WO2022255272A1 - Composition de résine aqueuse, film de revêtement, procédé de production de film de revêtement et ensemble de composition de résine aqueuse - Google Patents

Composition de résine aqueuse, film de revêtement, procédé de production de film de revêtement et ensemble de composition de résine aqueuse Download PDF

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Publication number
WO2022255272A1
WO2022255272A1 PCT/JP2022/021819 JP2022021819W WO2022255272A1 WO 2022255272 A1 WO2022255272 A1 WO 2022255272A1 JP 2022021819 W JP2022021819 W JP 2022021819W WO 2022255272 A1 WO2022255272 A1 WO 2022255272A1
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aqueous resin
resin composition
mass
copolymer
meth
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PCT/JP2022/021819
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English (en)
Japanese (ja)
Inventor
卓也 葛谷
直樹 村田
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昭和電工株式会社
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Priority to KR1020237041915A priority Critical patent/KR20240016291A/ko
Priority to CN202280038918.8A priority patent/CN117396555A/zh
Priority to JP2023525797A priority patent/JPWO2022255272A1/ja
Publication of WO2022255272A1 publication Critical patent/WO2022255272A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C09D5/08—Anti-corrosive 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
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type 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
    • 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
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to an aqueous resin composition, a coating film, a method for producing the same, and an aqueous resin composition set.
  • metal products In general, the surface of metal products is surface-treated.
  • metal products used outdoors and metal products expected to be exposed to moisture are often surface-coated in order to prevent the generation of rust.
  • Patent Document 1 describes a coating composition for thick coating containing an emulsion composition in which polymer particles are dispersed in an aqueous medium and an aggregate.
  • the polymer particles described in Patent Document 1 are composed of a structural unit obtained by polymerizing an alkyl (meth)acrylate monomer having an alkyl group having 4 to 14 carbon atoms, and an ethylenically unsaturated carboxylic acid monomer. and a structural unit obtained by polymerizing other monomers, in the presence of a compound having at least two epoxy groups in one molecule and a basic catalyst, by emulsion polymerization. is.
  • Patent Document 2 describes a composition comprising an aqueous dispersion of thermoplastic polymer particles imbibed with a thermosetting compound having oxirane groups.
  • US Pat. No. 6,200,001 describes that the polymer particles have a sufficient concentration of anti-aggregating functional groups to stabilize the latex against aggregation.
  • Patent Document 3 describes forming an acrylate resin (acrylic/epoxy latex) that absorbs an epoxy compound by mixing an epoxy emulsion with an emulsion of an acrylate resin.
  • a coating film formed using a paint containing an aqueous resin composition develops water resistance as the curing reaction of the resin contained in the coating progresses. For this reason, after the coating containing the water-based resin composition is applied to the metal product to form a coating film, before it fully cures, moisture due to rainfall etc. will penetrate the metal surface through the uncured coating film. There was a risk of reaching and rusting. For this reason, aqueous resin compositions used for the above applications are required to be hardened by curing at room temperature for a short period of time and capable of forming coating films exhibiting superior initial water resistance.
  • the present invention has been made in view of the above circumstances, and provides a coating film that can be cured at room temperature for a short period of time to form a coating film that has excellent initial water resistance, and that has good wet heat adhesion to metal materials.
  • An object of the present invention is to provide an aqueous resin composition and an aqueous resin composition set to be obtained.
  • Another object of the present invention is to provide a coating film comprising a cured product of the aqueous resin composition of the present invention, and a method for producing the coating film.
  • the present invention provides a composition of the following first aspect.
  • an aqueous resin emulsion ( ⁇ ); a curing agent ( ⁇ ); and a curing accelerator ( ⁇ ) comprises a copolymer (X), a polyepoxy compound (Y) having no ethylenically unsaturated bonds and having two or more epoxy groups in one molecule, and an aqueous medium (Z ), including
  • the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 1 to 40% by mass
  • the copolymer (X) contains a structural unit derived from (meth)acrylic acid ester (A) and a structural unit derived from ethylenically unsaturated carboxylic acid (B), The content of structural units derived from the (meth)acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy
  • the first aspect of the present invention has the following features. Combinations of two or more of the following features are also preferred.
  • [2] The water-based resin composition according to [1], wherein the (meth)acrylic acid ester (A) comprises a (meth)acrylic acid alkyl ester.
  • the ethylenically unsaturated carboxylic acid (B) is at least one selected from the group consisting of ⁇ , ⁇ -unsaturated monocarboxylic acids, ⁇ , ⁇ -unsaturated dicarboxylic acids, and vinyl compounds containing a carboxy group.
  • the aqueous resin composition according to [1] or [2] which contains seeds.
  • the polyepoxy compound (Y) is selected from bisphenol-type epoxy compounds, hydrogenated bisphenol-type epoxy compounds, diglycidyl ethers, triglycidyl ethers, tetraglycidyl ethers, diglycidyl esters, triglycidyl esters, and tetraglycidyl esters.
  • the aqueous resin composition according to any one of [1] to [3], which is at least one kind.
  • the copolymer (X) comprises a structural unit derived from the (meth)acrylic acid ester (A) and a structural unit derived from the ethylenically unsaturated carboxylic acid (B), [1] to [4 ] The water-based resin composition according to any one of the above.
  • the copolymer (X) includes a structural unit derived from an ethylenically unsaturated aromatic compound (C) having a benzene ring and an ethylenically unsaturated bond, any one of [1] to [4] The aqueous resin composition described. [7] The aqueous resin composition according to [6], wherein the ethylenically unsaturated aromatic compound (C) is an aromatic vinyl compound.
  • a 2 and A 3 each independently represent a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group; n is an integer of 1 to 12; show.
  • the curing accelerator ( ⁇ ) is at least one compound selected from the group consisting of tertiary aliphatic amines, tertiary alicyclic amines, and tertiary heteroaromatic amines, [1 ]
  • the water-based resin composition according to any one of [10].
  • the water-based resin emulsion ( ⁇ ) is obtained by emulsion polymerization of monomers that form the structural units of the copolymer (X) in the aqueous medium (Z) in the presence of the polyepoxy compound (Y).
  • the aqueous resin composition according to any one of [1] to [11], which is an emulsion.
  • a second aspect of the present invention provides a coating film as described below.
  • a coating film comprising a cured product of the aqueous resin composition according to any one of [1] to [14].
  • a third aspect of the present invention provides the manufacturing method described below.
  • the aqueous resin composition according to any one of [1] to [14] is prepared by mixing the aqueous resin emulsion ( ⁇ ), the curing agent ( ⁇ ), and the curing accelerator ( ⁇ ). a mixing step of A method for producing a coating film, comprising a coating step of applying the water-based resin composition to a surface to be coated.
  • the manufacturing method of the third aspect of the present invention preferably has the following features. [17] The method for producing a coating film according to [16], wherein the coating step is completed within 1 hour after the mixing step is completed.
  • a fourth aspect of the present invention provides an aqueous resin composition set described below.
  • the constituent components of the aqueous resin composition according to any one of [1] to [14] are stored separately in a first liquid and a second liquid,
  • the first liquid contains the aqueous resin emulsion ( ⁇ )
  • a water-based resin composition and a water-based resin that can be cured at room temperature for a short period of time to form a coating film having excellent initial water resistance and that can provide a coating film having good wet heat adhesion to metal materials.
  • a composition set can be provided. Further, according to the present invention, it is possible to provide a coating film comprising a cured product of the aqueous resin composition of the present invention and having good initial water resistance and wet heat adhesion to metal materials. Further, according to the present invention, it is possible to provide a method for producing a coating film comprising a cured product of the aqueous resin composition of the present invention.
  • aqueous resin composition Preferred examples of the aqueous resin composition, the coating film, the method for producing the coating film, and the aqueous resin composition set of the present invention are described below in detail.
  • this invention is not limited only to embodiment shown below.
  • the number, type, position, amount, ratio, material, configuration, etc. can be added, omitted, replaced, changed, etc. without departing from the gist of the present invention.
  • (Meth)acrylate means acrylate or methacrylate.
  • (meth)acryl means acryl or methacryl.
  • “Ethylenically unsaturated bond” means a double bond between carbon atoms, excluding carbon atoms forming an aromatic ring.
  • Weight average molecular weight is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
  • the structural unit derived from the compound having an ethylenically unsaturated bond includes the chemical structure of the portion other than the ethylenically unsaturated bond in the compound, and the It may mean a unit having the same chemical structure as the portion other than the portion corresponding to the ethylenically unsaturated bond of the structural unit in the polymer.
  • the ethylenically unsaturated bonds of the compounds may be converted to single bonds when forming the polymer.
  • the structural unit derived from methyl methacrylate is represented by -CH 2 -C(CH 3 )(COOCH 3 )-.
  • a structural unit (b) derived from an ethylenically unsaturated carboxylic acid (B) described later for structural units having an ionic functional group such as a carboxy group, whether or not part of the functional group is ion-exchanged, the structural unit derived from the same ionic compound may be
  • a structural unit represented by —CH 2 —C(CH 3 )(COONa)— may also be considered as a structural unit derived from methacrylic acid.
  • one or more ethylenically unsaturated bonds may remain inside the structural unit as the structural unit of the polymer of the compound.
  • Multiple independent ethylenically unsaturated bonds may mean multiple ethylenically unsaturated bonds that do not form a conjugated diene with each other.
  • the structural unit derived from divinylbenzene has a structure that does not have an ethylenically unsaturated bond (the portions corresponding to the two ethylenically unsaturated bonds of divinylbenzene are both polymer chains It may be a form incorporated in), or a structure having one ethylenically unsaturated bond (a form in which only the portion corresponding to one ethylenically unsaturated bond is incorporated into the polymer chain).
  • the “Curing” means that the molecules contained in the raw material bond with each other through a chemical reaction to form a polymer with a network structure.
  • the “coating film” is composed of a cured product formed by curing the resin component contained in the aqueous resin composition of the present embodiment, and a method such as applying the aqueous resin composition to the surface to be coated and drying the medium. It is integrated with the surface to be coated obtained by.
  • the "film” is composed of a cured product formed by curing the resin component contained in the aqueous resin composition of the present embodiment, and is peeled off from the substrate after curing on the substrate.
  • the aqueous resin composition of the present embodiment contains an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), and a curing accelerator ( ⁇ ).
  • the aqueous resin composition of the present embodiment is produced by mixing an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), and a curing accelerator ( ⁇ ), as described later.
  • the aqueous resin emulsion ( ⁇ ) comprises a copolymer (X), a polyepoxy compound (Y) having no ethylenically unsaturated bonds and having two or more epoxy groups in one molecule, and an aqueous medium (Z).
  • the water-based resin emulsion ( ⁇ ) is an emulsion obtained by emulsion polymerization of monomers that form the structural units of the copolymer (X) in the presence of the polyepoxy compound (Y) in the water-based medium (Z).
  • the water-based resin emulsion ( ⁇ ) is mixed with a curing agent ( ⁇ ) and a curing accelerator ( ⁇ ) described below and cured to form a cured product having high strength and high elongation.
  • copolymer (X) has a structural unit (a) derived from the (meth)acrylic acid ester (A) and a structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B).
  • the structural unit (a) derived from the (meth)acrylate (A) contains the structural unit (a1) derived from the hydrophilic (meth)acrylate (A1).
  • the copolymer (X) may consist of structural units (a) and structural units (b) (referred to as copolymer (X1)).
  • the copolymer (X) comprises a structural unit (a), a structural unit (b), and a structural unit (c) derived from an ethylenically unsaturated aromatic compound (C) having a benzene ring and an ethylenically unsaturated bond. ) and (referred to as a copolymer (X2)).
  • the copolymer (X2) may consist of structural units (a) to (c) only.
  • the copolymer (X) may have a structural unit (d) other than the structural units (a) to (c) (which is assumed to be a structural unit derived from another monomer (D)).
  • the amount of the copolymer (X) contained in the aqueous resin emulsion ( ⁇ ) can be arbitrarily selected. It is more preferably 25% by mass or more, and more preferably 25% by mass or more.
  • the amount of the copolymer (X) contained in the aqueous resin emulsion ( ⁇ ) can be arbitrarily selected, but it is preferably 60% by mass or less, preferably 50% by mass, based on the total amount of the aqueous resin emulsion ( ⁇ ). It is more preferably 40% by mass or less, more preferably 40% by mass or less. However, it is not limited only to these examples.
  • the content of the copolymer (X) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) described later is preferably 50% by mass or more, and preferably 60% by mass or more. More preferably, it is 65% by mass or more.
  • the content of the copolymer (X) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) described later is preferably 99% by mass or less, and preferably 94% by mass or less. More preferably, it is 88% by mass or less.
  • the (meth)acrylic acid ester (A) preferably contains a (meth)acrylic acid alkyl ester, and more preferably consists of a (meth)acrylic acid alkyl ester.
  • a (meth)acrylic acid alkyl ester having a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is more preferable.
  • Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.
  • Examples of the (meth)acrylic acid ester (A) may also include examples of the hydrophilic (meth)acrylic acid ester (A1) described later.
  • a (meth)acrylic acid ester having a carboxy group is not included in the (meth)acrylic acid ester (A), but is included in the ethylenically unsaturated carboxylic acid (B) described below.
  • the (meth)acrylic acid ester (A) preferably contains a compound with low hydrophilicity. This is because the rust prevention property of the coating film made of the cured product of the aqueous resin composition of the present embodiment is improved. For the same reason, the (meth)acrylic acid ester (A) may also contain a (meth)acrylic acid ester having an epoxy group.
  • Examples of (meth)acrylic acid esters having an epoxy group include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexyl.
  • Examples include methyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, and 3,4-epoxycyclohexylpropyl (meth)acrylate.
  • Structural unit (a) may contain structural units derived from only one of these compounds, or may contain structural units derived from two or more of these compounds. Furthermore, among these compounds, the structural unit (a) preferably contains a structural unit derived from glycidyl (meth)acrylate.
  • the (meth)acrylic acid ester (A) may be a (meth)acrylic acid ester that is neither an alkyl (meth)acrylic acid ester nor a compound having an epoxy group.
  • examples of such (meth)acrylic acid esters include (meth)acrylic acid esters having a hydroxy group.
  • Examples of (meth)acrylic acid esters having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, polyethylene glycol Mono(meth)acrylic acid esters, mono(meth)acrylic acid esters of polyalkylene glycol such as mono(meth)acrylic acid esters of polypropylene glycol, and the like. These hydroxy group-containing (meth)acrylic acid esters may be used alone, or two or more of them may be used in combination.
  • the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) is 20% by mass or more with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y). This is because the dispersibility of the monomer of the copolymer (X) and the polyepoxy compound (Y) can be improved in the method for producing the aqueous resin emulsion ( ⁇ ) described later. From this point of view, the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 35% by mass or more. is preferred, 45% by mass or more is more preferred, and 60% by mass or more is even more preferred.
  • the content of the structural unit derived from the compound contained in the copolymer may mean a value calculated based on the mass of the compound used as the raw material of the copolymer.
  • the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is the total It may mean the mass ratio (% by mass) of the (meth)acrylic acid ester (A) used in the production of the copolymer (X) with respect to the amount.
  • the copolymer (X) is composed of the structural unit (a) and the structural unit (b), i.e., when the copolymer (X1) is a copolymer (X1), a monomer to form the copolymer (X1) and a polyepoxy compound From the viewpoint of improving dispersibility with (Y), the following proportions are preferred. That is, the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) with respect to the total amount of the copolymer (X1) and the polyepoxy compound (Y) is 50% by mass or more. More preferably, it is particularly preferably 60% by mass or more.
  • the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) is 98% by mass or less with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y). This is because if the amount exceeds 98% by mass, the dispersibility of the aqueous resin emulsion ( ⁇ ) tends to decrease. From this point of view, the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 92% by mass or less. is preferred, and 87% by mass or less is more preferred.
  • the copolymer (X) has the structural unit (a), the structural unit (b), and the structural unit (c), that is, when the copolymer (X) is the copolymer (X2)
  • the aqueous Since the dispersibility of the resin emulsion ( ⁇ ) tends to decrease, the following proportions are preferred.
  • the content of the structural unit (a) derived from the (meth)acrylic acid ester (A) in the copolymer (X2) is more preferably 75% by mass or less, particularly preferably 65% by mass or less.
  • Hydrophilic (meth)acrylic acid ester (A1) The structural unit derived from the (meth)acrylate (A) includes a structural unit derived from the hydrophilic (meth)acrylate (A1).
  • the number of carbon atoms in the moieties other than the acryloyloxy group may be, for example, 1 or 2.
  • hydrophilic (meth)acrylic acid ester (A1) examples include methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate.
  • the hydrophilic (meth)acrylic acid ester (A1) is preferably an alkyl (meth)acrylic acid ester in which the alcohol-derived moiety has 2 or less carbon atoms, more preferably methyl methacrylate.
  • the content of the structural unit (a1) derived from the hydrophilic (meth)acrylic acid ester (A1) is 15% by mass or more with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y).
  • the content of the structural unit (a1) derived from the hydrophilic (meth)acrylic acid ester (A1) is less than 15% by mass, the aqueous resin emulsion ( ⁇ ), the curing agent ( ⁇ ) containing the aromatic polyamine, This is because gelation proceeds rapidly by mixing with the curing accelerator ( ⁇ ).
  • the content of the structural unit (a1) derived from the hydrophilic (meth)acrylic acid ester (A1) relative to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 15% by mass or more, and 20% by mass. It is preferably at least 30% by mass, more preferably at least 40% by mass. This is because the water resistance and rust resistance of the coating film made of the cured product of the aqueous resin composition of the present embodiment are further improved.
  • the content of the structural unit (a1) may be 45% by mass or more or 50% by mass or more.
  • the upper limit of the content of the structural unit (a1) derived from the hydrophilic (meth)acrylate (A1) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is (meth)acrylate Structural unit derived from (A) is the same as the upper limit of the content described in (a). That is, the upper limit is 98% by mass or less, preferably 92% by mass or less, and more preferably 87% by mass or less.
  • the structural unit (a1 ) is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less. This is to improve the affinity between the copolymer (X) and the polyepoxy compound (Y).
  • Ethylenically unsaturated carboxylic acid (B) is a compound having an ethylenically unsaturated bond and a carboxy group.
  • Ethylenically unsaturated carboxylic acid (B) includes ⁇ , ⁇ -unsaturated monocarboxylic acid, ⁇ , ⁇ -unsaturated dicarboxylic acid, monoalkyl ester of ⁇ , ⁇ -unsaturated dicarboxylic acid, and vinyl containing a carboxy group. It preferably contains at least one of the group consisting of compounds, and at least It is preferred that one species is included.
  • Examples of ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, and fumaric acid.
  • Examples of vinyl compounds containing a carboxy group include monohydroxyethyl phthalate (meth)acrylate and monohydroxypropyl oxalate (meth)acrylate.
  • Structural unit (b) may be a structural unit derived from only one of these compounds, or may contain structural units derived from two or more of these compounds.
  • the ethylenically unsaturated carboxylic acid (B) includes a compound having a (meth)acryloyl group and a carboxy group, or consists only of a compound having a (meth)acryloyl group and a carboxy group. is preferred. It is also preferable that the ethylenically unsaturated carboxylic acid (B) contains (meth)acrylic acid or consists only of (meth)acrylic acid.
  • Structural unit (b) preferably consists of only structural units derived from a compound having a (meth)acryloyl group and a carboxy group, and further preferably contains structural units derived from (meth)acrylic acid.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) is 0.1% by mass or more with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y). This is for improving the dispersibility of the aqueous resin emulsion ( ⁇ ).
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 0.3% by mass or more. It is preferably 0.5% by mass or more, and more preferably 0.5% by mass or more.
  • the content of the structural unit (b) may be 0.8% by mass or more, or 1.0% by mass or more.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) is 10% by mass or less with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y). This is for suppressing gelling of the copolymer (X) in a high-temperature environment and improving the high-temperature stability of the aqueous resin emulsion ( ⁇ ).
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 7% by mass or less. is preferable, and it is more preferably 5% by mass or less.
  • the content of the structural unit (b) may be 4% by mass or less, or 3% by mass or less.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) is preferably 0.2% by mass or more, and 0.5% by mass. It is more preferably 0.8% by mass or more, and more preferably 0.8% by mass or more.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) is preferably 12% by mass or less, more preferably 8% by mass or less. It is preferably 5% by mass or less, more preferably 3% by mass or less.
  • the ethylenically unsaturated aromatic compound (C) is neither a (meth)acrylic acid ester (A) nor an ethylenically unsaturated carboxylic acid (B), and has a benzene ring and an ethylenically unsaturated bond. is a compound.
  • the ethylenically unsaturated aromatic compound (C) is preferably an aromatic vinyl compound.
  • aromatic vinyl compound as the ethylenically unsaturated aromatic compound (C) examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, tert-butoxystyrene, vinyltoluene, divinyltoluene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrene sulfone acids and salts thereof, ⁇ -methylstyrenesulfonic acid and salts thereof, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isoprop
  • Structural unit (c) may be derived from only one of these compounds, or may include structural units derived from two or more of these compounds.
  • the structural unit (c) is more preferably composed of a structural unit derived from a hydrocarbon, and particularly preferably a structural unit derived from styrene.
  • the copolymer (X) contains the structural unit (c) derived from the ethylenically unsaturated aromatic compound (C), i.e. when the copolymer (X) is the copolymer (X2)
  • the copolymer The content of structural unit (c) with respect to the total amount of (X2) and polyepoxy compound (Y) is preferably 5% by mass or more. This is for improving the water resistance of the coating film made of the cured product of the aqueous resin composition of the present embodiment. From this point of view, the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is more preferably 10% by mass or more, and more preferably 15% by mass or more. is even more preferred.
  • the content of structural unit (c) may be 18% by mass or more, 20% by mass or more, or 23% by mass or more.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is 50% by mass or less.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is more preferably 40% by mass or less, more preferably 35% by mass or less. is more preferred.
  • the content of structural unit (c) may be 33% by mass or less, 30% by mass or less, or 28% by mass or less.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 25% by mass or more. preferable.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) is preferably 55% by mass or less, more preferably 45% by mass or less, and further preferably 35% by mass or less. preferable.
  • the other monomer (D) is none of the (meth)acrylic acid ester (A), the ethylenically unsaturated carboxylic acid (B), and the ethylenically unsaturated aromatic compound (C), and It is a compound having an ethylenically unsaturated bond that can be copolymerized with the compound used for synthesizing the copolymer (X).
  • Other monomers (D) include, for example, conjugated diene compounds, maleimide compounds, vinyl ether compounds, allyl ether compounds, dialkyl esters of unsaturated dicarboxylic acids, and vinyl compounds having a cyano group.
  • conjugated diene compound examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3 butadiene, and chloroprene (2-chloro-1,3-butadiene). etc. These conjugated diene compounds may be used alone or in combination of two or more.
  • maleimide compound examples include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4- methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide, N-(4-hydroxy phenyl)maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These maleimide compounds may be used alone or in combination of two or more.
  • vinyl ether compound examples include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, and hydroxyl group-containing alkyl vinyl ethers in which some hydrogen atoms are substituted with hydroxyl groups.
  • allyl ether compounds include allyl alkyl ethers such as allyl methyl ether and allyl ethyl ether, hydroxyl group-containing allyl alkyl ethers in which some hydrogen atoms are substituted with hydroxyl groups, and allyl glycidyl ethers.
  • dialkyl esters of unsaturated dicarboxylic acids include unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. dialkyl esters of These dialkyl esters of unsaturated dicarboxylic acids may be used alone or in combination of two or more.
  • vinyl compounds having a cyano group examples include acrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -fluoroacrylonitrile. These cyano group-containing vinyl monomers may be used alone or in combination of two or more.
  • Polyepoxy compound (Y) is a compound having no ethylenically unsaturated bond and having two or more epoxy groups in one molecule.
  • the polyepoxy compound (Y) is at least one selected from bisphenol-type epoxy compounds, hydrogenated bisphenol-type epoxy compounds, diglycidyl ethers, triglycidyl ethers, tetraglycidyl ethers, diglycidyl esters, triglycidyl esters, and tetraglycidyl esters. Seeds are preferred.
  • Examples of compounds having two or more epoxy groups in one molecule include diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol F, and glycerin.
  • the polyepoxy compound (Y) is more preferably a bisphenol type epoxy compound or a hydrogenated bisphenol type epoxy compound, more preferably a bisphenol A type epoxy compound or a hydrogenated bisphenol A type epoxy compound. Epoxy compounds are more preferred. This is because the water resistance and rust resistance of the coating film made of the cured product of the aqueous resin composition of the present embodiment are further improved.
  • the weight average molecular weight of the polyepoxy compound (Y) is not particularly limited, it is preferably 1000 or less, more preferably 800 or less, and still more preferably 500 or less.
  • the compatibility of the polyepoxy compound (Y) with the copolymer (X) is improved, and an aqueous resin emulsion ( ⁇ ) having excellent dispersibility and storage stability can be obtained.
  • the lower limit of the weight-average molecular weight of the polyepoxy compound (Y) can be arbitrarily selected, and may be, for example, 200 or 300, but is not limited to these.
  • the epoxy equivalent of the polyepoxy compound (Y) (mass of the polyepoxy compound (Y) per 1 mol of epoxy group) is preferably 500 g/mol or less, more preferably 350 g/mol or less, and 250 g/mol. It is more preferably 200 g/mol or less, particularly preferably 200 g/mol or less. This is because the strength of the film made of the cured product of the aqueous resin composition of the present embodiment is increased.
  • the lower limit of the epoxy equivalent can be arbitrarily selected, and may be, for example, 70 g/mol or more, or 120 g/mol or more, but is not limited to these examples.
  • the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 1% by mass or more. This is because a coating film having excellent rust resistance can be obtained by curing the aqueous resin composition. From this point of view, the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is preferably 5% by mass or more, and 8% by mass or more. is more preferable, and 10% by mass or more is even more preferable. If necessary, it may be 12% by mass or more, or 20% by mass or more.
  • the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 40% by mass or less. This is because a highly dispersible aqueous resin emulsion ( ⁇ ) can be obtained. From this point of view, the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is preferably 35% by mass or less, more preferably 30% by mass or less. is more preferred.
  • the amount of the polyepoxy compound (Y) contained in the aqueous resin emulsion ( ⁇ ) is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total amount of the aqueous resin emulsion ( ⁇ ). It is preferably 4% by mass or more, and more preferably 4% by mass or more.
  • the amount of the polyepoxy compound (Y) contained in the aqueous resin emulsion ( ⁇ ) is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the aqueous resin emulsion ( ⁇ ). It is preferably 15% by mass or less, and more preferably 15% by mass or less.
  • Aqueous medium (Z) > Any aqueous medium (Z) can be selected, and water is preferably used. However, as long as the dispersibility of the copolymer (X) and the polyepoxy compound (Y) is not impaired, for example, water to which a water-soluble solvent has been added may be used as the aqueous medium (Z).
  • the hydrophilic (water-soluble) solvent to be added to water can be arbitrarily selected, and examples thereof include methanol, ethanol, N-methylpyrrolidone, and the like.
  • the amount of the aqueous medium (Z) in the aqueous resin emulsion ( ⁇ ) can be selected as necessary, but it is preferably an amount such that the concentration of non-volatile matter in the aqueous resin emulsion ( ⁇ ) is 20% by mass or more. , more preferably 30% by mass or more, more preferably 40% by mass or more.
  • the amount of the aqueous medium (Z) in the aqueous resin emulsion ( ⁇ ) can be selected as required, but is preferably 80% by mass or less, more preferably 70% by mass or less.
  • the concentration of nonvolatile matter in the aqueous resin emulsion ( ⁇ ) may be 50 to 70% by mass, or 55 to 65% by mass.
  • a method for producing an aqueous resin emulsion ( ⁇ ) comprises a monomer containing a (meth)acrylic acid ester (A) and an ethylenically unsaturated carboxylic acid (B) in the presence of a polyepoxy compound (Y). (That is, the monomers for constituting the copolymer (X)) can be emulsion-polymerized in the aqueous medium (Z).
  • the content of each raw material in the total raw materials used for the production of the aqueous resin emulsion ( ⁇ ) is the same as the content of the structural unit derived from the raw material or the compound corresponding to the raw material in the aqueous resin emulsion ( ⁇ ). .
  • Emulsion polymerization in the method for producing the aqueous resin emulsion ( ⁇ ) of the present embodiment, a method of collectively charging each component including a monomer, a method of polymerizing while continuously supplying each component, and the like can be used. Stirring is preferred during the polymerization reaction.
  • Emulsion polymerization is preferably carried out at an arbitrarily selected temperature, for example, a temperature of 30 to 90°C, more preferably a temperature of 40 to 80°C, and even more preferably a temperature of 40 to 70°C. . This is to prevent the carboxy group contained in the monomer from reacting with the epoxy group contained in the polyepoxy compound (Y).
  • An emulsifier may be used for emulsion polymerization.
  • the emulsifier to be used can be arbitrarily selected, for example, nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, alkyl sulfate salts, alkyl benzene
  • Anionic surfactants such as sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyalkylene alkyl sulfates, and polyoxyalkylene alkyl phosphates are included. These may be used individually by 1 type, and may be used in combination of 2 or more type. Preferred as these emulsifiers are alkylbenzenesulfonates, more preferably sodium dodecylbenzenesulfonate.
  • a polymerization initiator In emulsion polymerization, it is preferable to use a polymerization initiator.
  • the polymerization initiator it is preferable to use, for example, a peroxide.
  • peroxides used as polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, and hydrogen peroxide.
  • a redox initiator can also be used in combination with a peroxide and a reducing agent.
  • reducing agents include sodium sulfoxylate formaldehyde, ascorbic acid, sulfites, tartaric acid and salts thereof. Alcohols and mercaptans may also be used as chain transfer agents, if necessary.
  • an aqueous resin emulsion ( ⁇ ) in which the polyepoxy compound (Y) is uniformly dispersed in the particles of the copolymer (X) produced is obtained.
  • uniformly dispersed does not necessarily mean that the copolymer (X) and the polyepoxy compound (Y) are compatible with each other. and the surface side, the domains of the polyepoxy compound (Y) should be present evenly.
  • the pH of the aqueous resin emulsion ( ⁇ ) is preferably 2-10, more preferably 5-9. When the pH is within this range, the mechanical stability and chemical stability of the aqueous resin emulsion ( ⁇ ) can be improved.
  • the pH is a value measured at a liquid temperature of 25° C. using a pH meter with a hydrogen ion concentration indicator using a glass electrode as a standard electrode.
  • the pH can be adjusted by adding a basic substance to the aqueous resin emulsion ( ⁇ ) during or after emulsion polymerization. Examples of basic substances used for pH adjustment include ammonia, triethylamine, ethanolamine, caustic soda, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Non-volatile content concentration of aqueous resin emulsion ( ⁇ ) The non-volatile content concentration of the aqueous resin emulsion ( ⁇ ) is preferably 10 to 65% by mass, more preferably 15 to 60% by mass, and more preferably 20 to 55% by mass. The nonvolatile content concentration may be 30 to 50% by mass, or 35 to 45% by mass.
  • the concentration of non-volatile matter in the water-based resin emulsion ( ⁇ ) is determined in the step of mixing the water-based resin emulsion ( ⁇ ), the curing agent ( ⁇ ), the curing accelerator ( ⁇ ), etc. described later, or in the coating step of the water-based resin composition. It can be determined as appropriate in consideration of workability.
  • the concentration of non-volatile matter in the aqueous resin emulsion ( ⁇ ) can be appropriately adjusted by adjusting the amount of the aqueous medium (Z) added.
  • the non-volatile content concentration of the aqueous resin emulsion ( ⁇ ) was determined by the method shown below. 1 g of the water-based resin emulsion ( ⁇ ) was weighed into an aluminum dish with a diameter of 5 cm, dried at 105° C. for 1 hour at atmospheric pressure in a drier while air was circulated, and then the mass of the resulting residue was measured. . The ratio (% by mass) of the measured mass of the residue to the mass of the water-based resin emulsion ( ⁇ ) before drying was determined as the non-volatile content of the water-based resin emulsion ( ⁇ ).
  • the viscosity of the aqueous resin emulsion ( ⁇ ) is measured at 23°C.
  • the viscosity of the water-based resin emulsion ( ⁇ ) was measured using a Brookfield viscometer at a rotational speed of 60 rpm with a rotor selected according to the viscosity of the water-based resin emulsion.
  • rotor No. Measured using 1.
  • the viscosity may be, for example, 0.1 to 300 mPa ⁇ s, 1 to 100 mPa ⁇ s, 3 to 50 mPa ⁇ s, or 5 to 25 mPa ⁇ s. .
  • the glass transition point Tg of the copolymer (X) is calculated based on the glass transition point of the homopolymer of each monomer used to synthesize the copolymer (X).
  • both Tg and Tg i are calculated using absolute temperature (K) values.
  • 1/Tg ⁇ (X i /Tg i ) (1)
  • the glass transition point of the homopolymer used to calculate the Tg the value described in the publicly known document shall be used. Specifically, numerical values are listed in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989). For monomers for which multiple types of values are listed in the above Polymer Handbook, the highest value is adopted.
  • the glass transition point Tg of the copolymer (X) is preferably -30°C (243K) or higher. This is because the strength of the film made of the cured product of the aqueous resin composition of the present embodiment is improved. From this point of view, the glass transition point Tg of the copolymer (X) is preferably ⁇ 10° C. (263 K) or higher, more preferably 0° C. (273 K) or higher. The glass transition point Tg of the copolymer (X) may be 5°C or higher, or 10°C or higher. The glass transition point Tg of the copolymer (X) is preferably 100°C (373K) or lower, more preferably 80°C (353K) or lower.
  • the glass transition point Tg of the copolymer (X) is more preferably 60° C. (333 K) or lower, particularly preferably 50° C. (323 K) or lower. This is because in the case of such a range, the flexibility of the coating film made of the cured product of the aqueous resin composition of the present embodiment can be improved.
  • the glass transition point Tg of the copolymer (X) may be 40°C or lower, or 30°C or lower.
  • Epoxy group content in aqueous resin emulsion ( ⁇ ) The content of epoxy groups in the aqueous resin emulsion ( ⁇ ) is the ratio of the number of moles of epoxy groups contained in 1 g of the aqueous resin emulsion ( ⁇ ).
  • the method for determining the amount N 1 [mol/g] of the epoxy groups contained per 1 g of the aqueous resin emulsion ( ⁇ ) is as described in Examples described later.
  • Epoxy group content in total amount of copolymer (X) and polyepoxy compound (Y) contains an epoxy group.
  • the content of epoxy groups in the total amount of copolymer (X) and polyepoxy compound (Y) is preferably 0.50 ⁇ 10 ⁇ 4 mol/g or more, more preferably 1.0 ⁇ 10 ⁇ 4 It is more preferably at least 4.0 ⁇ 10 ⁇ 4 mol/g, even more preferably at least 6.0 ⁇ 10 ⁇ 4 mol/g. This is because the water resistance, rust resistance, and adhesion to the substrate of the coating film made of the cured product of the water-based resin composition of the present embodiment can be enhanced.
  • the content of epoxy groups in the total amount of copolymer (X) and polyepoxy compound (Y) is preferably 50 ⁇ 10 ⁇ 4 mol/g or less, and 30 ⁇ 10 ⁇ 4 mol/g or less. is more preferably 20 ⁇ 10 ⁇ 4 mol/g or less.
  • the content of epoxy groups in the total amount of the copolymer (X) and the polyepoxy compound (Y) is 15 ⁇ 10 ⁇ 4 mol/g or less, or even if it is 10 ⁇ 10 ⁇ 4 mol/g or less. good.
  • the epoxy group content in the non-volatile matter of the aqueous resin emulsion ( ⁇ ) is preferably 0.50 ⁇ 10 ⁇ 4 mol/g or more, more preferably 3.0 ⁇ 10 ⁇ 4 mol/g or more. More preferably, it is 5.0 ⁇ 10 ⁇ 4 mol/g or more. This is because the water resistance, rust resistance, and adhesion to the substrate of the coating film made of the cured product of the water-based resin composition of the present embodiment can be enhanced.
  • the epoxy group content in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) may be 1.0 ⁇ 10 ⁇ 4 mol/g or more, or 6.0 ⁇ 10 ⁇ 4 mol/g or more.
  • the epoxy group content in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) is preferably 50 ⁇ 10 ⁇ 4 mol/g or less, more preferably 30 ⁇ 10 ⁇ 4 mol/g or less, and 20 It is more preferably not more than ⁇ 10 -4 mol/g.
  • the epoxy group content in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) may be 15 ⁇ 10 ⁇ 4 mol/g or less, or 10 ⁇ 10 ⁇ 4 mol/g or less.
  • Carboxy group content in aqueous resin emulsion ( ⁇ ) The content of carboxy groups in the aqueous resin emulsion ( ⁇ ) is the ratio of the number of moles of carboxy groups contained in 1 g of the aqueous resin emulsion ( ⁇ ).
  • the method for determining the number of moles of carboxyl groups contained per 1 g of the aqueous resin emulsion ( ⁇ ) is as described in the examples below.
  • Carboxy group content in total amount of copolymer (X) and polyepoxy compound (Y) In the present embodiment, one or both of the copolymer (X) and the polyepoxy compound (Y) contained in the aqueous resin emulsion ( ⁇ ) contain a carboxy group, and the copolymer (X) contains a carboxy group. is preferably included.
  • the content of carboxy groups in the total amount of copolymer (X) and polyepoxy compound (Y) is preferably 0.10 ⁇ 10 ⁇ 4 mol/g or more, more preferably 0.50 ⁇ 10 ⁇ 4 mol /g or more, and more preferably 1.0 ⁇ 10 ⁇ 4 mol/g or more. This is because aggregation of the copolymer (X) can be suppressed during storage of the aqueous resin emulsion ( ⁇ ) during and after polymerization.
  • the content of carboxy groups in the total amount of copolymer (X) and polyepoxy compound (Y) is preferably 10 ⁇ 10 ⁇ 4 mol/g or less, more preferably 5.0 ⁇ 10 ⁇ 4 mol/g. g or less is more preferable. It may be 3.0 ⁇ 10 ⁇ 4 mol/g or less, 2.5 ⁇ 10 ⁇ 4 mol/g or less, or 2.0 ⁇ 10 ⁇ 4 mol/g or less.
  • Carboxy group content in non-volatile matter of aqueous resin emulsion ( ⁇ ) is preferably 0.10 ⁇ 10 ⁇ 4 mol/g or more, more preferably 0.50 ⁇ 10 ⁇ 4 mol/g or more. More preferably, it is 1.0 ⁇ 10 ⁇ 4 mol/g or more. This is because aggregation of the copolymer (X) can be suppressed during storage of the aqueous resin emulsion ( ⁇ ) during and after polymerization.
  • the content of carboxy groups in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) is preferably 10 ⁇ 10 ⁇ 4 mol/g or less, more preferably 5.0 ⁇ 10 ⁇ 4 mol/g or less. . It may be 3.0 ⁇ 10 ⁇ 4 mol/g or less, 2.5 ⁇ 10 ⁇ 4 mol/g or less, or 2.0 ⁇ 10 ⁇ 4 mol/g or less.
  • the carboxy group includes not only —COOH but also a structure in which a cation other than a hydrogen ion is bonded with —COO 2 — .
  • the content of carboxy groups in the non-volatile matter of the water-based resin emulsion ( ⁇ ) is, as shown by the following formula, the content of carboxy groups in the raw materials, the functional groups that react with the carboxy groups in the raw materials, polymerization It is obtained from the value obtained by subtracting the amount of decrease before and after.
  • the raw materials refer to the components used for the synthesis of the aqueous resin emulsion ( ⁇ ).
  • the functional group that reacts with the carboxy group is an epoxy group, and the hydroxy group is not considered as a functional group that reacts with the carboxy group.
  • the method for determining the content R CX [mol/g] of carboxy groups in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) will be described in detail below.
  • the total amount of carboxyl groups in the raw material (including initiator, solvent, other additives, etc.) is N 3 [mol/g]
  • the total amount of epoxy groups in the raw material (including initiator, solvent, other additives, etc.) is N 2 [mol/g]
  • the amount of epoxy groups contained per 1 g of the aqueous resin emulsion ( ⁇ ) is N 1 [mol/g].
  • the non-volatile content concentration of the aqueous resin emulsion ( ⁇ ) is defined as C S [% by mass].
  • R CX is represented by the formula (3). How to obtain N1 and N2 will be described later in Examples. N2 can be obtained by calculation.
  • R CX [mol/g] ⁇ N 3 ⁇ (N 2 ⁇ N 1 ) ⁇ /(C S /100) (3)
  • the curing agent ( ⁇ ) contains an aromatic polyamine (F) having active hydrogens with reactivity towards epoxy groups.
  • the active hydrogen having reactivity with the epoxy group means that the amino group of the aromatic polyamine (F) forms a bond by nucleophilic attack on the epoxy group, and then can be eliminated from the nitrogen atom. means a hydrogen atom.
  • the amino group of the aromatic polyamine (F) consists of an unsubstituted amino group (--NH 2 (no substituent), an amino group having only one substituent (--NHR (R is a substituent)). Any one selected from the group is preferable.
  • the aromatic polyamine (F) having active hydrogen has a benzene ring and two or more amino groups in one molecule.
  • the aromatic polyamine (F) having active hydrogen may be a compound having only one type of amino group, or a compound having two or more types of amino groups.
  • the curing agent ( ⁇ ) may contain only one type of aromatic polyamine (F) having active hydrogen, or may contain two or more types thereof.
  • Examples of the aromatic polyamine (F) having active hydrogen include m-xylylenediamine (hereinafter sometimes referred to as "MXDA”), diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, and these Modified products and the like can be mentioned.
  • the modified product is preferably a compound obtained by an addition reaction in which an atom or atomic group is bonded to the amino group of MXDA.
  • the curing agent ( ⁇ ) contains the aromatic polyamine (F) having the active hydrogen, it cures at room temperature for a short period of time, and exhibits excellent initial water resistance and wet heat adhesion to metal materials. It becomes the water-based resin composition which can form the coating film which has. Therefore, the water-based resin composition of the present embodiment can be suitably used for anti-corrosion coating of metal products such as iron. Although the reason for such an effect is not clear, the curing agent ( ⁇ ) containing the aromatic polyamine (F) having active hydrogen can easily penetrate into the particles of the aqueous resin emulsion ( ⁇ ).
  • the hardening acceleration function of the curing agent ( ⁇ ) with respect to the polyepoxy compound (Y) contained in the aqueous resin emulsion ( ⁇ ) becomes remarkable, and it is considered that the aqueous resin composition cures in a short time. .
  • the aromatic compounds are more hydrophobic. It is presumed that the aromatic polyamine (F) having active hydrogen contained in the curing agent ( ⁇ ) is more hydrophobic than the aqueous resin emulsion ( ⁇ ). For this reason, it is considered that the aromatic polyamine (F) having active hydrogen is less likely to stay in the aqueous layer of the aqueous resin composition and is likely to be distributed inside the particles of the aqueous resin emulsion ( ⁇ ).
  • the aromatic polyamine (F) having active hydrogen is more likely to enter the inside of the particles of the aqueous resin emulsion ( ⁇ ) than, for example, an aliphatic polyamine having a similar molecular weight. It is easy to approach the epoxy group of ( ⁇ ).
  • the aqueous resin composition of the present embodiment containing the aromatic polyamine (F) having the active hydrogen has a higher concentration in the aqueous resin emulsion ( ⁇ ) than the case where the aliphatic polyamine having the same molecular weight is contained. It is considered that the contained polyepoxy compound (Y) is easily cured, and the curing speed of the water-based resin composition is increased.
  • the aromatic polyamine (F) having active hydrogen is an aromatic polyamine (F ), more preferably an aromatic polyamine (F) having 3 or more benzene rings in one molecule.
  • the aromatic polyamine (F) having two or more benzene rings in one molecule is compared with the aromatic polyamine (F) having only one benzene ring in one molecule. As a result, it is even more hydrophobic. Therefore, the aromatic polyamine (F) having two or more benzene rings in one molecule more easily penetrates into the inside of the particles of the aqueous resin emulsion ( ⁇ ), and has only one benzene ring in one molecule.
  • the aromatic polyamine (F) having active hydrogen preferably contains an aromatic polyamine (F) having 13 or less benzene rings in one molecule. It is more preferable to contain the aromatic polyamine (F) having the following benzene rings.
  • Examples of the aromatic polyamine (F) having two or more benzene rings in one molecule include compounds represented by the following general formula (1-1) and compounds represented by the following general formula (1-2). etc.
  • a 2 and A 3 each independently represent a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group; n is an integer of 1 to 12; show.
  • a 1 represents a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.
  • Each of A 2 and A 3 in formula (1-1) and A 1 in formula (1-2) is a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.
  • represents A 2 and A 3 in the formula (1-1) and A 1 in the formula (1-2) facilitate the curing reaction of the water-based resin composition.
  • a phenylene group is preferred.
  • a 2 contained in a repeating unit (A 2 described in parentheses) and A 3 not contained in a repeating unit (A 3 described outside the parentheses) may be the same or different. Further, in the compound represented by formula (1-1), when n is 2 to 12, A 2 contained in the repeating unit may all be the same, or different ones may be included. good. Since the compound represented by formula (1-1) can be easily produced, it is preferable that A 2 and A 3 contained in the compound are all the same.
  • n the number of repeating units in parentheses, represents an integer of 1-12.
  • the aromatic polyamine (F) having active hydrogen a plurality of types of compounds having different numbers of repeating units (number of n) in formula (1-1) may be used.
  • the number of n in formula (1-1) is preferably 2 or more from the viewpoint that the curing reaction of the aqueous resin composition proceeds more easily. Further, the number of n in the formula (1-1) is preferably 9 or less because the aromatic polyamine (F) having active hydrogen has good water solubility and is easily available.
  • the number of n in the general formula (1-1) is 1.
  • the content of a certain compound is preferably 10% by mass to 35% by mass, more preferably 15% by mass to 30% by mass, and even more preferably 18% by mass to 25% by mass.
  • the compound represented by general formula (1-1) is more hydrophobic than the compound represented by general formula (1-2). Therefore, the compound represented by general formula (1-1) is more likely to approach the epoxy groups of the polyepoxy compound (Y) contained in the aqueous resin emulsion ( ⁇ ). Therefore, when the aromatic polyamine (F) having active hydrogen contains the compound represented by the general formula (1-1), the water-based resin composition can form a coating film having superior initial water resistance.
  • the aromatic polyamine (F) having active hydrogen contains a compound represented by general formula (1-1) and MXDA.
  • the resulting water-based resin composition can form a coating film having superior initial water resistance. It is presumed that this is due to the synergistic effect of the effect resulting from the high hydrophobicity of the compound represented by the general formula (1-1) and the effect resulting from the small steric hindrance of MXDA.
  • the aromatic polyamine (F) having the active hydrogen is more likely to approach the epoxy groups contained in the aqueous resin emulsion ( ⁇ ), and the polyamine contained in the aqueous resin emulsion ( ⁇ ) It is presumed that the curing of the epoxy compound (Y) is accelerated and the curing speed of the water-based resin composition is increased. Furthermore, when the aromatic polyamine (F) having active hydrogen contains the compound represented by the general formula (1-1) and MXDA, the synergistic effect promotes curing of the aqueous resin composition. Therefore, a cured product having higher film yield strength can be formed.
  • the content of MXDA in the aromatic polyamine (F) having active hydrogen is preferably 10% by mass to 40% by mass, more preferably 20% by mass to 30% by mass, even more preferably 24% by mass to 28% by mass.
  • the compound represented by general formula (1-1) in the aromatic polyamine (F) having active hydrogen is preferably 60% by mass to 90% by mass, more preferably 70% by mass to 80% by mass. is more preferable, and 72% by mass to 76% by mass is even more preferable. This is because the compound represented by the general formula (1-1) and MXDA have a more pronounced synergistic effect.
  • the content of the compound in which the number of n in general formula (1-1) is 1 is based on the total amount of the aromatic polyamine (F) having active hydrogen. It is preferably 10% by mass to 35% by mass, more preferably 15% by mass to 30% by mass, even more preferably 18% by mass to 25% by mass.
  • aromatic polyamine (F) having active hydrogen Commercially available products may be used as the aromatic polyamine (F) having active hydrogen.
  • Commercially available products containing an aromatic polyamine (F) having two or more benzene rings in one molecule include, for example, Gaskamine 328 (trade name, Mitsubishi Gas Chemical Company, Inc.); Gaskamine 240 (trade name, Mitsubishi Gas Chemical Company, Inc.) ) and the like. Both Gaskamine328 and Gaskamine240 are mixtures containing modified MXDA and MXDA.
  • Gaskamine 328 contains a compound represented by general formula (1-1) as a modified MXDA.
  • Gaskamine 240 contains a compound represented by general formula (1-2) as a modified MXDA.
  • Gaskamine 328 contains MXDA and the compound represented by formula (1-1), which is an aromatic polyamine consisting of a reaction product of epichlorohydrin and MXDA.
  • Gaskamine328 is a compound represented by the formula (1-1) (A 2 and A 3 in the formula (1-1) are all 1,3-phenylene groups; n is 1 to 12; ) contains 73.3% by mass.
  • the content of compounds in which n is 1 among the compounds represented by formula (1-1) contained in Gaskamine 328 was 20.9% by mass.
  • Gaskamine328 contains 26.7% by mass of MXDA.
  • Gaskamine 240 contains MXDA and a compound represented by formula (1-2), which is an aromatic polyamine consisting of a reaction product of styrene and MXDA. Specifically, Gaskamine 240 contains 99% by mass or more of the compound represented by formula (1-2) (in formula (1-2), A 1 is a 1,3-phenylene group). Gaskamine 240 also contains less than 1% by weight of MXDA.
  • each component of the curing agent ( ⁇ ) contained in the aqueous resin composition and the content of each component are determined using chromatographic analysis such as gas chromatography (GC) analysis and gel filtration chromatography (GPC) analysis. I can confirm.
  • chromatographic analysis such as gas chromatography (GC) analysis and gel filtration chromatography (GPC) analysis. I can confirm.
  • the content of the aromatic polyamine (F) having active hydrogen contained in the curing agent ( ⁇ ) is contained in the aromatic polyamine (F) with respect to 1 equivalent of the epoxy group contained in the aqueous resin emulsion ( ⁇ ).
  • Active hydrogen is 0.10 equivalents or more, preferably 0.20 equivalents or more, and more preferably 0.30 equivalents or more.
  • Initial water resistance and film yield strength are improved by increasing the cross-linking density of the water-based resin composition after curing. This is because adhesion is improved.
  • the content of the aromatic polyamine (F) having active hydrogen contained in the curing agent ( ⁇ ) is contained in the aromatic polyamine (F) with respect to 1 equivalent of the epoxy group contained in the aqueous resin emulsion ( ⁇ ).
  • Active hydrogen is 1.50 equivalents or less, preferably 1.3 equivalents or less, more preferably 1.2 equivalents or less. This is because excessive curing shrinkage of the water-based resin composition can be suppressed, and a cured product having good wet-heat adhesion to metal materials can be formed.
  • the curing accelerator ( ⁇ ) has the function of accelerating the curing of the water-based resin composition and forming a film with high film yield strength.
  • Curing accelerators ( ⁇ ) include tertiary amines that do not have active hydrogens that are reactive towards epoxy groups.
  • the tertiary amine in this embodiment is represented by NR 1 R 2 R 3 (wherein R 1 R 2 R 3 is a substituent group, each of which may be different or two or more of which are the same). R 1 R 2 R 3 may combine with each other to form a ring.).
  • the curing accelerator ( ⁇ ) directly binds to nitrogen atoms of tertiary aliphatic amines, tertiary alicyclic amines, tertiary heteroaromatic amines, and tertiary amines (NR 1 R 2 R 3 ).
  • it is at least one compound selected from the group consisting of tertiary aromatic amines having a phenyl group that does not have a phenyl group. This is because the nucleophilicity of the curing accelerator ( ⁇ ) is increased and the curing reaction proceeds efficiently.
  • tertiary aliphatic amines examples include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, and tri-n-hexylamine.
  • Tertiary alicyclic amines include, for example, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8 -diazabicyclo[5.4.0]undec-7-ene, and the like.
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • 1,5-diazabicyclo[4.3.0]non-5-ene 1,8 -diazabicyclo[5.4.0]undec-7-ene, and the like.
  • a compound having an imidazole skeleton it is preferable to use a compound having an imidazole skeleton, and specific examples include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and the like.
  • Tertiary aromatic amines having a phenyl group not directly bonded to the nitrogen atom of the tertiary amine include dimethylbenzylamine, diethylbenzylamine, tribenzylamine, 2,4, 6-trisdimethylaminomethylphenol, 2-phenylimidazole and the like.
  • curing accelerators ( ⁇ ) it is particularly preferable to use the following compounds (i) and/or (ii).
  • Tertiary alicyclic amines include, for example, 1,4-diazabicyclo[2.2.2]octane (DABCO).
  • Tertiary heteroaromatic amines include, for example, imidazole.
  • the curing accelerator ( ⁇ ) may be used singly or in combination of two or more.
  • the content of the curing accelerator ( ⁇ ) is 0.0070 mol or more, preferably 0.070 mol or more, and 0.18 mol or more, relative to 1 equivalent of the epoxy group contained in the aqueous resin emulsion ( ⁇ ). more preferably 0.30 mol or more. This is because the film formed of the cured product of the aqueous resin composition of the present embodiment has a high film yield strength.
  • the content of the curing accelerator ( ⁇ ) is 1.5 mol or less, preferably 1.0 mol or less, and 0.70 mol or less with respect to 1 equivalent of the epoxy group contained in the aqueous resin emulsion ( ⁇ ). more preferably 0.44 mol or less, still more preferably 0.40 mol or less, and particularly preferably 0.38 mol or less. This is because the cured product of the water-based resin composition of the present embodiment forms a coating film having good wet heat adhesion to metal materials. Further, when the content of the curing accelerator ( ⁇ ) is 1.5 mol or less, gelling of the water-based resin composition in a short time can be suppressed, and a cured product with good rust resistance can be obtained.
  • the aqueous resin composition according to this embodiment may contain a pigment.
  • pigments include titanium oxide, talc, barium sulfate, carbon black, red iron oxide, calcium carbonate, silicon oxide, talc, mica, kaolin, clay, ferrite, and silica sand.
  • the pigment may contain only one compound, or may contain two or more compounds.
  • the pigment content in the aqueous resin composition is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass. This is for improving the concealability of the coating film.
  • the aqueous resin composition contains a filler, an organic or inorganic hollow balloon, a dispersing agent (e.g., amino alcohol, polycarboxylate, etc.), a surfactant, a coupling agent (e.g., silane coupling agent, etc.), and a defoaming agent.
  • a dispersing agent e.g., amino alcohol, polycarboxylate, etc.
  • a surfactant e.g., silane coupling agent, etc.
  • a coupling agent e.g., silane coupling agent, etc.
  • defoaming agent e.g., silane coupling agent, etc.
  • preservatives e.g., biocides, fungicides, fungicides, algaecides, and combinations thereof, etc.
  • flow agents e.g., leveling agents, neutralizing agents (e.g., hydroxides, amines, ammonia, carbonic acid salt etc.) etc.
  • Silane coupling agents include epoxysilane compounds. Specific examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexy)ethyl trimethoxysilane and the like.
  • the amount of the silane coupling agent added is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the aqueous resin emulsion. This is because the cured water-based resin composition has improved rust resistance and adhesion to metal materials.
  • the aqueous resin composition of the present embodiment is produced by a method of mixing an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), a curing accelerator ( ⁇ ), and optionally other components. can.
  • a method for mixing each component contained in the aqueous resin composition of the present embodiment a known method can be used.
  • the aqueous resin composition of this embodiment contains an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), and a curing accelerator ( ⁇ ). For this reason, it cures at room temperature for a short period of time, and a coating film having good initial water resistance and wet heat adhesion to metal materials can be obtained.
  • the coating film of the present embodiment is composed of a cured product of the aqueous resin composition of the present embodiment.
  • the coating film of the present embodiment is, if necessary, an undercoat layer provided as a lower layer of a coating film made of a cured product of the aqueous resin composition of the present invention, and / or a topcoat layer provided as an upper layer. It may be provided in a layered manner with the film.
  • a method for producing a coating film composed of a cured product of the aqueous resin composition of the present embodiment will be described in detail.
  • an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), a curing accelerator ( ⁇ ), and optionally other components are mixed.
  • the aqueous resin composition of the present embodiment is prepared (mixing step).
  • the aqueous resin composition obtained in the mixing step is applied to the surface to be coated (application step).
  • the aqueous resin emulsion ( ⁇ ), the curing agent ( ⁇ ), the curing accelerator ( ⁇ ), and optionally other components are mixed and stirred by a known method.
  • an aqueous resin composition in which each component is dispersed is obtained.
  • Stirring in the mixing step can be performed, for example, by Robomics (manufactured by Primix Co., Ltd.).
  • stirring in the mixing step is preferably performed for 5 minutes or longer.
  • the stirring time is preferably within 1 hour.
  • the aqueous resin composition is applied to the surface of the article to be coated.
  • materials forming the surface to be coated include metallic materials such as iron.
  • the surface to be coated may be previously subjected to a surface treatment such as a primer or an undercoat.
  • a method for applying the aqueous resin composition a known method can be used, and examples thereof include, but are not limited to, methods using a brush, a roller, and the like.
  • the coating process is preferably completed within 1 hour after the mixing process is completed, and the coating process is completed within 30 minutes. It is more preferable to complete within
  • the method for producing a coating film of the present embodiment it is preferable to perform a curing step of curing the coating film obtained by coating the surface to be coated after the coating step.
  • the surface of the object coated with the aqueous resin composition is dried and cured to cure the resin component contained in the aqueous resin composition.
  • Curing time varies depending on the temperature of the curing atmosphere. For example, at normal temperature (20° C.), the time is preferably 5 hours or more, at 40° C. it is preferably 1 hour or more, and at 60° C. it is preferably 5 minutes or more.
  • the coating film of the present embodiment is composed of a cured product of the aqueous resin composition of the present embodiment. Therefore, the initial water resistance and wet heat adhesion to metal materials are good. Further, in the method for producing a coating film of the present embodiment, the aqueous resin composition is prepared by mixing the aqueous resin emulsion ( ⁇ ), the curing agent ( ⁇ ), and the curing accelerator ( ⁇ ), and Apply to surface to be coated. Therefore, the coating film of this embodiment can be formed from the cured product of the aqueous resin composition of this embodiment.
  • aqueous resin composition set of this embodiment the constituent components of the aqueous resin composition of the present embodiment are stored separately into the first liquid and the second liquid.
  • the first liquid in the aqueous resin composition set of the present embodiment contains the aqueous resin emulsion ( ⁇ ).
  • the second liquid contains a curing agent ( ⁇ ) and a curing accelerator ( ⁇ ).
  • the coating film of this embodiment may be produced using the aqueous resin composition set of this embodiment. That is, the aqueous resin composition of the present embodiment is prepared by mixing the first liquid and the second liquid in the aqueous resin composition set of the present embodiment (mixing step). Thereafter, the water-based resin composition is applied to the surface to be coated in the same manner as in the method for producing a coating film described above (coating step).
  • the aqueous resin composition set of the present embodiment is divided into a first liquid containing the aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), and a second liquid containing the curing accelerator ( ⁇ ) and stored. . Therefore, the aqueous resin composition set of the present embodiment is excellent in storage stability because the resin component contained in the aqueous resin emulsion ( ⁇ ) does not react with the curing agent ( ⁇ ) during storage and is cured.
  • the first liquid and the second liquid may be stored in separate containers or the like. The shape and material of the container can be arbitrarily selected.
  • the container containing the first liquid and the container containing the second liquid may be separated from each other or may be in contact with each other.
  • a coating film having good initial water resistance and wet heat adhesion to metal materials can be obtained. .
  • the aqueous resin composition of the present invention is useful in various fields.
  • the water-based resin composition of the present invention is particularly suitable for use as an anticorrosive paint to be applied to the surfaces of metal products used outdoors such as steel towers, bridges, ships, port facilities and the like.
  • An article on which a coating film comprising a cured product of the aqueous resin composition of the present invention is formed, that is, an object to be coated with the aqueous resin composition of the present invention can be selected arbitrarily.
  • Specific examples of applicable objects include steel towers, bridges, ships, metal products used outdoors such as port facilities, various household goods, home appliances such as refrigerators, and installations in amusement parks and parks. playground equipment, sporting goods, buildings (interior, exterior, etc.), various industrial goods and their parts including transportation machinery and machine tools, automobile bodies and chassis, railway vehicle bodies and underfloor equipment, ships, marine containers, aircraft etc.
  • aqueous resin emulsion ( ⁇ )> (Aqueous resin emulsion ( ⁇ -1))
  • An emulsion comprising the amounts (parts by mass) shown in Table 1 of methyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid, hydrogenated bisphenol A type epoxy, sodium dodecylbenzenesulfonate as an emulsifier, and 356 parts by mass of deionized water. was added dropwise over 3 hours.
  • 1.2 parts by mass of potassium persulfate as an oxidizing agent dissolved in 41 parts by mass of ion-exchanged water and 0.4 parts by mass of sodium bisulfite as a reducing agent were dissolved in 21 parts by mass of ion-exchanged water. was added dropwise at 60° C. over 3.3 hours to polymerize. After completion of dropping, the mixture was aged for 1.5 hours. After cooling, 0.8 parts by mass of aqueous ammonia as a basic substance was added to obtain an aqueous resin emulsion ( ⁇ -1).
  • Table 1 shows the amount (parts by mass) of each material used in the synthesis of the aqueous resin emulsion ( ⁇ -1).
  • the numerical value of "ion-exchanged water” shown in Table 1 indicates the content of ion-exchanged water contained in the synthesized aqueous resin emulsion ( ⁇ -1).
  • the values in parentheses for the contents of the copolymer (X) and the polyepoxy compound (Y) are the total amount (100%) of the copolymer (X) and the polyepoxy compound (Y). Shows the ratio (mass%) of each material to
  • polyepoxy compound (Y) shown in Table 1 the following compounds were used. Hydrogenated bisphenol A epoxy (epoxy equivalent: 215 g/mol; manufactured by Kyoei Chemical Co., Ltd.; Epolite 4000) Bisphenol A type epoxy (epoxy equivalent: 190 g/mol; manufactured by Mitsubishi Chemical Corporation; JER828) 1,6-hexanediol diglycidyl ether (epoxy equivalent 160 g/mol; manufactured by Kyoei Chemical Co., Ltd.; Epolite 1600)
  • Hydrogenated bisphenol A epoxy epoxy equivalent: 215 g/mol; manufactured by Kyoei Chemical Co., Ltd.; Epolite 4000
  • Bisphenol A type epoxy epoxy equivalent: 190 g/mol; manufactured by Mitsubishi Chemical Corporation; JER828) 1,6-hexanediol diglycidyl ether (epoxy equivalent 160 g/mol; manufactured by Kyoei Chemical Co., Ltd.; Epolite 1600)
  • Aqueous resin emulsion ( ⁇ -2) to ( ⁇ -6) Aqueous resin emulsions ( ⁇ -2) to ( ⁇ -6) were prepared in the same manner as the aqueous resin emulsion ( ⁇ -1) except that each material shown in Table 1 was used in the amount (parts by mass) shown in Table 1. ) was synthesized.
  • the numerical value of "ion-exchanged water" shown in Table 1 is the same as the synthesized aqueous resin emulsion ( ⁇ -1).
  • the contents of ion-exchanged water contained in aqueous resin emulsions ( ⁇ -2) to ( ⁇ -6) are shown.
  • aqueous resin emulsion ( ⁇ ) > The following items were evaluated for each of the aqueous resin emulsions ( ⁇ -1) to ( ⁇ -6). Table 2 shows the results.
  • the water-based resin emulsion ( ⁇ -6) having an excessive content of the polyepoxy compound (Y) was not evaluated because it aggregated during synthesis.
  • the aqueous resin emulsions ( ⁇ -1) to ( ⁇ -6) may be collectively referred to as the aqueous resin emulsion ( ⁇ ).
  • the residual ratio of epoxy groups in the water-based resin emulsion ( ⁇ ) is the amount N 1 [mol/g] of the epoxy groups contained in the water-based resin emulsion ( ⁇ ) after synthesis. It is the ratio to the total amount N 2 [mol/g] of epoxy groups contained in components (including raw materials, initiators, solvents, other additives, etc.).
  • the amount N 1 [mol/g] of epoxy groups in the aqueous resin emulsion ( ⁇ ) after synthesis was measured by the following method. An excess amount of hydrogen chloride was added to the total amount of epoxy groups contained in the components (raw materials) used in the synthesis of the aqueous resin emulsion ( ⁇ ) to react with the epoxy groups. Next, the amount of remaining hydrogen chloride was confirmed by titrating unreacted hydrogen chloride with potassium hydroxide. At this time, potassium hydroxide is consumed by reaction with acidic components such as carboxylic acid contained in the aqueous resin emulsion ( ⁇ ). Therefore, the amount of acidic components was titrated in advance by blank measurement without using hydrogen chloride, and the result of this measurement was corrected. Specific measurement procedures are as follows (i) to (ii).
  • the amount of the potassium hydroxide/ethanol solution used for titration is defined as V KOH1 [mL].
  • the solution was titrated with a 0.1 M potassium hydroxide/ethanol solution while stirring. After the potassium hydroxide/ethanol solution was added dropwise, the point at which the purple color persisted for 30 seconds was taken as the equivalence point.
  • the amount of potassium hydroxide/ethanol solution used for titration is defined as V KOH2 [mL].
  • N 1 (0.2 ⁇ V HCl /1000 ⁇ 0.1 ⁇ V KOH2 /1000)/W 2 +(0.1 ⁇ V KOH1 /1000)/W 1 (4)
  • the components used for the synthesis of the aqueous resin emulsion ( ⁇ ) mean all the components listed in Table 1 as raw materials for the aqueous resin emulsion ( ⁇ ).
  • N 2 ⁇ (m i /EP i )/ ⁇ m i (5)
  • 1/EP i 0 for compounds that do not contain an epoxy group, such as methyl methacrylate and ion-exchanged water. From the amount of epoxy groups determined in this way, the residual rate of epoxy groups in the aqueous resin emulsion ( ⁇ ) is expressed as 100 ⁇ N 1 /N 2 [mol %].
  • the epoxy group content R EP [mol/g] in the non-volatile matter was obtained based on the above-described formula (2).
  • R EP N 1 /(C S /100) (2)
  • N 3 ⁇ (m i /CX i )/ ⁇ m i (6) From the N3 obtained here, the content rate R CX [mol/g] of carboxy groups in the nonvolatile matter of the aqueous resin emulsion ( ⁇ ) was obtained based on the above-described formula (3).
  • R CX ⁇ N 3 -(N 2 -N 1 ) ⁇ /(C S /100) (3)
  • the glass transition point Tg of copolymer (X) is a value calculated by the above formula (1).
  • the high-temperature stability of the aqueous resin emulsion ( ⁇ ) was evaluated as follows. First, the water-based resin emulsion ( ⁇ ) was put into a 70 ml glass bottle, and the bottle was sealed and allowed to stand at 60° C. for 7 days. After that, the state of the aqueous resin emulsion ( ⁇ ) in the glass bottle was visually observed and evaluated according to the following criteria. ⁇ (Possible): Aggregation, thickening, precipitation, separation, and gelation were not observed. ⁇ (improper): At least one of aggregation, thickening, precipitation, separation, and gelation was observed.
  • Examples 1 to 10 and Comparative Examples 1 to 15 (Preparation of aqueous resin composition)> 100 parts by mass of the aqueous resin emulsion ( ⁇ ) shown in Tables 3 to 5 (nonvolatile content of 40% by mass), 60 parts by mass of ion-exchanged water, and the curing agent ( ⁇ ) shown in Tables 3 to 5 A curing accelerator ( ⁇ ) was added in the amounts (parts by mass) shown in Tables 3 to 5 and stirred for 10 minutes to prepare aqueous resin compositions of Examples 1 to 10 and Comparative Examples 1 to 15. .
  • the "active hydrogen equivalent to epoxy group" in each curing agent ( ⁇ ) is the active hydrogen contained in the curing agent ( ⁇ ) with respect to 1 equivalent of the epoxy group contained in the aqueous resin emulsion ( ⁇ ). It is a numerical value indicating the equivalent of active hydrogen contained in the aromatic polyamine (F) having The "number of moles per epoxy group” in the curing accelerator ( ⁇ ) is a numerical value indicating the number of moles of the curing accelerator ( ⁇ ) per equivalent of epoxy groups contained in the aqueous resin emulsion ( ⁇ ).
  • "MXDA content [% by mass]” is a numerical value indicating the content of MXDA in the aromatic polyamine (F) having active hydrogen contained in the curing agent ( ⁇ ).
  • Gaskamine 328 (Mitsubishi Gas Chemical Company, Inc.) or m-xylylenediamine (MXDA) (Mitsubishi Gas Chemical Company, Inc.) was used as the aromatic polyamine (F) shown in Tables 3 to 5.
  • the equivalent weight of active hydrogen contained in MXDA is 34 g/mol.
  • the equivalent of active hydrogen contained in Gaskamine 328 is 55 g/mol.
  • Gaskamine 328 is a mixture containing modified MXDA and MXDA.
  • Gaskamine 328 contains 73.3% by mass of the compound represented by general formula (1-1), which is a modified MXDA.
  • Gaskamine 328 contains 26.7% by weight of MXDA.
  • EH-8051 (trade name; ADEKA HARDNER EH-8051, manufactured by ADEKA Corporation) or ED-600 (trade name; JEFFAMINE ED-600, Huntsman Japan Co., Ltd.) company) was used.
  • the equivalent weight of active hydrogen contained in ADEKA HARDNER EH-8051 is 180 g/mol.
  • the equivalent weight of active hydrogen contained in JEFFAMINE ED-600 is 132 g/mol.
  • the water-based resin composition was applied by drooling so as to spread over the entire surface of a horizontally placed rectangular polyethylene film having a length of 90 mm and a width of 190 mm. After drying this at 23° C. for 72 hours, it was cured at 50° C. for 24 hours to prepare a coating film having a thickness of about 300 ⁇ m. The resulting coating film was peeled off from the plate. A film obtained by peeling the coating film from the flat plate was cut into a rectangle having a width of 10 mm and a length of 30 mm to obtain a test piece.
  • the following tests were performed with the longitudinal direction of this test piece as the tensile direction.
  • the thickness of the test piece was measured using Quick Micro (registered trademark) MDQ-MX manufactured by Mitutoyo Corporation. Each test piece was measured at three locations, and the average value of the measurement results at the three locations was taken as the thickness t [mm] of the test piece.
  • the thickness of the specimen was about 300 ⁇ m.
  • the coating yield strength test was performed using Autograph AG-X (manufactured by Shimadzu Corporation) according to the method shown below. With the chuck-to-chuck distance set to 10 mm, both longitudinal sides of the test piece were gripped by chucks. The test piece was pulled at a speed of 100 mm/min in an atmosphere with a temperature of 23° C. and a relative humidity (RH) of 50%.
  • RH relative humidity
  • the strain S is 100 It is calculated by ⁇ L/L [%].
  • the load applied to the test piece is F [N]
  • the maximum value of the load until the test piece breaks is F max [N]
  • the following conditions are initially applied from the start of the test. Let the point that satisfies the conditions be the yield point Y (S y , F y ).
  • the coating yield strength which is the stress ⁇ y applied to the test piece at the yield point Y, is calculated by the following formula.
  • ⁇ y [N/mm 2 ] F y /(W ⁇ t) (W in the formula is the width [mm] of the test piece, and t is the thickness [mm] of the test piece.)
  • the water-based resin composition was applied to the surface of a cold-rolled steel plate (thickness: 800 ⁇ m) using a brush so as to have a basis weight of 50 g/m 2 , and dried at 23° C. for 1 day (24 hours). As a result, a rectangular test piece having a coating film on the surface and measuring 70 mm long and 150 mm wide was formed. The thickness of the coating film on the specimen was about 100 ⁇ m.
  • test piece thus prepared was immersed in deionized water, sealed, and stored at 23° C. for 7 days. After that, the test piece was taken out from the ion-exchanged water. For the test piece taken out, the rusted area in the test region (area%) and the blistered area in the test region (area%) were measured by the method described below.
  • the test area was a rectangular area of 45 mm long and 125 mm wide in the coating film of the test piece.
  • the appearance of the test piece was visually observed, and the area where the surface of the coating film turned brown or black due to storage was defined as the area where rust occurred.
  • the dimensions of each rusted area within the test area were measured using a ruler, and the total area of the rusted areas within the test area was calculated. Using the results, the ratio of the rusted area (%) to the area of the test region was determined.
  • the appearance of the test piece was visually observed and evaluated by finger touch, and the presence or absence of an area where the surface of the coating film had blister due to storage was examined. As a result, the planar shape of each bulging region was substantially circular.
  • each bulging region was assumed to be a perfect circle, and the maximum straight distance connecting the contour lines of the bulging region was measured with a ruler, and the result was taken as the diameter. Then, using the diameter of each swollen region, the total area of swollen regions in the test region was calculated, and the ratio of the swollen area (%) to the area of the test region was determined.
  • the water-based resin composition was applied to the surface of a cold-rolled steel plate (thickness: 800 ⁇ m) using a brush so as to have a basis weight of 50 g/m 2 , and dried at 23° C. for 7 days. As a result, a rectangular test piece having a coating film on the surface and measuring 70 mm long and 150 mm wide was formed. The test area was a rectangular area of 45 mm long and 125 mm wide in the coating film of the test piece. The thickness of the coating film on the specimen was about 100 ⁇ m.
  • the test piece thus prepared was stored in a constant temperature bath at 40°C and 98% relative humidity (RH) for 3 days. After that, according to JIS K-5400 (1990) "8.5.2 Cross-cut tape method", a cutter was used to cut a cross-cut at 1 mm intervals so as to penetrate the coating film formed in the test area of the test piece. A cut (100 squares) was made, and Sellotape (registered trademark) was pasted. One hour after lamination, the sellotape (registered trademark) was peeled off, and the number of squares remaining without peeling of the coating film from the steel plate was counted. Then, the wet heat adhesion of the coating film to the metal material was evaluated based on the number of squares remaining without being peeled off.
  • the coating films made of the cured products of the resin compositions of Examples 1 to 10 cured by curing at room temperature all had a wet heat adhesion result to metal materials of 100/100, and the wet heat adhesion to metal materials was 100/100. It was good.
  • the films made of the cured products of the aqueous resin compositions of Comparative Examples 1 to 15 all had a film yield strength of 10 [N/mm 2 ] or more, and the film yield strength was was high.
  • Comparative Examples 1 to 6, 8 to 10, 12 to 14 using an aliphatic polyamine as the curing agent ( ⁇ ) Comparative Examples 7 and 11 containing 1.5 equivalents or more of the curing agent ( ⁇ ) which is an aromatic polyamine
  • the coating film made of the cured product of the aqueous resin composition of Comparative Example 15 containing 1.5 mol or more of the curing accelerator ( ⁇ ) with respect to 1 equivalent of the epoxy group, all of the aqueous resin compositions of Examples 1 to 10 Compared with a coating film made of a cured product, the result of wet heat adhesion to metal materials was inferior.
  • a water-based resin composition and a water-based resin that can be cured at room temperature for a short period of time to form a coating film having excellent initial water resistance and that can provide a coating film having good wet heat adhesion to metal materials.
  • a composition set can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition de résine aqueuse comprenant une émulsion de résine aqueuse (α), un agent de durcissement (β) et un accélérateur de durcissement (γ), l'émulsion de résine aqueuse (α) contient un copolymère (X), un composé polyépoxy (Y) et un milieu aqueux (Z), le copolymère (X) comprend des motifs structuraux dérivés de l'ester d'acide (méth)acrylique (A) et des motifs structuraux dérivés d'un acide carboxylique éthyléniquement insaturé (B), les motifs structuraux dérivés de l'ester d'acide (méth)acrylique (A) comprennent un motif structural dérivé d'un ester d'acide (méth)acrylique hydrophile (A1), au moins un élément parmi le copolymère (X) et le composé polyépoxy (Y) comprend un groupe carboxy, l'agent de durcissement (β) contient une polyamine aromatique (F) comprenant de l'hydrogène actif et l'accélérateur de durcissement (γ) contient une amine tertiaire n'ayant pas d'hydrogène actif.
PCT/JP2022/021819 2021-06-02 2022-05-27 Composition de résine aqueuse, film de revêtement, procédé de production de film de revêtement et ensemble de composition de résine aqueuse WO2022255272A1 (fr)

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KR1020237041915A KR20240016291A (ko) 2021-06-02 2022-05-27 수성 수지 조성물, 도막, 도막의 제조 방법, 수성 수지 조성물 세트
CN202280038918.8A CN117396555A (zh) 2021-06-02 2022-05-27 水性树脂组合物、涂膜、涂膜的制造方法、水性树脂组合物套装
JP2023525797A JPWO2022255272A1 (fr) 2021-06-02 2022-05-27

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08188605A (ja) * 1995-01-11 1996-07-23 Asahi Chem Ind Co Ltd 水性樹脂分散体の製造法
JPH08231616A (ja) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd 硬化性水性樹脂組成物
WO2020100790A1 (fr) * 2018-11-13 2020-05-22 昭和電工株式会社 Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse
WO2021112042A1 (fr) * 2019-12-02 2021-06-10 昭和電工株式会社 Composition de resine aqueuse, film et procede de formation de film

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5333152B2 (ja) 2009-10-26 2013-11-06 東亞合成株式会社 厚塗り用塗料組成物
JP5443526B2 (ja) 2011-03-01 2014-03-19 ローム アンド ハース カンパニー エポキシ樹脂吸収ポリマー粒子
US11261356B2 (en) 2015-12-22 2022-03-01 Dow Global Technologies Llc Acrylic/epoxy hybrid materials for laminating adhesive applications

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231616A (ja) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd 硬化性水性樹脂組成物
JPH08188605A (ja) * 1995-01-11 1996-07-23 Asahi Chem Ind Co Ltd 水性樹脂分散体の製造法
WO2020100790A1 (fr) * 2018-11-13 2020-05-22 昭和電工株式会社 Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse
WO2021112042A1 (fr) * 2019-12-02 2021-06-10 昭和電工株式会社 Composition de resine aqueuse, film et procede de formation de film

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