preferable chain transfer agents include n-lauryl mercaptan and tert-lauryl mercaptan.
  • the amount used is not particularly limited. For example, it can be about 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the monomer raw material, and is usually preferably 0.01 to 0.1 parts by mass.
  • the Mw of the obtained resin is typically 10 ⁇ 10 4 or more, and usually 20 ⁇ 10 4 or more is suitable. From the viewpoint of suitably achieving both adhesive strength and the cohesive strength, Mw is preferably 30 ⁇ 10 4 or more, more preferably 40 ⁇ 10 4 or more (e.g., 50 ⁇ 10 4 or more).
  • the upper limit of Mw is not particularly limited, for example, 500 ⁇ 10 4 or less, typically 200 ⁇ 10 4 or less, preferably may be 0.99 ⁇ 10 4 or less.
  • Mw is, for example, the type and amount of polymerization initiator, polymerization temperature, type and amount of emulsifier, presence or absence of use of chain transfer agent and type and amount used, composition of monomer raw material, type of cross-linking and It can be adjusted according to the degree (gel fraction) and the like.
  • the water-dispersible resin composition of the present embodiment may contain a release agent, a film forming aid, or a cross-linking agent.
  • the release agent is an additive that adjusts the adhesive force of the formed coating film and helps the release from the adherend.
  • At least one or more compounds selected from surfactants, polyhydric alcohols, waxes and the like can be preferably used. These can be used either dissolved or dispersed in water, or in powder form.
  • anionic surfactant examples include fatty acid salts such as sodium oleate, semi-cured beef fat soda, and potassium oleate, lauryl sulfate ester soda, higher alcohol sulfate ester soda, lauryl alcohol sulfate ester triethanolamine salt, and lauryl alcohol sulfate.
  • Higher alcohol sulfate ester salts such as ester ammonium salt, alkylbenzene sulfonate such as sodium dodecylbenzene sulphonate, alkylnaphthalenzulfonate such as sodium alkylnaphthalenzulfonate, formalin condensate sodium naphthalenzulfonate, sodium dioctyl sulphonate, etc.
  • Dialkyl sulpho amber salt, alkyl phosphate, and the above-mentioned anionic surfactant with ethylene oxide added can be used alone or in combination of two or more. You may.
  • a phosphoric acid ester type surfactant for example, Phosphanol RS-410 (manufactured by Toho Chemical Industry Co., Ltd.)
  • the amount used thereof is 0.001 to 0.001 in the peelable resin composition of the present invention. It is 5% by mass, preferably 0.005 to 3% by mass, and more preferably 0.005 to 1% by mass.
  • anionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene octylphenyl ether.
  • Polyoxyethylene sorbitan alkyl ester such as rate, polyoxyethylene polypropylene block polymer and the like can also be used in combination.
  • amphoteric surfactants such as betaine-type amphoteric surfactants such as dimethylalkylbetaine, laurylbetaine and stearylbetaine, and a small amount of cationic surfactants can be used in combination.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, glycerin, catechol, butanediol, pentanediol, erythritol, glycerin monoalkyl ester, polyethylene glycol, polypropylene glycol and the like, and ethylene glycol, propylene glycol and glycerin are preferable.
  • Specific waxes include plant-based; candeli wax, carnauba wax, rice wax, wood wax, jojoba oil, etc., animal-based; mitsuro, lanolin, whale wax, etc., mineral-based; montan wax, ozokelite, ceresin, etc.
  • the film forming aid is an additive that helps to form a coating film.
  • the film-forming auxiliary has a temporary plasticizing function that evaporates relatively quickly after the coating film is formed to improve the strength of the coating film, and is an organic solvent having a boiling point of 110 to 200 ° C. Is preferably used.
  • the MFT Minimum film forming temperature
  • the MFT can be set to room temperature (15 to 35 ° C.) or higher by adding a film forming aid. Even with the resin component of, film formation is possible in a room temperature environment, and a highly uniform coating film can be obtained.
  • texanol propylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-normal-butyl ether, diethylene glycol diethyl ether, dipropylene glycol monopropyl ether, carbitol, butyl.
  • examples thereof include carbitol, dibutylcarbitol, N-methyl-2-pyrrolidone, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and benzyl alcohol.
  • texanol and ethylene glycol mono-normal-butyl ether are particularly preferable because they have a high film forming aid effect in a small amount.
  • These film forming aids are preferably contained in the water-dispersed resin composition in an amount of 0.5 to 15% by mass.
  • cross-linking agent examples include a photo-curable monomer, a photo-curing agent such as a photo-curable oligomer, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a carbodiimide-based cross-linking agent, and a metal chelate-based cross-linking agent.
  • examples include agents. These cross-linking agents react with functional groups such as hydroxy groups and carboxy groups introduced into the base polymer to form a cross-linked structure.
  • cross-linking agent a photocurable monomer, a photo-curable oligomer, or an isocyanate-based cross-linking agent is preferable because it has high reactivity with the hydroxy group and carboxy group of the base polymer and it is easy to introduce a cross-linked structure.
  • cross-linking agent only one type may be used alone, or two or more types may be used in combination.
  • the water-dispersible resin composition contains, for example, an acrylic resin as the resin (resin component), it is preferable to further contain a release agent or a film-forming auxiliary, and texanol or peeling as the film-forming auxiliary. It is preferable to include a phosphoric acid ester type surfactant as the agent. It is preferable that the water-dispersible resin composition contains an acrylic resin as a resin and further contains a release agent.
  • the water-dispersible resin composition contains a urethane-based resin as the resin (resin component), it is preferable to further contain a film forming aid or a cross-linking agent.
  • a film forming aid or a cross-linking agent it is preferable to contain ethylene glycol mono-normal-butyl ether as the film forming aid, or an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent as the cross-linking agent.
  • the water-dispersible resin composition contains a urethane-based resin as a resin and further contains a film-forming aid or a cross-linking agent.
  • the water-dispersible resin composition of the present embodiment may contain any suitable oil as long as the effects of the present invention are not impaired.
  • suitable oils include silicone oils, liquid paraffins, surfactants, liquid hydrocarbons, fluorinated oils, waxes, petrolatams, animal fats, fatty acids and the like. These may be only one kind or two or more kinds.
  • the antifouling effect of the coating film may be more sufficiently exhibited, and the adhesion of stains may be more effectively prevented over a long period of time.
  • surfactant examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and the like.
  • Anionic surfactants include, for example, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfo fatty acids or esters, alkane sulfonates, saturated or unsaturated.
  • Saturated fatty acid salts, alkyl or alkenyl ether carboxylic acid salts, amino acid-type surfactants, N-acylamino acid-type surfactants, alkyl or alkenyl phosphate esters or salts thereof and the like can be mentioned.
  • the anionic surfactant may be only one kind or two or more kinds.
  • Nonionic surfactants include, for example, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester, alkyl. Examples include amine oxides.
  • the nonionic surfactant may be only one kind or two or more kinds.
  • amphoteric surfactant examples include a carboxy type or sulfobetaine type amphoteric surfactant.
  • the amphoteric surfactant may be only one kind or two or more kinds.
  • Examples of the cationic surfactant include a quaternary ammonium salt and the like.
  • the cationic surfactant may be only one kind or two or more kinds.
  • the water-dispersible resin composition may contain any suitable other additive as long as the effect of the present invention is not impaired.
  • suitable other additives include thickeners (for example, associative type, synthetic polymer type, alkaline thickening type, etc.), colorants, and weather resistant agents such as ultraviolet absorbers, light stabilizers, antibacterial agents, and oxidations.
  • thickeners for example, associative type, synthetic polymer type, alkaline thickening type, etc.
  • colorants such as ultraviolet absorbers, light stabilizers, antibacterial agents, and oxidations.
  • weather resistant agents such as ultraviolet absorbers, light stabilizers, antibacterial agents, and oxidations.
  • examples thereof include inhibitors, antifoaming agents, diatomaceous adhesion inhibitors, pesticides, pharmaceuticals (medetomidin, etc.), enzyme activity inhibitors (alkylphenol, alkylresorcinol, etc.), biological repellents, fillers, and the like.
  • antibacterial agent any appropriate antibacterial agent can be adopted as long as the effect of the present invention is not impaired.
  • antibacterial agent examples include so-called antibacterial agents and antifungal agents.
  • antibacterial agents include, for example, azoxystrobin, benaraxil, benomil, bitertanol, bromconazole, captahole, captan, carvendadim, quinomethionate, chlorotalonyl, clozolinate, cyprodinyl, diclofluanide, diclofen, dichromedin, dichloran, Dietofencarb, dimethomorph, diniconazole, dithianone, epoxyconazole, famoxadon, phenalimol, fenbuconazole, fenfuram, fenpicronyl, fentin, fluazinum, fludioxonyl, fluorimide, fluquinconazole, flusulfamide, flutranyl, holpet, hexachlorobenzene, hexaconazole, Benconazole, Ipoconazole, Iprodion, Cresoximemethyl, Manze
  • antibacterial agents for natural products include Chinese herbal ingredients such as Meng Soutake extract, hinokithiol, garlic extract, and kanzo.
  • examples thereof include inorganic antibacterial agents such as silver, copper, zinc, tin, lead and gold. If necessary, zeolite, hydroxyapatite, calcium carbonate, silica gel, aluminum silicate calcium, polysiloxane compound, zirconium phosphate, zirconium sulfate, ion exchanger, zinc oxide, etc. are used as carriers for these inorganic antibacterial agents. it can.
  • Examples of the synthetic antibacterial agent include 2-pyridinethiol-1-oxide, p-chloro-m-cresol, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, benzisothiazolin, 5-. Chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2'-dithio-bis- (pyridine-1-oxide) and the like can be mentioned.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof.
  • a filler or the like can be added to the water-dispersible resin composition in order to improve the strength.
  • the filler include silica particles, mica, kaolin, talc, diatomaceous earth and the like.
  • the particle size is preferably such that the average particle size is 5 nm to 300 nm.
  • the amount of the particles added is preferably 0.1% by mass to 10% by mass with respect to the total mass of the resin component.
  • the surface-treated particles are preferable from the viewpoint of improving the antifouling property of the coating film.
  • the particles whose surface is hydrophobically treated include hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd. Specifically, the trade name "AEROSIL (registered trademark) RX series” manufactured by Nippon Aerosil Co., Ltd. ( RX50, RX200, RX300, etc.), “AEROSIL® RY Series” (RY50, RY200, RY200S, etc.), “AEROSIL® NY50 Series", “AEROSIL® NAX Series", “AEROSIL (Registered Trademark)” Trademark) R series ”and the like.
  • AEROSIL registered trademark
  • RX series manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL® RY Series RY50, RY200, RY200S, etc.
  • AEROSIL® NY50 Series "AEROSIL® NAX Series
  • the water-dispersible resin composition can be applied to an adherend and dried to form a coating film.
  • a highly uniform coating film can be obtained even when dried at room temperature (25 ° C.).
  • it can be directly coated on any adherend by a known coating method such as spray, brush coating, roller, curtain flow, roll, dip, coater and the like.
  • As a drying method for example, it is dried at a temperature of 0 ° C. to 250 ° C. (preferably a temperature of room temperature (25 ° C.) to 180 ° C., more preferably a temperature of room temperature to 160 ° C.) for 2 minutes to 12 hours. Can be (first drying). If necessary, further, for example, at a temperature of 0 ° C.
  • the second drying is preferably performed at a temperature 0 to 20 ° C. higher than the first drying temperature and for a shorter time than the first drying temperature.
  • adherend examples include metal products, woodwork products, plastic products, glass products, medical members (for example, catheters, stents, gloves, tweezers, containers, guides, trays, etc.), and structures (inner and outer wall surfaces). , Floor surface, and ceiling surface), electronic devices, transportation devices (for example, vehicles such as automobiles, motorcycles and railroads, and ships, etc.) and the like.
  • the water-dispersible resin composition Since the water-dispersible resin composition has an extremely low content of organic solvent, it is used in petri dishes for cell culture, plates such as microwells, transport trays, containers, tanks, guides, food manufacturing equipment, hospitals, nursing homes and kindergartens. It can also be used for coating on walls, tables, and places where food is handled. It can be used for forming an antifouling coating film for medical use such as medical equipment.
  • the coating film of the present embodiment is a coating film formed by the above-mentioned water-dispersible resin composition, and is useful for preventing the adhesion of stains. That is, the coating film of the present embodiment is a case where the aqueous dispersion type resin composition is dried at 25 ° C. for 12 hours to form a film, and further dried at 35 ° C. for 4 hours to obtain a coating film having a thickness of 230 ⁇ 170 ⁇ m. In addition, the coating film satisfies the following (1) and (2). (1) The water content of the coating film after being immersed in a 5% ethanol aqueous solution at 25 ° C. for 2 hours is 110% or less.
  • the coating film has a peelability represented by the following formula (2a).
  • the index is more than 2.5 and the adhesive strength is 0.5 N / 20 mm or more.
  • Peelability index (tensile breaking strength (MPa)) / ⁇ adhesive strength (N) / (thickness (mm) x width (mm) )) ⁇ ... Equation (2a)
  • the thickness of the coating film any appropriate thickness can be adopted depending on the intended use and usage environment.
  • the thickness of the coating film is preferably 10 ⁇ m to 5000 ⁇ m. When the thickness of the coating film is within the above range, the antifouling effect is sufficiently long and works effectively. When the thickness of the coating film is 10 ⁇ m or more, the antifouling effect is effectively exhibited and it is practical. When the thickness of the coating film is 5000 ⁇ m or less, the work efficiency is excellent.
  • the film thickness of the coating film can be measured using, for example, RI-205 manufactured by PEAKOCK.
  • the coating film may be used as an undercoat layer, and an antifouling layer, a rust preventive paint, a hard coat, or the like may be further provided on the coating film.
  • an antifouling layer for example, a hydrophilic coating such as a silica-based overcoat or a betaine-based polymer brush, or a hydrophobic coating such as a silicone-based resin or a fluoropolymer can be used.
  • the hydrophilic coating has self-cleaning performance and is therefore preferable from the viewpoint of antifouling property. Since the coating film does not swell easily, the adhesion between the undercoat layer and the antifouling layer does not deteriorate for a long period of time even when an antifouling layer or the like is laminated on the coating film.
  • the rust preventive paint and the hard coat antifouling layer may contain any suitable other additives as long as the effects of the present invention are not impaired.
  • suitable other additives include ultraviolet absorbers, light stabilizers, fillers and the like.
  • Acrylic resin 1 (acrylic resin, trade name “AP-3720N”, manufactured by Showa Denko Co., Ltd.): 100 parts by mass, film-forming aid (texanol, trade name “CS-12”, manufactured by JNC Co., Ltd.) ): Mix 6 parts by mass, stir with a disper at a rotation speed of 3000 rpm for 3 minutes or more, and vacuum defoam at 2200 rpm for 5 minutes with Awatori Rentaro (manufactured by Shinky Co., Ltd.) to disperse the water of Example 1.
  • a mold resin composition was prepared.
  • Examples 2 to 7, Comparative Examples 1 to 16 The aqueous dispersion type resin compositions of Examples 2 to 7 and Comparative Examples 1 to 16 were prepared in the same manner as in Example 1 except that the types and blending amounts of the resin and the additive were changed as shown in Table 1.
  • the water-dispersed resin compositions of each Example and Comparative Example were coated on the surface of a PET film having a thickness of 75 ⁇ m (product name “Lumilar S10”, manufactured by Toray Co., Ltd.) with an applicator to a wet thickness of 250 ⁇ m. Similarly, the water-dispersed resin compositions of each Example and Comparative Example were applied to a SUS plate with a wet thickness of 500 ⁇ m. The coating film formed by drying at room temperature (25 ° C.) for 12 hours was further dried at 35 ° C. for 4 hours to prepare a sample for measurement.
  • BCA method A sample film (measurement sample using the above PET film) punched to a diameter of 6 mm was placed in a 96-well plate made of polystyrene, and 250 ⁇ L of bovine serum albumin (BSA) solution (3 mg / mL in pure water) was placed therein. Was added and kept at 37 ° C. for 2 hours. The sample was removed from the well, washed twice with pure water and then transferred to another well. 150 ⁇ L of “Micro BSA Protein Assay Kit” (trade name) (manufactured by Thermo Fisher Scientific Co., Ltd.) and 150 ⁇ L of pure water were added thereto as a BCA solution, and the mixture was kept at 37 ° C. for 2 hours. After returning the BCA solution after the reaction to room temperature, the absorbance at 570 nm was measured with a spectrophotometer to determine the residual amount of BSA ( ⁇ g / cm 2 ) per membrane area.
  • BSA bovine serum albumin
  • the water-dispersed resin composition of each Example and Comparative Example was applied to the surface of a PET base film (product name "Lumilar S10", manufactured by Toray Co., Ltd.) having a thickness of 75 ⁇ m with an applicator, and at room temperature (25 ° C.). ) was dried for 12 hours. Further, the sample is dried at 35 ° C. for 4 hours to prepare a sample having the thickness (tensile thickness) shown in Table 2, and then the obtained coating film is cut to a size of 20 mm ⁇ 20 mm and peeled off from the PET substrate. The mass was measured without.
  • a water-dispersible resin composition was applied to the surface of a PET base film having a thickness of 75 ⁇ m (product name “Lumilar S10”, manufactured by Toray Co., Ltd.) with an applicator, and dried at room temperature for 12 hours. The obtained film was further dried at 35 ° C. for 4 hours to prepare a sample having the thickness (tensile film thickness) shown in Table 2, and then cut to a size of 20 mm ⁇ 80 mm.
  • the water-dispersed resin composition peeled off from the PET base film is tensioned using a tensile tester (device name "AUTOGRAPH AGS-X", manufactured by Shimadzu Corporation) at an initial length of 60 mm and a tensile speed of 300 mm / min. The breaking strength was evaluated.
  • a coating film was prepared by the following method, and the adhesive strength was measured.
  • a water-dispersed resin composition is applied to a SUS plate (SUS304) with an applicator, dried at room temperature for 12 hours, and further dried at 35 ° C. for 4 hours to obtain a sample having the thickness (peel thickness) shown in Table 2.
  • the other parts were removed so that the coating film had a size of 20 mm ⁇ 100 mm.
  • the force when the coating film is peeled off from the SUS substrate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is measured as the adhesive force. did.
  • the adhesive strength was measured twice, and the first and second times were set to n1 and n2, respectively.
  • peelability index (tensile breaking strength (MPa)) / ⁇ adhesive strength (N) / (thickness (mm) x width (mm)) ⁇ ... Equation (2a)
  • Table 2 shows the composition of the water-dispersed resin composition and the measurement / test results for each Example and Comparative Example.
  • FIG. 1 is a diagram showing the relationship between the swelling property of the coating film and the antifouling effect (residual amount of BSA ( ⁇ g / cm 2 )). As is clear from FIG. 1, there is a correlation between the swelling property (moisture content) of the coating film and the antifouling effect, and if the water content is about 110% or less, BSA does not adhere and the antifouling effect is exhibited. It was confirmed to be high.
  • FIG. 2 is a diagram showing the relationship between the swellability and the peelability of the coating film.
  • the swelling property moisture content
  • the peelability index is low when the water content is about 110% or less.
  • the coating film produced in the above-mentioned Examples / Comparative Examples is produced on a SUS substrate having a size of 40 mm ⁇ 60 mm, if the peelability index is 2.5 or less, the coating film is torn. If the peelability index was more than 2.5, it could be peeled off without tearing.

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une composition de résine type dispersion aqueuse pour former un film de revêtement, lorsque la composition de résine type dispersion aqueuse est séchée durant 12 heures à 25 °C pour former un film, et en outre séchée durant 4 heures à 35 °C pour obtenir un film de revêtement avec une épaisseur de 230 ± 170 µm, le film de revêtement satisfait les conditions suivantes (1) et (2).　(1) : Après que le film de revêtement a été immergé durant 2 heures dans une solution aqueuse d'éthanol à 5 % à 25 °C, la teneur en eau du film de revêtement est de 110 % ou moins.　(2) : Le film de revêtement présente un indice de propriété de décollement, tel qu'indiqué par la formule (2a) suivante, supérieur à 2,5, et une force d'adhésion de 0,5 N/20 mm ou plus.　Formule (2a) : Indice de propriété de décollement = (résistance à la rupture sous traction (MPa))/{force adhésive (N)/(épaisseur du film (mm) x largeur (mm))}
PCT/JP2020/012797 2019-03-28 2020-03-23 Composition de résine type dispersion aqueuse et film de revêtement WO2020196433A1 (fr)

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WO2021193169A1 (fr) * 2020-03-24 2021-09-30 日東電工株式会社 Composition pour formation de film de revêtement, et film de revêtement

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KR102457035B1 (ko) * 2020-10-26 2022-10-24 주식회사 현대엘앤씨 인간 친화적인 천연소재를 이용한 유해 미생물과 유해가스 제거 기술이 적용된 표면마감재

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744679A (en) * 1980-08-29 1982-03-13 Toyobo Co Ltd Strippable coating material
JPS6096671A (ja) * 1983-10-31 1985-05-30 Nippon Carbide Ind Co Ltd 剥離性樹脂組成物用水分散樹脂
JPH0931413A (ja) * 1995-07-14 1997-02-04 Sunstar Eng Inc 自動車塗装面等の保護膜形成方法
JP2002322335A (ja) * 2001-04-25 2002-11-08 Kuraray Co Ltd 水性エマルジョン組成物
JP2009167237A (ja) * 2008-01-11 2009-07-30 Rinrei:Kk 可剥離性床用被覆組成物
JP2015501230A (ja) * 2011-09-30 2015-01-15 コーロン インダストリーズ インク 水分散組成物およびこれを用いた光学フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744679A (en) * 1980-08-29 1982-03-13 Toyobo Co Ltd Strippable coating material
JPS6096671A (ja) * 1983-10-31 1985-05-30 Nippon Carbide Ind Co Ltd 剥離性樹脂組成物用水分散樹脂
JPH0931413A (ja) * 1995-07-14 1997-02-04 Sunstar Eng Inc 自動車塗装面等の保護膜形成方法
JP2002322335A (ja) * 2001-04-25 2002-11-08 Kuraray Co Ltd 水性エマルジョン組成物
JP2009167237A (ja) * 2008-01-11 2009-07-30 Rinrei:Kk 可剥離性床用被覆組成物
JP2015501230A (ja) * 2011-09-30 2015-01-15 コーロン インダストリーズ インク 水分散組成物およびこれを用いた光学フィルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021193169A1 (fr) * 2020-03-24 2021-09-30 日東電工株式会社 Composition pour formation de film de revêtement, et film de revêtement

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