WO2020189714A1 - 水性塗料用樹脂組成物及び塗膜 - Google Patents

水性塗料用樹脂組成物及び塗膜 Download PDF

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WO2020189714A1
WO2020189714A1 PCT/JP2020/011949 JP2020011949W WO2020189714A1 WO 2020189714 A1 WO2020189714 A1 WO 2020189714A1 JP 2020011949 W JP2020011949 W JP 2020011949W WO 2020189714 A1 WO2020189714 A1 WO 2020189714A1
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Prior art keywords
fatty acid
mass
unsaturated fatty
salt
acid salt
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PCT/JP2020/011949
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English (en)
French (fr)
Japanese (ja)
Inventor
祐紀 大橋
悠太 加賀
陽介 荒木
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ハリマ化成株式会社
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Application filed by ハリマ化成株式会社 filed Critical ハリマ化成株式会社
Priority to MYPI2021005419A priority Critical patent/MY196253A/en
Priority to SG11202109832P priority patent/SG11202109832PA/en
Priority to CN202080022181.1A priority patent/CN113597454B/zh
Priority to AU2020240710A priority patent/AU2020240710B2/en
Priority to JP2021507393A priority patent/JP7341222B2/ja
Publication of WO2020189714A1 publication Critical patent/WO2020189714A1/ja

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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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to a resin composition for a water-based paint and a coating film.
  • solvent-based paints have been widely used for painting the surface of building materials such as exterior materials used for building construction.
  • a solvent-based resin used in the solvent-based paint a styrene- (meth) acrylate copolymer containing styrene and (meth) acrylate as a main monomer unit is used because it has excellent initial gloss and initial water resistance. It is commonly used.
  • Patent Document 1 describes a resin composition for paints containing a resin emulsion obtained by emulsion-polymerizing a monomer component, and a plurality of emulsifiers are used when the monomer component is emulsion-polymerized.
  • the resin composition for paints is disclosed.
  • the coating film of the water-based paint produced by using the above resin composition for paint has a problem that the initial glossiness is still insufficient.
  • the coating film of the water-based paint produced by using the above resin composition for paint has a problem that the gloss is lowered with time (the initial water resistance is insufficient) due to the adhesion of water or the like. Have.
  • the present invention provides a resin composition for a water-based paint capable of producing a water-based paint capable of forming a coating film having excellent initial gloss and initial water resistance.
  • the resin composition for water-based coating materials of the present invention contains a styrene-based monomer unit, an acrylic-based monomer unit, and an unsaturated fatty acid salt unit, and contains a copolymer having a glass transition temperature of -4 to 40 ° C. It is a feature.
  • the coating film of the present invention is characterized by being a solidified coating layer on an object to be coated of the above-mentioned resin composition for water-based coating material.
  • the resin composition for a water-based paint of the present invention can produce a water-based paint capable of forming a coating film having excellent initial gloss and initial water resistance.
  • the resin composition for water-based coating materials of the present invention contains a styrene-based monomer unit, an acrylic-based monomer unit, and an unsaturated fatty acid salt unit, and contains a copolymer having a glass transition temperature of -4 to 40 ° C. It is a feature.
  • the resin composition for water-based paints contains a copolymer containing a styrene-based monomer, an acrylic-based monomer unit, and an unsaturated fatty acid salt unit.
  • the styrene-based monomer constituting the copolymer is not particularly limited, and examples thereof include styrene, ⁇ -methylstyrene, p-methylstyrene, methylstyrene, tert-butylstyrene, chlorostyrene, vinyltoluene and the like.
  • styrene is preferable from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint.
  • the styrene-based monomer may be used alone or in combination of two or more.
  • the styrene-based monomer has an alkyl group such as a methyl group and a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group and a functional group such as a halogen atom on the benzene ring. May be good.
  • the content of the styrene-based monomer unit in the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. By mass% or more is more preferable, 20% by mass or more is more preferable, and 25% by mass or more is particularly preferable.
  • the content of the styrene-based monomer unit in the copolymer is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass, from the viewpoint of weather resistance of the coating film formed from the resin composition for water-based coating materials. % Or less is more preferable, and 35% by mass or less is particularly preferable.
  • the acrylic monomer constituting the copolymer is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl.
  • Examples thereof include (meth) acrylic monomers, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, lanic acid, fumaric acid, citraconic acid, (anhydrous) maleic acid, and (anhydrous) citraconic acid.
  • the acrylic monomer is preferably alkyl (meth) acrylate and (meth) acrylic acid, more preferably containing alkyl (meth) acrylate and methacrylic acid, and particularly preferably containing alkyl acrylate, alkyl methacrylate and methacrylic acid. ..
  • the acrylic monomer may be used alone or in combination of two or more.
  • (Meta) acrylate means acrylate or methacrylate.
  • (Meta) acrylic acid means acrylic acid or methacrylic acid.
  • the content of the acrylic monomer unit in the copolymer is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass from the viewpoint of weather resistance of the coating film formed from the resin composition for water-based coating materials. % Or more is more preferable, and 55% by mass or more is particularly preferable.
  • the content of the acrylic monomer unit in the copolymer is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. Mass% or less is particularly preferable.
  • the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based coating materials.
  • the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate is preferably 15 or less, more preferably 12 or less, and particularly preferably 10 or less, from the viewpoint of the drying property of the water-based paint formed from the resin composition for water-based paint.
  • the alkyl (meth) acrylate preferably contains methyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate, and methyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl acrylate. And n-butyl acrylate are more preferred.
  • the content of the alkyl (meth) acrylate unit in the copolymer is preferably 30% by mass or more, more preferably 40% by mass or more, from the viewpoint of weather resistance of the coating film formed from the resin composition for water-based coating materials. 50% by mass or more is more preferable, and 55% by mass or more is particularly preferable.
  • the content of the alkyl (meth) acrylate unit in the copolymer is preferably 80% by mass or less, more preferably 75% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based coating materials. , 70% by mass or less is particularly preferable.
  • the content of the (meth) acrylic acid unit in the copolymer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of stability of the emulsion particles in the aqueous coating material, and is 0. 1% by mass or more is particularly preferable.
  • the content of the (meth) acrylic acid unit in the copolymer is preferably 4% by mass or less, more preferably 3% by mass or less, from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based coating materials. 2, 2% by mass or less is more preferable, and 1% by mass or less is particularly preferable.
  • the content of the methacrylic acid unit in the copolymer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass, from the viewpoint of stability of the emulsion particles in the aqueous coating material.
  • the above is particularly preferable.
  • the content of the methacrylic acid unit in the copolymer is preferably 4% by mass or less, more preferably 3% by mass or less, and 2% by mass from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based coating materials. The following is more preferable, and 1% by mass or less is particularly preferable.
  • the unsaturated fatty acid salt that constitutes the copolymer is a reactive emulsifier.
  • the reactive emulsifier has an emulsifying action.
  • the unsaturated fatty acid salt is a salt of a monocarboxylic acid represented by RCOOH, and the substituent represented by R contains at least one unsaturated bond.
  • the unsaturated fatty acid salt is incorporated into the polymerized chain of the copolymer by radical polymerization at an unsaturated bond.
  • the unsaturated fatty acid salt may be used alone or in combination of two or more.
  • the copolymer By containing the unsaturated fatty acid salt unit in the copolymer, the copolymer has a hydrophobic portion and a hydrophilic portion.
  • the copolymer has a micellar structure in which the hydrophobic portion is on the inside and the hydrophilic portion is on the outside, so that the copolymer can be dispersed in an aqueous medium and can form an aqueous coating material.
  • the aqueous medium is not particularly limited, and is, for example, water, an alcohol solvent (for example, methanol, ethanol, propanol, isopropanol, butanol, etc.), a glycol ether solvent (for example, ethylene glycol monoethyl ether, propylene glycol monomethyl). Ether, butyl diglycol, etc.), and water is preferable.
  • the unsaturated fatty acid salt contains an unsaturated bond in the substituent R.
  • the substituent R has a bent structure at the unsaturated bond portion. By adopting a bent structure of the substituent R, the hydrophobic portion of the copolymer is bent and contained in the micelle in a good appearance, and the dispersibility of the copolymer in the aqueous medium is improved.
  • the unsaturated bond in the substituent R is not particularly limited, but is an ethylenically unsaturated bond such as an ethylenically unsaturated double bond (carbon-carbon double bond) and an ethylenically unsaturated triple bond (carbon-carbon triple bond). Is preferred, and ethylenically unsaturated double bonds are more preferred.
  • the ethylenically unsaturated double bond has a cis-double bond and a trans-double bond, but since it can fit nicely inside the micelle while encapsulating the hydrophobic part in the copolymer, the cis-2 bond. Double bonds are preferred.
  • the number of unsaturated bonds in the substituent R is preferably 1 to 6, more preferably 1 to 5, and particularly preferably 1 to 4.
  • an unsaturated bond is formed between the third and subsequent carbons counting from the carbon at the end of the substituent R (the end of the longest chain in the substituent R). It is more preferable to have an unsaturated bond between the fifth and subsequent carbons counting from the carbon at the end of the substituent R, and it is more preferable to have an unsaturated bond at the end of the substituent R. It is particularly preferable to have an unsaturated bond between the sixth and subsequent carbons counting from the carbon and the carbon.
  • the carbon number of the unsaturated fatty acid salt (total carbon number of the unsaturated fatty acid salt) is preferably 4 or more, more preferably 12 or more, and particularly preferably 16 or more, from the viewpoint of stability of the emulsion particles in the aqueous coating material.
  • the carbon number of the unsaturated fatty acid salt (total carbon number of the unsaturated fatty acid salt) is preferably 30 or less, more preferably 28 or less, and particularly preferably 26 or less, from the viewpoint of water solubility of the unsaturated fatty acid salt.
  • the unsaturated fatty acid (IUPAC name) used as a raw material for the unsaturated fatty acid salt is not particularly limited, and for example, butenoic acid (C4), pentenic acid (C5), hexenoic acid (C6), heptenoic acid (C7), and octene.
  • Acid (C8) nonenic acid (C9), decenoic acid (C10), undecenoic acid (C11), dodecenoic acid (C12), tridecenoic acid (C13), tetradecenoic acid (C14), pentadecenoic acid (C15), hexadecenoic acid ( C16), heptadecenoic acid (C17), octadecenoic acid (C18), nonadecenoic acid (C19), icosenoic acid (C20), henicosenoic acid (C21), docosenoic acid (C22), tricosenoic acid (C23), tetracosenoic acid (C24) , Pentacosenoic acid (C25), hexacosenoic acid (C26), heptacosenoic acid (C27), octacosenoic acid (C28), nonacocenoic acid (C29), tri
  • unsaturated fatty acids that are raw materials for unsaturated fatty acid salts include myristoleic acid (C14, 1, B5), palmitrenic acid (C16, 1, B7), and stearidonic acid (C18).
  • the unsaturated fatty acid salt may be used alone or in combination of two or more, or a salt of an animal or vegetable oil fatty acid containing a plurality of types of unsaturated fatty acids may be used.
  • animal and vegetable oil fatty acid salts include soybean oil fatty acid salt, cottonseed oil fatty acid salt, tall oil fatty acid salt (salt of a mixture of palmitic acid, stearic acid, oleic acid and linoleic acid), corn oil fatty acid salt, rice bran oil fatty acid salt, and the like. Red flower oil fatty acid salt, sunflower oil fatty acid salt, flaxseed oil fatty acid salt, fish oil fatty acid salt, dehydrated sunflower oil fatty acid salt, palm oil fatty acid salt, beef fat fatty acid salt, rapeseed oil fatty acid salt, olive oil fatty acid salt, etc. Is preferable.
  • the unsaturated fatty acid salt may be a derivative thereof.
  • the derivative of the unsaturated fatty acid salt is not particularly limited, and for example, a polymerized fatty acid salt, a salt of an unsaturated carboxylic acid adduct, an epoxidized unsaturated fatty acid salt, a hydroxyated unsaturated fatty acid salt, or an epoxy.
  • Examples thereof include salts of unsaturated fatty acids that have been modified and hydroxylated, salts of unsaturated fatty acids that have been sulfonated, and the like, preferably polymerized fatty acid salts, more preferably dimerates and trimers, and particularly preferably dimerates.
  • the unsaturated fatty acid salt derivative needs to have an unsaturated bond in the molecule.
  • the polymerized fatty acid salt is a salt of a compound obtained by polymerizing an unsaturated fatty acid in the presence of a catalyst such as clay as needed.
  • a catalyst such as clay as needed.
  • dimerate a dimer salt of an unsaturated fatty acid
  • trimeric acid Trimeric salt of unsaturated fatty acid
  • tetramer acid tetrameric salt of unsaturated fatty acid
  • trimerate tetrameric salt of unsaturated fatty acid
  • the polymerized fatty acid salt may be used alone or in combination of two or more.
  • the polymerized fatty acid salt may be partially hydrogenated, but it is necessary that unsaturated bonds remain.
  • Examples of the salt of the unsaturated carboxylic acid adduct include a salt of a compound obtained by addition-reacting ⁇ , ⁇ -unsaturated carboxylic acid to the unsaturated bond of the unsaturated fatty acid. Specific examples thereof include a salt of an unsaturated fatty acid maleic acid or an adduct thereof, and a salt of an unsaturated fatty acid acrylic acid adduct.
  • the salt of the unsaturated carboxylic acid adduct needs to have an unsaturated bond remaining.
  • the epoxidized unsaturated fatty acid salt is a salt of a compound in which the unsaturated bond of the unsaturated fatty acid is epoxidized with, for example, peracetic acid or hydrogen peroxide.
  • the hydroxylated unsaturated fatty acid salt is obtained by hydrolyzing the epoxidized unsaturated fatty acid salt to introduce two hydroxyl groups.
  • the sulfonated unsaturated fatty acid salt is a salt of a compound in which the unsaturated bond of the unsaturated fatty acid is sulfonated with sulfuric acid or the like.
  • the epoxidized unsaturated fatty acid salt, the hydroxylated unsaturated fatty acid salt and the sulfonated unsaturated fatty acid salt need to have unsaturated bonds remaining.
  • the content of the unsaturated fatty acid salt unit in the copolymer is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and more preferably 1.0% by mass, from the viewpoint of the stability of the emulsion particles in the aqueous coating material.
  • the above is particularly preferable.
  • the content of the unsaturated fatty acid salt unit in the copolymer is preferably 5.0% by mass or less, preferably 4.5% by mass or less, from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based coatings. Is more preferable.
  • the content of the dimer acid salt is preferably 5% by mass or more, more preferably 15% by mass or more, and more preferably 40% by mass or more, from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based paint.
  • mass% or more is more preferable, 60% by mass or more is more preferable, 70% by mass or more is more preferable, and 80% by mass or more is particularly preferable.
  • the content of the dimer acid salt in the polymerized fatty acid salt is preferably 99% by mass or less, more preferably 97% by mass or less, and more preferably 95% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. It is more preferably mass% or less, and particularly preferably 87 mass% or less.
  • the content of the trimerate is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based paint.
  • mass% or more is more preferable, 7% by mass or more is more preferable, 10% by mass or more is more preferable, and 13% by mass or more is particularly preferable.
  • the content of the trimerate in the polymerized fatty acid salt is preferably 95% by mass or less, more preferably 85% by mass or less, and more preferably 40% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. It is more preferably mass% or less, more preferably 30 mass% or less, and particularly preferably 20 mass% or less.
  • the unsaturated fatty acid salt preferably contains a monomeric unsaturated fatty acid salt (monomeric acid salt), a dimer acid salt and a trimer acid salt.
  • the monomeric unsaturated fatty acid salt means an unsaturated fatty acid salt that has not been polymerized.
  • the content of the monomeric acid salt in the unsaturated fatty acid salt is a coating film formed from a resin composition for an aqueous coating material. From the viewpoint of the initial glossiness of the above, 0.5% by mass or more is preferable, 1% by mass or more is more preferable, 2% by mass or more is more preferable, and 3% by mass or more is particularly preferable.
  • the content of the monomeric acid salt in the unsaturated fatty acid salt is preferably 10% by mass or less, more preferably 8% by mass or less, from the viewpoint of the initial water resistance of the coating film formed from the resin composition for water-based paint. It is preferable, 6% by mass or less is more preferable, and 5% by mass or less is particularly preferable.
  • the content of the dimer acid salt in the unsaturated fatty acid salt is a coating film formed from the resin composition for an aqueous coating material. From the viewpoint of initial water resistance, 10% by mass or more is preferable, 20% by mass or more is more preferable, 50% by mass or more is more preferable, and 70% by mass or more is particularly preferable.
  • the content of the dimer acid salt in the unsaturated fatty acid salt is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. It is preferable, and 85% by mass or less is particularly preferable.
  • the content of the trimer acid salt in the unsaturated fatty acid salt is a coating film formed from the resin composition for an aqueous coating material.
  • 0.5% by mass or more is preferable, 1% by mass or more is more preferable, 10% by mass or more is more preferable, and 70% by mass or more is particularly preferable.
  • the content of the trimerate in the unsaturated fatty acid salt is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of the initial glossiness of the coating film formed from the resin composition for water-based paint. It is preferable, and 80% by mass or less is particularly preferable.
  • the copolymer may contain a reactive emulsifier other than the unsaturated fatty acid salt as a monomer unit.
  • Reactive emulsifiers other than unsaturated fatty acid salts have an emulsifying action.
  • Reactive emulsifiers other than unsaturated fatty acid salts have at least one unsaturated bond in the molecule and are incorporated into the copolymer by radical polymerization at the unsaturated bond.
  • an ethylenically unsaturated double bond is more preferred.
  • a plurality of unsaturated bonds may be present in the molecule.
  • the ethylenically unsaturated double bond is an unsaturated bond contained in a functional group such as an alkenyl group, a (meth) allyloxyalkyl group, or a (meth) acryloyl group.
  • a functional group such as an alkenyl group, a (meth) allyloxyalkyl group, or a (meth) acryloyl group.
  • (meth) allyl means allyl or methallyl.
  • (Meta) acryloyl means acryloyl or methacryloyl.
  • alkenyl group examples include a vinyl group, a (meth) allyl group, a 1-propenyl group, a 2-methyl-1-propenyl group, an isopropenyl group and the like.
  • the reactive emulsifier other than the unsaturated fatty acid salt is not particularly limited, and for example, a sulfate ester salt of polyoxyalkylene phenyl ether having at least one functional group containing an ethylenically unsaturated double bond in the molecule, in the molecule.
  • Polyoxyethylene alkyl ether sulfosuccinate ester salt (sodium ester salt, ammonium ester salt, etc.) having at least one functional group containing an ethylenically unsaturated double bond in the molecule, containing an ethylenically unsaturated double bond in the molecule
  • Sulfate ester salts of polyoxyethylene alkyl ethers having at least one functional group (sodium ester salts, ammonium ester salts, etc.), polyoxyethylene alkyl having at least one functional group containing an ethylenically unsaturated double bond in the molecule
  • Phosphosuccinic acid ester salt of phenyl ether (sodium ester salt, ammonium ester salt, etc.), sulfate ester salt of polyoxyalkylene ether having at least one functional group containing an ethylenically unsaturated double bond in the molecule (sodium ester salt, ester sodium salt, etc.)
  • Reactive emulsifiers other than unsaturated fatty acid salts preferably have an ethylenically unsaturated double bond near the end of the molecule.
  • the "near molecular end" is formed by a terminal carbon and the second and third carbons counting from the terminal carbon (first) in a molecular chain composed of carbon bonds. A carbon-carbon bond portion.
  • Reactive emulsifiers other than unsaturated fatty acid salts have an ethylenically unsaturated double bond between the terminal carbon (first carbon) and the carbon bonded to this terminal carbon (second carbon). Is preferable.
  • Reactive emulsifiers other than unsaturated fatty acid salts preferably have an ethylenically unsaturated double bond between the second and third carbons, counting from the terminal carbon.
  • a sulfate ester salt of polyoxyalkylene phenyl ether having at least one functional group containing an ethylenically unsaturated double bond in the molecule is preferable, and the ethylenically unsaturated binary in the molecule is preferable.
  • a ammonium sulfate ester ammonium salt of a polyoxyalkylene phenyl ether having at least one functional group containing a double bond is more preferable, and a polyoxyethylene phenyl ether having at least one functional group containing an ethylenically unsaturated double bond in the molecule.
  • a ammonium sulfate ester ammonium salt is more preferred.
  • the sulfate ester salt of polyoxyalkylene phenyl ether having at least one functional group containing an ethylenically unsaturated double bond in the molecule is polyoxyethylene styrenated propenylphenyl ether ammonium sulfate, polyoxyethylene styrenated propenylphenyl ether sulfate.
  • polyoxyethylene propenylphenyl ether ammonium sulfate polyoxyethylene propenylphenyl ether sodium sulfate
  • polyoxyethylene styrenated propenylphenyl ether ammonium sulfate and polyoxyethylene styrenated propenylphenyl ether sodium sulfate are more preferable. preferable.
  • Examples of the reactive emulsifier other than the unsaturated fatty acid salt include acid anhydride modified products of rosing ricidyl ester acrylate (Japanese Patent Laid-Open No. 4-256429), and dispersants described in Japanese Patent Application Laid-Open No. 63-23725. Examples thereof include the dispersant described in Japanese Patent Application Laid-Open No. 63-240931 and the dispersant described in Japanese Patent Application Laid-Open No. 62-104802.
  • the reactive emulsifier can also be obtained as a commercial product.
  • Examples of such commercially available products include KAYAMER PM-1 (manufactured by Nippon Kayaku), KAYAMER PM-2 (manufactured by Nippon Kayaku), KAYAMER PM-21 (manufactured by Nippon Kayaku), and SE-10N (Asahi Denka Kogyo).
  • NE-10 Manufactured by Asahi Denka Kogyo
  • NE-20 Manufactured by Asahi Denka Kogyo
  • NE-30 Manufactured by Asahi Denka Kogyo
  • New Frontier A229E Manufactured by Dai-ichi Kogyo Seiyaku
  • New Frontier N-117E Daiichi Kogyo Seiyaku Co., Ltd., New Frontier N250Z (Daiichi Kogyo Seiyaku Co., Ltd.), Aquaron RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), Aquaron RN-2025 (Daiichi Kogyo Seiyaku Co., Ltd.), Aquaron BC-1025 (Daiichi Kogyo Seiyaku) Aqualon AR-1025 (manufactured by Dai-ichi Kogyo Seiyaku), Aquaron HS-10 (
  • the content of the monomer unit due to the reactive emulsifier other than the unsaturated fatty acid salt is 0 because the initial water resistance of the coating film formed from the resin composition for water-based paint is improved. It is preferably from 70% by mass, more preferably from 0 to 50% by mass, and particularly preferably from 0 to 30% by mass. In addition, "0% by mass" means that the copolymer does not contain a monomer unit caused by a reactive emulsifier other than the unsaturated fatty acid salt.
  • the copolymer contains a reactive emulsifier containing an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt as a monomer unit, in the copolymer from the viewpoint of stability of the emulsion particles in the aqueous coating material.
  • the content of the monomer unit resulting from all the reactive emulsifiers is preferably 0.5% by mass or more.
  • the copolymer contains a reactive emulsifier containing an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt as a monomer unit, the initial water resistance of the coating film formed from the resin composition for water-based coating material is important. Therefore, 4% by mass or less is preferable, 2% by mass or less is more preferable, and 1% by mass or less is more preferable.
  • the copolymer contains a reactive fatty acid salt containing an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt as a monomer unit, the unsaturated fatty acid salt with respect to the total amount of the unsaturated fatty acid salt in the reactive fatty acid salt.
  • the ratio of the total amount of the compounds other than the above is preferably 0.2 or more.
  • the ratio of the total amount of compounds other than unsaturated fatty acid salts to the total amount of unsaturated fatty acid salts is preferably 3 or less, preferably 2 or less. Is more preferable, 1.5 or less is more preferable, and 0.5 or less is more preferable.
  • the ratio of the total amount of the compounds other than the unsaturated fatty acid salt to the total amount of the unsaturated fatty acid salt is 0.2 or more, the stability of the emulsion particles in the aqueous coating material is improved, which is preferable.
  • the ratio of the total amount of the compounds other than the unsaturated fatty acid salt to the total amount of the unsaturated fatty acid salt is 3 or less, the initial glossiness and the initial water resistance of the coating film formed from the resin composition for water-based paints are improved, which is preferable. ..
  • the copolymer may contain a fatty acid-modified monomer unit.
  • the fatty acid-modified monomer is a compound obtained by reacting a drying oil fatty acid and / or a semi-drying oil fatty acid with an epoxy group-containing polymerizable unsaturated monomer by a known method.
  • An unsaturated fatty acid (non-polymerized unsaturated fatty acid) may be used instead of the drying oil fatty acid and the semi-drying oil fatty acid, or in combination with the drying oil fatty acid and / or the semi-drying oil fatty acid.
  • Unsaturated fatty acids may be used alone or in combination of two or more.
  • the content of the fatty acid-modified monomer unit in the copolymer is preferably 1% by mass or more, more preferably 2% by mass or more, because the initial water resistance of the coating film formed from the resin composition for water-based coatings is improved. 3% by mass or more is particularly preferable.
  • the content of the fatty acid-modified monomer unit in the copolymer is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 6% by mass or less, from the viewpoint of stability of the emulsion particles in the aqueous coating material.
  • Drying oil fatty acid and semi-drying oil fatty acid are fatty acids having an oxidative curing type polymerizable unsaturated group.
  • Examples of the dry oil fatty acid and the semi-dry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, flaxseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, and grape.
  • Examples thereof include nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, and rubber seed oil fatty acid, and tall oil fatty acid is preferable.
  • Drying oil fatty acids and / or semi-drying oil fatty acids are, as required, non-drying oil fatty acids such as, for example, coconut oil fatty acids, hydrogenated coconut oil fatty acids, palm oil fatty acids; caproic acid, capric acid, lauric acid, myristic acid. , Palmitic acid, stearic acid and the like may be used in combination.
  • Examples of the epoxy group-containing polymerizable unsaturated monomer include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxycyclohexylpropyl (meth).
  • Examples thereof include acrylate and allyl glycidyl ether, and glycidyl (meth) acrylate is preferable, and glycidyl methacrylate is more preferable.
  • the salt of the unsaturated fatty acid salt is not particularly limited, and for example, an alkali metal salt such as sodium, potassium and lithium; an alkaline earth metal salt such as calcium and barium; an alkanol such as monoethanolamine, diethanolamine and triethanolamine.
  • Organic amine salts such as amines and triethylamine; ammonium salts and the like, preferably alkali metal salts and alkaline earth metal salts, more preferably alkali metal salts, more preferably sodium salts and potassium salts, and particularly preferably potassium salts.
  • the glass transition temperature Tg of the copolymer constituting the resin composition for water-based paint is -4 ° C or higher because the initial water resistance and gloss retention of the coating film formed from the resin composition for water-based paint are improved. Is preferable, 1 ° C. or higher is more preferable, and 6 ° C. or higher is particularly preferable.
  • the glass transition temperature Tg of the copolymer constituting the resin composition for water-based paint is preferably 40 ° C. or lower, preferably 35 ° C. or lower, because the initial glossiness of the coating film formed from the resin composition for water-based paint is improved. The following is more preferable, 25 ° C. or lower is more preferable, 23 ° C. or lower is more preferable, and 19 ° C. or lower is particularly preferable.
  • the glass transition temperature (Tg) of the copolymer refers to the temperature measured using a differential scanning calorimetry (DSC) device according to JIS K7121-1987.
  • the method for producing the copolymer constituting the resin composition for water-based coating material is not particularly limited, and for example, (1) a monomer composition containing a styrene-based monomer, an acrylic-based monomer, and an unsaturated fatty acid salt which is a reactive emulsifier.
  • Examples thereof include a production method for producing a copolymer by radical polymerization of a product in an organic solvent (for example, xylene, toluene, methylisobutylketone, etc.) in the presence of a general-purpose radical polymerization initiator, and the remaining solvent. From the viewpoint of quantity, the production method (1) is preferable.
  • the copolymer is produced by the production method (2) above, the obtained copolymer is isolated, and the isolated copolymer has a high energy shearing ability in an aqueous medium as required. It may be dispersed using a disperser.
  • the radical polymerization initiator include azo compounds, peroxide compounds, sulfides, sulfins, diazo compounds and the like.
  • a water-based paint can be produced by dispersing the resin composition for water-based paint in a water-based medium.
  • the content (content of solid content) of the copolymer constituting the resin composition for water-based paint is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and 20 to 20 to 80% by mass. 60% by mass is particularly preferable.
  • the copolymer constituting the resin composition for an aqueous coating material contains an unsaturated fatty acid salt which is a reactive emulsifier as its monomer unit, it is well emulsionized and dispersed in an aqueous medium. However, a substantially homogeneous water-based paint can be formed. Further, in dispersing the resin composition for an aqueous coating material in an aqueous medium, the amount of the emulsifier used can be suppressed without using an emulsifier.
  • general-purpose additions such as non-reactive emulsifiers, pigments, film-forming aids, defoamers, thickeners, preservatives, fungicides, pH adjusters, and metal dryers are added to water-based paints.
  • the agent may be contained.
  • non-reactive emulsifier examples include anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers and the like, and anionic emulsifiers are preferable.
  • the non-reactive emulsifier may be used alone or in combination of two or more.
  • anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, and polyoxyethylene alkyl.
  • polyoxyalkylene polycyclic phenyl ether sulfate eg, polyoxyethylene polycyclic phenyl ether sulfate sodium, polyoxyethylene polycyclic phenyl ether sulfate ammonium, polyoxypropylene polycyclic phenyl ether sulfate sodium, Polyoxypropylene polycyclic phenyl ether sulfate ammonium ester, etc.
  • polyoxyalkylene polycyclic phenyl ether sulfate eg, polyoxyethylene polycyclic phenyl ether sulfate sodium, polyoxyethylene polycyclic phenyl ether sulfate ammonium, polyoxypropylene polycyclic phenyl ether sulfate sodium, Polyoxypropylene polycyclic phenyl ether sulfate ammonium ester, etc.
  • a polyoxyalkylene polycyclic phenyl ether sulfate ester salt is preferable, a polyoxyethylene polycyclic phenyl ether sulfate ester salt is preferable, and a polyoxyethylene polycyclic phenyl ether sulfate ammonium ester is more preferable.
  • Examples of the cationic emulsifier include alkyltrimethylammonium chloride and the like.
  • nonionic emulsifier examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene polyoxypropylene block polymer. These can be used alone or in combination of two or more.
  • the content of the non-reactive emulsifier in the water-based paint is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, and even more preferably 0 to 2 parts by mass with respect to 100 parts by mass of the copolymer.
  • 0 part by mass means that a non-reactive emulsifier is not contained in the water-based paint.
  • an object to be painted for example, a building material such as an exterior material used for building construction
  • a coating layer is formed, and the aqueous medium in the coating layer is evaporated and removed to solidify the coating layer to form a coating film, and the surface of the object to be coated can be coated with this coating film.
  • the copolymer constituting the resin composition for water-based paint contains an unsaturated fatty acid salt unit, which is a reactive emulsifier, as a monomer unit in the molecule. Since the unsaturated fatty acid salt has an unsaturated bond in the molecule, it is bonded and incorporated into the copolymer by a copolymerization reaction, and further, since it has an aliphatic group, it is an aqueous coating material. When the coating film formed from the resin composition for use is exposed to water, it is possible to prevent elution of the coating film components. Therefore, in the coating film formed from the water-based coating film, the unsaturated fatty acid salt units constituting the copolymer do not liberate from the copolymer and bleed out to the surface of the coating film.
  • an unsaturated fatty acid salt unit which is a reactive emulsifier
  • the use of an emulsifier can be eliminated or the amount of the emulsifier used can be reduced as described above.
  • the amount of the liberated emulsifier in the coating film formed from the water-based coating film is extremely small, and the voids caused by the bleed-out of the emulsifier are coated in the state of being exposed to water during or after the coating film formation. The formation on the film surface is reduced or suppressed.
  • the permeation of water into the coating film through the voids on the surface of the coating film is reduced or suppressed, and the coating film has excellent initial water resistance.
  • the unsaturated fatty acid salt unit in the copolymer improves the leveling property at the time of forming the coating film, and is also excellent in the initial glossiness of the coating film.
  • [emulsifier] (Synthesis of unsaturated fatty acid salts 1) 344.92 parts by mass of distilled water and 44.73 parts by mass of a 48% by mass potassium hydroxide aqueous solution were supplied into the reaction vessel and kept at 95 ° C. for about 1 hour with stirring. Next, 110.35 parts by mass of the unsaturated fatty acid shown below was supplied into the reaction vessel and reacted at 95 ° C. for 3 hours with stirring to obtain an unsaturated fatty acid having a solid content concentration of 25% by mass. A potassium salt (reactive emulsifier) was obtained.
  • each of the obtained potassium salts of unsaturated fatty acids is described by adding "K salt” to the end of the trade name of the reactive emulsifier used as a raw material.
  • “potassium salt” will be referred to as "K salt”.
  • Unsaturated fatty acid 1 Harima Chemicals, Inc.
  • Unsaturated fatty acid 2 Made by Tsukino Food Industry Co., Ltd.
  • Unsaturated fatty acid 3 Made by Tsukino Food Industry Co., Ltd.
  • Synthesis of unsaturated fatty acid salts 2 An adduct was obtained by addition reaction of unsaturated fatty acid in tall oil fatty acid and maleic anhydride. This adduct was used as a potassium salt according to the method of Synthesis 1 of unsaturated fatty acid salt to obtain a potassium salt of unsaturated fatty acid having a solid content concentration of 25% by mass (BK-73BK salt, potassium salt of oleic acid) (reaction). Sexual emulsifier).
  • the tall oil fatty acid contained 2% by mass of palmitic acid and 2% by mass of stearic acid as saturated fatty acids, and 46% by mass of oleic acid and 41% by mass of linoleic acid as unsaturated fatty acids.
  • the tall oil fatty acid contained 2% by mass of palmitic acid and 2% by mass of stearic acid as saturated fatty acids, and 46% by mass of oleic acid and 41% by mass of linoleic acid as unsaturated fatty acids.
  • Table 1 shows the contents and iodine value (solid) of potassium monomeric acid salt (K salt monomeric acid), potassium dimerate salt (K salt dimer acid) and potassium trimerate salt (K salt trimerate) for the above emulsifiers. It was.
  • [Monomer composition] Prepare monomer compositions 1 to 16 containing predetermined amounts of styrene, methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, cyclohexyl methacrylate, fatty acid-modified monomer, diacetone acrylamide and methacrylic acid, respectively, as shown in Table 2. did.
  • Emulsifiers having the compositions (% by mass) shown in Tables 3 to 5 were prepared. Half the amount of the emulsifier and 91.5 parts by mass of distilled water shown in Tables 3 to 5 were supplied to the reaction vessel. Nitrogen gas was supplied into the reaction vessel, and the inside of the reaction vessel was stirred while substituting nitrogen, and water containing an emulsifier in the reaction vessel was heated to 90 ° C. and held.
  • the monomer emulsion was added dropwise into the reaction vessel over 3 hours.
  • the reaction solution in the reaction vessel was held at 90 ° C. for 2 hours to carry out a radical polymerization reaction to synthesize a copolymer.
  • the reaction solution in the reaction vessel was cooled to 40 ° C. or lower, and then adjusted to pH 9 with 28% by mass of aqueous ammonia so that the solid content (copolymer) concentration was 40% by mass.
  • %% Resin composition for water-based paint was obtained.
  • the emulsifier content (mass%) and supply amount (parts by mass) shown in Tables 3 to 5 indicate the amount of solid content.
  • the coating layer on the stainless steel sheet was dried in a room at 23 ° C. and a relative humidity of 50% for 16 hours to evaporate and remove the water contained in the coating layer to form a coating film.
  • the 20 ° mirror reflectance (20 ° G) of the obtained coating film was measured, and the measured value was converted to mirror gloss according to JIS Z8741.
  • the obtained mirror glossiness was defined as the "initial mirror glossiness" and used as a criterion for evaluating the initial glossiness.
  • a pipe made of polyvinyl chloride with an inner diameter of 43 mm was prepared, and silicone grease was applied to the entire end face of the first opening in the pipe.
  • the pipe was brought into close contact with the coating film.
  • the surface of the pipe coated with silicone grease was made to adhere to the coating film on the entire surface.
  • test piece After supplying 15 g of distilled water into the pipe, a test piece was prepared by closing the second opening in the pipe with a synthetic resin film so that the distilled water in the pipe would not evaporate. The test piece was allowed to stand in a room at 23 ° C. and 50% relative humidity for 24 hours.
  • the pipe was removed from the coating film to sufficiently wipe off the water on the coating film, and then the pipe was allowed to stand in a room at 23 ° C. and a relative humidity of 50% for 1 hour. ..
  • the mirror glossiness of the coating film after the water resistance test was measured in the same manner as the initial mirror glossiness.
  • the water-based coating material formed from the resin composition for water-based coating material of the present invention forms a coating film having excellent initial gloss and initial water resistance on the surface of an object to be coated such as a building material, and the surface of the object to be coated is formed. Can be painted.

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2020/011949 2019-03-19 2020-03-18 水性塗料用樹脂組成物及び塗膜 WO2020189714A1 (ja)

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CN202080022181.1A CN113597454B (zh) 2019-03-19 2020-03-18 水性涂料用树脂组合物以及涂膜
AU2020240710A AU2020240710B2 (en) 2019-03-19 2020-03-18 Resin composition for aqueous coating materials, and coating film
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01121351A (ja) * 1987-09-22 1989-05-15 Deutsche Texaco Ag 水性合成分散液
US5538760A (en) * 1995-05-22 1996-07-23 Eastman Chemical Company Alkyd/acrylic latexes for cleaning and protecting hard surfaces
WO2007042684A1 (fr) * 2005-10-14 2007-04-19 Rhodia Recherches Et Technologies Procede pour preparer un copolymere greffe par des acides gras polyinsatures, copolymere greffe par des acides gras polyinsatures susceptible d'etre obtenu par ce procede et ses utilisations
US20100247786A1 (en) * 2007-11-21 2010-09-30 Base Se New polymers by emulsion polymerization
JP2018521145A (ja) * 2015-04-27 2018-08-02 オールネックス オーストリア ゲーエムベーハー 水性分散体
CN109438635A (zh) * 2018-10-24 2019-03-08 北京金汇利应用化工制品有限公司 水性环氧酯改性石油树脂

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50161581A (enrdf_load_stackoverflow) * 1974-06-21 1975-12-27
CN1114632C (zh) * 1997-08-12 2003-07-16 伊斯曼化学公司 丙烯酸改性水性磺化醇酸分散液
WO2009121891A1 (en) * 2008-03-31 2009-10-08 Dsm Ip Assets Bv Coating composition comprising autoxidisable component

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01121351A (ja) * 1987-09-22 1989-05-15 Deutsche Texaco Ag 水性合成分散液
US5538760A (en) * 1995-05-22 1996-07-23 Eastman Chemical Company Alkyd/acrylic latexes for cleaning and protecting hard surfaces
WO2007042684A1 (fr) * 2005-10-14 2007-04-19 Rhodia Recherches Et Technologies Procede pour preparer un copolymere greffe par des acides gras polyinsatures, copolymere greffe par des acides gras polyinsatures susceptible d'etre obtenu par ce procede et ses utilisations
US20100247786A1 (en) * 2007-11-21 2010-09-30 Base Se New polymers by emulsion polymerization
JP2018521145A (ja) * 2015-04-27 2018-08-02 オールネックス オーストリア ゲーエムベーハー 水性分散体
CN109438635A (zh) * 2018-10-24 2019-03-08 北京金汇利应用化工制品有限公司 水性环氧酯改性石油树脂

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