CN113597454A - Resin composition for aqueous coating material and coating film - Google Patents
Resin composition for aqueous coating material and coating film Download PDFInfo
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- CN113597454A CN113597454A CN202080022181.1A CN202080022181A CN113597454A CN 113597454 A CN113597454 A CN 113597454A CN 202080022181 A CN202080022181 A CN 202080022181A CN 113597454 A CN113597454 A CN 113597454A
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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
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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
Abstract
The present invention provides a resin composition for aqueous coating materials, which can produce an aqueous coating material capable of forming a coating film having excellent initial gloss, initial water resistance and gloss retention. The resin composition for an aqueous coating material of the present invention contains a copolymer which contains a styrene monomer unit, an acrylic monomer unit and an unsaturated fatty acid salt unit and has a glass transition temperature of-4 to 40 ℃, and can produce an aqueous coating material capable of forming a coating film having excellent initial gloss, initial water resistance and gloss retention.
Description
Technical Field
The present invention relates to a resin composition for aqueous coating materials and a coating film.
Background
Conventionally, solvent-based paints have been widely used for coating the surfaces of building materials such as exterior materials for building. As a solvent resin used for a solvent-based coating material, a styrene- (meth) acrylate copolymer having styrene and (meth) acrylate as main monomer units is generally used from the viewpoint of excellent initial gloss and initial water resistance.
On the other hand, in recent years, in the field of paints, in order to improve the burden on the use environment and the global environment due to volatile organic compounds, the transfer from solvent-based paints containing organic solvents to aqueous paints containing aqueous solvents is rapidly proceeding. With this shift to aqueous paints, resins for aqueous paints have been developed, but they have a problem that they are inferior to solvent-based resins such as styrene- (meth) acrylate copolymers in initial gloss and initial water resistance.
In view of the above, patent document 1 discloses a resin composition for coating containing a resin emulsion obtained by emulsion polymerization of a monomer component, which is a resin composition for coating using a plurality of emulsifiers when the monomer component is emulsion polymerized.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-125219
Disclosure of Invention
Technical problem to be solved by the invention
However, the coating film of the water-based paint produced by using the resin composition for paint still has a problem of insufficient initial gloss.
Further, a coating film of a water-based paint produced using the resin composition for paint has a problem that gloss is reduced with time (initial water resistance is insufficient) due to adhesion of water or the like.
The invention provides a resin composition for an aqueous coating material, which can produce an aqueous coating material capable of forming a coating film having excellent initial gloss and initial water resistance.
Means for solving the problems
The resin composition for aqueous coating material of the present invention contains: comprises a styrene monomer unit, an acrylic monomer unit and an unsaturated fatty acid salt unit, and has a glass transition temperature of-4 to 40 ℃.
The coating film of the present invention is a cured product of a coating layer formed by applying the resin composition for an aqueous coating material to an object to be coated.
ADVANTAGEOUS EFFECTS OF INVENTION
The resin composition for an aqueous coating material of the present invention can produce an aqueous coating material capable of forming a coating film having excellent initial gloss and initial water resistance.
Detailed description of the invention
The resin composition for aqueous coating material of the present invention contains: comprises a styrene monomer unit, an acrylic monomer unit and an unsaturated fatty acid salt unit, and has a glass transition temperature of-4 to 40 ℃.
The resin composition for aqueous coating material contains: a copolymer comprising a styrenic monomer, an acrylic monomer unit, and an unsaturated fatty acid salt unit.
The styrenic monomer constituting the copolymer is not particularly limited, and examples thereof include: styrene, α -methylstyrene, p-methylstyrene, t-butylstyrene, chlorostyrene, vinyltoluene, and the like, styrene is preferred from the viewpoint of the initial gloss of a coating film formed from the resin composition for an aqueous coating material. The styrene-based monomers may be used alone or in combination of two or more.
The styrene monomer may have a functional group such as an alkyl group such as a methyl group or a tert-butyl group, a nitro group, a nitrile group, an alkoxy group, an acyl group, a sulfone group, a hydroxyl group, or a halogen atom on the benzene ring.
The content of the styrene monomer unit in the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material. The content of the styrene monomer unit in the copolymer is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less, from the viewpoint of weather resistance of a coating film formed from the resin composition for an aqueous coating material.
The acrylic monomer constituting the copolymer is not particularly limited, and examples thereof include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, alicyclic (meth) acrylate such as adamantyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, nitrogen-containing (meth) acrylic monomer such as diacetone (meth) acrylamide, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, oleic acid, fumaric acid, citraconic acid, (anhydrous) maleic acid, (anhydrous) citraconic acid, and the like.
The acrylic monomer is preferably an alkyl (meth) acrylate and a (meth) acrylic acid, more preferably contains an alkyl (meth) acrylate and a methacrylic acid, and particularly preferably contains an alkyl acrylate, an alkyl methacrylate and a methacrylic acid. The acrylic monomer may be used alone or in combination of two or more. (meth) acrylate means acrylate or methacrylate. (meth) 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, more preferably 50% by mass or more, and particularly preferably 55% by mass or more, from the viewpoint of weather resistance of a coating film formed from the resin composition for an aqueous coating material. 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 particularly preferably 70% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
The alkyl group (meth) acrylate preferably has 1 or more, more preferably 2 or more, and particularly preferably 3 or more, in terms of initial gloss of a coating film formed from the aqueous coating resin composition. The alkyl group (meth) acrylate preferably has 15 or less, more preferably 12 or less, and particularly preferably 10 or less carbon atoms in the alkyl group from the viewpoint of drying properties of the aqueous coating material formed from the aqueous coating material resin composition.
The alkyl (meth) acrylate preferably comprises methyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate, and more preferably comprises methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate and n-butyl acrylate.
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, more preferably 50% by mass or more, and particularly preferably 55% by mass or more, from the viewpoint of weather resistance of a coating film formed from the resin composition for an aqueous coating material. 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, and particularly preferably 70% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
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, and particularly preferably 0.1% by mass or more, from the viewpoint of stability of the emulsion particles in the aqueous coating material. 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, more preferably 2% by mass or less, and particularly preferably 1% by mass or less, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
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 particularly preferably 0.1% by mass or more, from the viewpoint of stability of the emulsion particles in the aqueous coating material. The content of the methacrylic acid unit in the copolymer is preferably 4% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
The unsaturated fatty acid salt constituting the copolymer is a reactive emulsifier. The reactive emulsifier has an emulsifying effect. 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. In the case of the unsaturated fatty acid salt, it is incorporated into the polymer chain of the copolymer by radical polymerization at the unsaturated bond. The unsaturated fatty acid salts may be used alone or in combination of two or more.
Since the copolymer contains an unsaturated fatty acid salt unit, the copolymer has a hydrophobic portion and a hydrophilic portion. The copolymer can be dispersed in an aqueous medium by adopting a micelle structure in which the hydrophobic portion is on the inside and the hydrophilic portion is on the outside, and can constitute an aqueous coating material. The aqueous medium is not particularly limited, and examples thereof include: water, alcohol solvents (e.g., methanol, ethanol, propanol, isopropanol, butanol, etc.), glycol ether solvents (e.g., ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol butyl ether, etc.), etc., and water is preferred.
The unsaturated fatty acid salt contains an unsaturated bond in the substituent R. The substituent R takes a structure bent at the unsaturated bond portion. The substituent R has a bent structure, so that the hydrophobic portion of the copolymer is bent and appropriately accommodated in the micelle, thereby improving the dispersibility of the copolymer in an aqueous medium.
The unsaturated bond in the substituent R is not particularly limited, but 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 preferable, and an ethylenically unsaturated double bond is more preferable. The ethylenically unsaturated double bond includes a cis double bond and a trans double bond, and the hydrophobic moiety in the copolymer can be appropriately contained in the micelle while being included, and therefore the cis double bond is preferable.
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. When the number of carbon atoms of the substituent R is 11 or more, it is preferable that the number of carbon atoms counted from the carbon at the end of the substituent R (the end of the longest chain in the substituent R) is 3 or more, and the unsaturated bond is present between the 3 rd and subsequent carbons, more preferably the number of carbon atoms counted from the end of the substituent R, the unsaturated bond is present between the 5 th and subsequent carbons, particularly preferably the number of carbon atoms counted from the end of the substituent R, and the unsaturated bond is present between the 6 th and subsequent carbons.
The number of carbon atoms of the unsaturated fatty acid salt (the total number of carbon atoms 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 number of carbon atoms of the unsaturated fatty acid salt (the total number of carbon atoms 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) as a raw material of the unsaturated fatty acid salt is not particularly limited, and examples thereof include: butenoic acid (C4), pentenoic acid (C5), hexenoic acid (C6), heptenoic acid (C7), octenoic acid (C8), nonenoic 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), eicosenoic acid (C20), heneicosenoic acid (C21), docosenoic acid (C22), tricosenoic acid (C23), arachidonic acid (C24), pentacosenoic acid (C25), hexacosenoic acid (C26), heptacosenoic acid (C27), octacosenoic acid (C28), docosenoic acid (C29), triacontenoic acid (C30), and the like, preferably contains octadecenoic acid. In parentheses, the total number of carbon atoms of the unsaturated fatty acid is indicated.
Specific examples (common names) of unsaturated fatty acids as raw materials of the unsaturated fatty acid salt include, for example: myristoleic acid (C14, 1, B14), palmitoleic acid (C14, 1, B14), linoleic acid (C14, 4, B14, 6, 9, 12), vaccenic acid (C14, 1, B14), oleic acid (C14, 1, B14), elaidic acid (C14, 1, B14), linoleic acid (C14, 2, B14, 9), alpha-linolenic acid (C14, 3, B14, 6, 9), gamma-linolenic acid (C14, 3, B14, 9, 12), gadoleic acid (C14, 1, B14), arachidic acid (C14, 1, B14), eicosadienoic acid (C14, 2, B14, 9), arachidonic acid (C14, 3, B14, 9, dilute acid), eicosapentaenoic acid (C14, B365, B14, docosahexaenoic acid (C14, B14, C14, B3615), docosahexaenoic acid (C14, C14, B14, C14, B3615, docosahexaenoic acid, 14, C14, 3615, B14, docosahexaenoic acid (C14, C14, 3615, C14, C3615, C14, C3615, 1, B9), etc., preferably palmitoleic acid, oleic acid, and linoleic acid, more preferably oleic acid and linoleic acid, and particularly preferably oleic acid. Note that, symbols in parentheses sequentially represent: the number of total carbon atoms, the number of ethylenically unsaturated double bonds, and the position of the ethylenically unsaturated double bonds. Bn, m, p represents an ethylenically unsaturated double bond between the n-and (n +1) -th, m-and (m +1) -th, p-and (p +1) -th carbons, counting from the end of the substituent R.
The unsaturated fatty acid salt may be used alone, two or more kinds of the unsaturated fatty acid salts may be used in combination, or a salt of an animal or vegetable oil fatty acid containing a plurality of kinds of unsaturated fatty acids may be used.
Examples of the animal and vegetable oil fatty acid salt 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, safflower oil fatty acid salt, sunflower oil fatty acid salt, linseed oil fatty acid salt, fish oil fatty acid salt, dehydrated castor oil fatty acid salt, palm oil fatty acid salt, tallow fatty acid salt, rapeseed oil fatty acid salt, olive oil fatty acid salt, and the like, and preferably tall oil fatty acid salt.
The unsaturated fatty acid salt may also be a derivative thereof. The derivative of the unsaturated fatty acid salt is not particularly limited, and examples thereof include: the salts of the polymerized fatty acid, the salts of the unsaturated carboxylic acid adduct, the salts of the epoxidized unsaturated fatty acid, the salts of the hydroxylated unsaturated fatty acid, the salts of the epoxidized and hydroxylated unsaturated fatty acid, the salts of the sulfoneed unsaturated fatty acid, and the like are preferred, and the salts of the polymerized fatty acid, more preferred are the salts of the dimer acid and the salt of the trimer acid, and particularly preferred is the salt of the dimer acid. The derivative of the unsaturated fatty acid salt is required 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 radical in the presence of a catalyst such as clay as necessary, and examples thereof include: dimer acid salts (salts of dimers of unsaturated fatty acids), trimer acids (salts of trimers of unsaturated fatty acids), and tetramer acids (salts of tetramers of unsaturated fatty acids), and the like, and the dimer acid salts and the trimer acid salts are preferable, and the dimer acid salts and the trimer acid salts are preferably included. The polymerized fatty acid salts may be used alone or in combination of two or more.
The polymerized fatty acid salt may be partially hydrogenated, but needs to have an unsaturated bond left.
Examples of the salt of the unsaturated carboxylic acid adduct include salts of compounds obtained by addition reaction of an α, β -unsaturated carboxylic acid with an unsaturated bond of the unsaturated fatty acid. Specifically, for example, there can be mentioned: salts of adducts of maleic acid or anhydride thereof of unsaturated fatty acids, salts of acrylic acid adducts of unsaturated fatty acids, and the like. The salt of the unsaturated carboxylic acid adduct needs to leave an unsaturated bond.
The salt of an epoxidized unsaturated fatty acid is, for example, a salt of a compound obtained by epoxidizing an unsaturated bond of an unsaturated fatty acid with peracetic acid, hydrogen peroxide, or the like. The hydroxylated unsaturated fatty acid salt is a salt in which 2 hydroxyl groups are introduced by hydrolyzing an epoxidized unsaturated fatty acid salt. The salt of a sulfone-converted unsaturated fatty acid is a salt of a compound obtained by subjecting an unsaturated bond of an unsaturated fatty acid to a sulfone-conversion reaction with sulfuric acid or the like. Salts of epoxidized unsaturated fatty acids, salts of hydroxylated unsaturated fatty acids, and salts of sulfoneized unsaturated fatty acids need to have unsaturation left.
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 particularly preferably 1.0% by mass or more, from the viewpoint of stability of the emulsion particles in the aqueous coating material. The content of the unsaturated fatty acid salt unit in the copolymer is preferably 5.0% by mass or less, more preferably 4.5% by mass or less, from the viewpoint of initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
The content of the dimer acid salt in the polymerized fatty acid salt is preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
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, even more preferably 95% by mass or less, and particularly preferably 87% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
The content of the trimer salt in the polymerized fatty acid salt is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, more preferably 10% by mass or more, and particularly preferably 13% by mass or more, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
The content of the trimer salt in the polymerized fatty acid salt is preferably 95% by mass or less, more preferably 85% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
The unsaturated fatty acid salt preferably contains a monomeric unsaturated fatty acid salt (monomeric acid salt), a dimeric acid salt, and a trimeric acid salt. The monomeric unsaturated fatty acid salt (monomeric acid salt) means an unpolymerized unsaturated fatty acid salt.
When the unsaturated fatty acid salt contains a monomeric acid salt, a dimeric acid salt, and a trimeric acid salt, the content of the monomeric acid salt in the unsaturated fatty acid salt is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more, from the viewpoint of the initial gloss of a coating film formed from the aqueous coating material resin composition. 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, more preferably 6% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
When the unsaturated fatty acid salt contains a monomeric acid salt, a dimeric acid salt, and a trimeric acid salt, the content of the dimeric acid salt in the unsaturated fatty acid salt is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material. 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, and particularly preferably 85% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
When the unsaturated fatty acid salt contains a monomeric acid salt, a dimeric acid salt, and a trimeric acid salt, the content of the trimeric acid salt in the unsaturated fatty acid salt is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 70% by mass or more, from the viewpoint of the initial water resistance of a coating film formed from the resin composition for an aqueous coating material. The content of the trimer salt in the unsaturated fatty acid salt is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, from the viewpoint of initial gloss of a coating film formed from the resin composition for an aqueous coating material.
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. The reactive emulsifier other than the unsaturated fatty acid salt has at least 1 unsaturated bond in the molecule, and is incorporated into the copolymer by radical polymerization at the unsaturated bond.
The unsaturated bond is not particularly limited, but an ethylenically unsaturated bond such as an ethylenically unsaturated double bond (carbon-carbon double bond, C ═ C) or an ethylenically unsaturated triple bond (carbon-carbon triple bond) is preferable, and an ethylenically unsaturated double bond is more preferable. It is possible to have a plurality of unsaturated bonds in the molecule.
Examples of the ethylenically unsaturated double bond include unsaturated bonds contained in functional groups such as an alkenyl group, a (meth) allyloxyalkyl group, and a (meth) acryloyl group. The term (meth) allyl means allyl or methallyl. (meth) acryloyl means acryloyl or methacryloyl.
Examples of the alkenyl group include: vinyl, (meth) allyl, 1-propenyl, 2-methyl-1-propenyl, isopropenyl and the like.
The reactive emulsifier other than the unsaturated fatty acid salt is not particularly limited, and examples thereof include: sulfuric acid ester salts of polyoxyalkylene phenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule, sulfosuccinic acid ester salts of polyoxyethylene alkyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule (ester sodium salt, ester ammonium salt, etc.), sulfuric acid ester salts of polyoxyethylene alkyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule (ester sodium salt, ester ammonium salt, etc.), sulfosuccinic acid ester salts of polyoxyethylene alkylphenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule (ester sodium salt, ester ammonium salt, etc.), sulfuric acid ester salts of polyoxyalkylene alkylphenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule (ester sodium salt, ester ammonium salt, etc.), sulfuric acid ester salts, sulfuric acid esters, sulfuric acid, Ester ammonium salts, etc.), acidic phosphoric acid (meth) acrylate dispersants having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule, and the like. The reactive emulsifiers other than the unsaturated fatty acid salt may be used alone, or two or more kinds may be used in combination.
The reactive emulsifier other than the unsaturated fatty acid salt preferably has an ethylenically unsaturated double bond in the vicinity of the molecular end. The term "molecular terminal vicinity" refers to a carbon-carbon bonding portion formed by a terminal carbon and the 2 nd and 3 rd carbons counted from the terminal carbon (1 st) in a molecular chain to which carbon atoms are bonded. The reactive emulsifier other than the unsaturated fatty acid salt preferably has an ethylenically unsaturated double bond between a terminal carbon (1 st carbon) and a carbon (2 nd carbon) bonded to the terminal carbon. Reactive emulsifiers other than unsaturated fatty acid salts, counted from the terminal carbon, preferably have an ethylenically unsaturated double bond between the 2 nd and 3 rd carbons.
The reactive emulsifier other than the unsaturated fatty acid salt is preferably a sulfuric acid ester salt of a polyoxyalkylene phenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule, more preferably a sulfuric acid ester ammonium salt of a polyoxyalkylene phenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule, and more preferably a sulfuric acid ester ammonium salt of a polyoxyethylene phenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule.
The sulfuric acid ester salt of polyoxyalkylene phenyl ether having at least 1 functional group containing an ethylenically unsaturated double bond in the molecule is preferably polyoxyethylene styrenated propenyl phenyl ether sulfuric acid ammonium salt, polyoxyethylene styrenated propenyl phenyl ether sulfuric acid sodium salt, polyoxyethylene propenyl phenyl ether sulfuric acid ammonium salt, polyoxyethylene propenyl phenyl ether sulfuric acid sodium salt, more preferably polyoxyethylene styrenated propenyl phenyl ether sulfuric acid ammonium salt and polyoxyethylene styrenated propenyl phenyl ether sulfuric acid sodium salt.
Examples of the reactive emulsifier other than the unsaturated fatty acid salt include: acid anhydride-modified products of glycidyl acrylate rosin (JP-A-4-256429), dispersants as described in JP-A-63-23725, dispersants as described in JP-A-63-240931, dispersants as described in JP-A-62-104802, and the like.
The reactive emulsifier is available as a commercial product. Examples of such commercially available products include: KAYAMER PM-1 (manufactured by JASCO chemical Co., Ltd.), KAYAMER PM-2 (manufactured by JASCO chemical Co., Ltd.), KAYA MER PM-21 (manufactured by JASCO chemical Co., Ltd.), SE-10N (manufactured by Asahi electric chemical industry Co., Ltd.), NE-20 (manufactured by Asahi electric chemical industry Co., Ltd.), NE-30 (manufactured by Asahi electric chemical industry Co., Ltd.), NEW FRONTIER A229E (manufactured by first Industrial pharmaceutical Co., Ltd.), NEW FRONTIER N-117E (manufactured by first Industrial pharmaceutical Co., Ltd.), NEW FRONTIER N250Z (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron (アクアロン, Hitenol) RN-20 (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron-2025 (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron BC-1025 (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron AR-1025 (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron AR-10 (manufactured by first Industrial pharmaceutical Co., Ltd.), Akuaron KH-H-1025 (manufactured by first Industrial pharmaceutical Co., Ltd.) Eleminor JS-2 (manufactured by Sanyo chemical Co., Ltd.), Late mul K-180 (manufactured by King of flowers), and Late mul PD-104 (manufactured by King of flowers). The reactive emulsifier is preferably Akua ron AR-1025 (first Industrial pharmaceutical).
The content of the monomer unit derived from the reactive emulsifier other than the unsaturated fatty acid salt in the emulsifier component of the copolymer is preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and particularly preferably 0 to 30% by mass, from the viewpoint of improving the initial water resistance of a coating film formed from the resin composition for an aqueous coating material. The phrase "0% by mass" means that the copolymer does not contain a monomer unit derived from a reactive emulsifier other than the unsaturated fatty acid salt.
When 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 content of all monomer units derived from the reactive emulsifier in the copolymer is preferably 0.5% by mass or more from the viewpoint of stability of emulsion particles in the aqueous coating material. The copolymer may contain a reactive emulsifier containing an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt as a monomer unit, and is preferably 4% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less, from the viewpoint of initial water resistance of a coating film formed from the resin composition for an aqueous coating material.
In the copolymer, when a reactive emulsifier containing an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt is contained as a monomer unit, the ratio of the total amount of the compound other than the unsaturated fatty acid salt to the total amount of the unsaturated fatty acid salt (total amount of the compound other than the unsaturated fatty acid salt/unsaturated fatty acid salt) in the reactive emulsifier is preferably 0.2 or more. In the reactive emulsifier, the ratio of the total amount of compounds other than the unsaturated fatty acid salt to the total amount of the unsaturated fatty acid salt (total amount of compounds other than the unsaturated fatty acid salt/unsaturated fatty acid salt) is preferably 3 or less, more preferably 2 or less, more preferably 1.5 or less, and more preferably 0.5 or less. When 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. When the ratio of the total amount of the compound other than the unsaturated fatty acid salt to the total amount of the unsaturated fatty acid salt is 3 or less, the initial gloss and the initial water resistance of a coating film formed from the resin composition for an aqueous coating material are improved, which is preferable.
The copolymer may contain fatty acid-modified monomer units. 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. Unsaturated fatty acids (unpolymerized unsaturated fatty acids) may be used in place of or in combination with the drying oil fatty acid and/or the semi-drying oil fatty acid. The 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, and particularly preferably 3% by mass or more, from the viewpoint of improving the initial water resistance of a coating film formed from the resin composition for an aqueous coating material. 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.
The drying oil fatty acid and the semi-drying oil fatty acid are fatty acids having an oxidative curing type polymerizable unsaturated group. Examples of the drying oil fatty acid and the semi-drying oil fatty acid include: fish oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, perilla oil fatty acids, sesame oil fatty acids, grape seed oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower seed oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, and the like, and preferably tall oil fatty acids.
The drying oil fatty acid and/or the half-drying oil fatty acid radical may be, for example, a non-drying oil fatty acid such as coconut oil fatty acid, hydrogenated coconut oil fatty acid, palm oil fatty acid; caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like are used in combination.
Examples of the polymerizable unsaturated monomer containing an epoxy group include: glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether and the like, with glycidyl (meth) acrylate being preferred and glycidyl methacrylate being more preferred.
The salt of the unsaturated fatty acid salt is not particularly limited, and examples thereof include: alkali metal salts of sodium, potassium, lithium, etc.; alkaline earth metal salts of calcium, barium, etc.; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and organic amine salts such as triethylamine; ammonium salts and the like are preferred, and alkali metal salts and alkaline earth metal salts are more preferred, and alkali metal salts are still more preferred, sodium salts and potassium salts are still more preferred, and potassium salts are still more preferred.
The glass transition temperature Tg of the copolymer constituting the resin composition for aqueous coating materials is preferably-4 ℃ or higher, more preferably 1 ℃ or higher, and particularly preferably 6 ℃ or higher, from the viewpoint of improving the initial water resistance and gloss retention of a coating film formed from the resin composition for aqueous coating materials. The glass transition temperature Tg of the copolymer constituting the resin composition for aqueous coating materials is preferably 40 ℃ or lower, more preferably 35 ℃ or lower, even more preferably 25 ℃ or lower, even more preferably 23 ℃ or lower, and particularly preferably 19 ℃ or lower, from the viewpoint of improving the initial gloss of a coating film formed from the resin composition for aqueous coating materials.
The glass transition temperature (Tg) of the copolymer was measured by using a Differential Scanning Calorimetry (DSC) apparatus in accordance with JIS K7121-1987.
The method for producing the copolymer constituting the resin composition for aqueous coating materials is not particularly limited, and examples thereof include: (1) a method for producing a copolymer by emulsion-polymerizing a monomer composition comprising a styrene-based monomer, an acrylic monomer, and an unsaturated fatty acid salt as a reactive emulsifier in an aqueous medium in the presence of a widely used radical polymerization initiator; (2) a method for producing a copolymer by radical polymerization of a monomer composition containing a styrene-based monomer, an acrylic monomer and an unsaturated fatty acid salt in an organic solvent (e.g., xylene, toluene, methyl isobutyl ketone, etc.) in the presence of a widely used radical polymerization initiator, and the production method (1) is preferred from the viewpoint of the amount of the remaining solvent. When a copolymer is produced by the production method of the above (2), the obtained copolymer may be separated, and the separated copolymer may be dispersed in an aqueous medium by using a dispersing machine having a high energy shearing capability as required. Examples of the radical polymerization initiator include azo compounds, peroxide compounds, sulfide compounds, sulfoxide compounds, and diazo compounds.
The resin composition for aqueous coating materials can be dispersed in an aqueous medium to produce an aqueous coating material. The content (solid content) of the copolymer constituting the resin composition for an aqueous coating material in the aqueous coating material is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 20 to 60% by mass.
Further, since the copolymer constituting the resin composition for an aqueous coating material contains an unsaturated fatty acid salt as a reactive emulsifier as a monomer unit thereof, it is possible to form a somewhat homogeneous aqueous coating material which is dispersed in an aqueous medium with good opalescence. Further, when the resin composition for an aqueous coating material is dispersed in an aqueous medium, the emulsifier may not be used, or the amount of the emulsifier used may be suppressed.
The aqueous coating composition may contain, if necessary, a widely used additive such as a non-reactive emulsifier, a pigment, a film-forming aid, a defoaming agent, a thickener, a preservative, a mildewproofing agent, a pH adjuster, a metal drier, and the like.
Examples of the non-reactive emulsifier include anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers, and anionic emulsifiers are preferable. The non-reactive emulsifier may be used alone or in combination of two or more.
Examples of the anionic emulsifier include: sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene alkylsulfosuccinate, polyoxyalkylene polycyclic phenyl ether sulfate ester salts (for example, sodium polyoxyethylene polycyclic phenyl ether sulfate, ammonium polyoxyethylene polycyclic phenyl ether sulfate, sodium polyoxypropylene polycyclic phenyl ether sulfate, ammonium polyoxypropylene polycyclic phenyl ether sulfate, etc.), and the like. The anionic emulsifier is preferably polyoxyalkylene polycyclic phenyl ether sulfate, preferably polyoxyethylene polycyclic phenyl ether sulfate, and more preferably polyoxyethylene polycyclic phenyl ether sulfate ammonium.
Examples of the cationic emulsifier include: alkyl trimethyl ammonium chlorides, and the like.
Examples of the nonionic emulsifier include: polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, and the like. These may be used alone or in combination of 2 or more.
The content of the non-reactive emulsifier in the aqueous coating material is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, and still more preferably 0 to 2 parts by mass, based on 100 parts by mass of the copolymer. The phrase "0 part by mass" means that the water-based paint does not contain a non-reactive emulsifier.
The surface of an object to be coated (for example, a building material such as an exterior material used for building construction) is coated with the obtained aqueous coating material, and the surface of the object to be coated can be coated with a coating film formed by applying the aqueous coating material to the surface of the object to be coated and then evaporating and removing the aqueous medium in the coating layer to cure the coating film.
Here, the copolymer constituting the resin composition for an aqueous coating material contains, as a monomer unit, an unsaturated fatty acid salt unit as a reactive emulsifier in the molecule, as described above. The unsaturated fatty acid salt has an unsaturated bond in the molecule, and therefore bonds to be incorporated into the copolymer by a copolymerization reaction, and further has an aliphatic group, and therefore, even when a coating film formed from the resin composition for an aqueous coating material is exposed to water, elution of the coating film component can be prevented. Therefore, in the coating film formed from the aqueous coating material, the unsaturated fatty acid salt unit constituting the copolymer does not release from the copolymer and flows out from the surface of the coating film.
Further, when the resin composition for an aqueous coating material is dispersed in an aqueous medium to prepare an aqueous coating material, as described above, it is possible to eliminate the need for using an emulsifier or reduce the amount of the emulsifier used.
Therefore, the amount of free emulsifier in the coating film formed from the aqueous coating material is extremely small, and voids caused by the outflow of the emulsifier formed on the surface of the coating film are reduced or suppressed in the state of being exposed to water during the formation of the coating film or after the formation of the coating film.
Therefore, the penetration of water into the interior of 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. Further, the unsaturated fatty acid salt unit in the copolymer can improve leveling property at the time of forming a coating film, and the initial gloss of the coating film is also excellent.
Examples
[ Synthesis of fatty acid-modified monomer ]
The compounds shown below were supplied to a reaction vessel, and reacted at 160 ℃ while stirring in the reaction vessel, so that tall oil fatty acid and glycidyl methacrylate were subjected to addition reaction for about 90 minutes to obtain a fatty acid-modified monomer. After the completion of the reaction, 0.08 part by mass of hydroquinone was supplied into the reaction vessel. Tall oil fatty acid contains 2 mass% palmitic acid and 2 mass% stearic acid as saturated fatty acids, and 46 mass% oleic acid and 41 mass% linoleic acid as unsaturated fatty acids. The addition reaction of the epoxy group of glycidyl methacrylate and the carboxyl group of tall oil fatty acid was monitored by measuring the amount of the remaining acid component.
Tall oil fatty acid: 260.00 parts by mass
Glycidyl methacrylate: 136.00 parts by mass
4-methoxyphenol (p-Hydroxynisol): 0.70 parts by mass
Tetrabutylphosphonium bromide: 0.40 parts by mass
Triphenylphosphine: 0.40 parts by mass
[ emulsifiers ]
(Synthesis of unsaturated fatty acid salt 1)
344.92 parts by mass of distilled water and 44.73 parts by mass of a 48% by mass aqueous solution of potassium hydroxide were supplied into the reaction vessel, and the temperature was maintained at 95 ℃ for about 1 hour while stirring. Next, 110.35 parts by mass of an unsaturated fatty acid shown below was supplied into the reaction vessel, and the reaction was carried out while maintaining 95 ℃ for 3 hours under stirring, whereby a potassium salt of an unsaturated fatty acid (reactive emulsifier) having a solid content concentration of 25 mass% was obtained. In table 1, the obtained potassium salts of unsaturated fatty acids are represented by adding "K salt" to the suffix of the trade name of the reactive emulsifier as the raw material. Hereinafter, "potassium salt" is represented by "K salt".
Unsaturated fatty acid 1: harima chemical company, product name "Haridimer 200 (DA-200)"
Unsaturated fatty acid 2: trade name "Tsunodome 395" manufactured by Shuangye food industry Co., Ltd "
Unsaturated fatty acid 3: product name "Tsunodome 228" manufactured by Shuangye food industry Co., Ltd "
(Synthesis of unsaturated fatty acid salt 2)
Unsaturated fatty acid in tall oil fatty acid and maleic anhydride are subjected to addition reaction to obtain an adduct. This adduct was prepared as a potassium salt according to the method of synthesis 1 of unsaturated fatty acid salt, and a potassium salt of unsaturated fatty acid (BK-73B K salt, potassium salt of oleic acid) (reactive emulsifier) having a solid content concentration of 25 mass% was obtained.
Tall oil fatty acid contains 2 mass% of palmitic acid and 2 mass% of stearic acid as saturated fatty acids, and contains 46 mass% of oleic acid and 41 mass% of linoleic acid as unsaturated fatty acids.
(Synthesis of unsaturated fatty acid salt 3)
A reaction product obtained by reacting an unsaturated fatty acid (trade name "Haridimer 200 (DA-200)" manufactured by Harima chemical company) with N, N-dimethylaminoethanol was prepared as a potassium salt according to the method for synthesizing an unsaturated fatty acid salt 1, and a potassium salt of an unsaturated fatty acid (DA-200Mabs salt) (a reactive emulsifier) having a solid content concentration of 25 mass% was obtained.
(Synthesis of unsaturated fatty acid salt 4)
471.91 parts by mass of distilled water and 47.38 parts by mass of a 48 mass% aqueous solution of potassium hydroxide were supplied into the reaction vessel, and the temperature was maintained at 95 ℃ for about 1 hour while stirring. Next, 110.08 parts by mass of tall oil fatty acid (trade name "Hartall FA-1" manufactured by Harima chemical company) was supplied into the reaction vessel, and the reaction was carried out while maintaining the temperature at 95 ℃ for 3 hours under stirring, whereby a potassium salt of tall oil fatty acid (FA-1K salt) (reactive emulsifier) having a solid content of 19.4 mass% was obtained. The potassium salt of tall oil fatty acid comprises the potassium salt of oleic acid and the potassium salt of linoleic acid.
Tall oil fatty acid contains 2 mass% of palmitic acid and 2 mass% of stearic acid as saturated fatty acids, and contains 46 mass% of oleic acid and 41 mass% of linoleic acid as unsaturated fatty acids.
(Synthesis of saturated fatty acid salt 1)
676.89 parts by mass of distilled water and 46.83 parts by mass of a 48 mass% aqueous solution of potassium hydroxide were supplied into the reaction vessel, and the temperature was maintained at 95 ℃ for about 1 hour while stirring. Next, 109.67 parts by mass of stearic acid as a saturated fatty acid was supplied into the reaction vessel, and the reaction was carried out while maintaining 95 ℃ for 3 hours under stirring, whereby a potassium salt of stearic acid (stearic acid K salt) (non-reactive emulsifier) having a solid content concentration of 15 mass% was obtained.
(other emulsifiers)
First Industrial pharmaceutical Co., Ltd, trade name "Akuaron AR-1025" (reactive emulsifier, polyoxyethylene styrenated propenyl phenyl ether ammonium sulfate)
Polyoxyethylene polycyclic phenyl ether sulfate
Trade name "Newcol 707-SF" (non-reactive emulsifier) manufactured by Japan emulsifier Co., Ltd
f-O-(CH2CH2O)n-SO3X
f: polycyclic phenyl, X: na or NH4
First Industrial pharmaceutical company, product name "Hitenol (ハイテノール) LA-12" (non-reactive emulsifier)
Ammonium polyoxyethylene lauryl ether sulfate
With respect to the emulsifier, the contents of potassium salt of monomer acid (monomer acid K salt), potassium salt of dimer acid (dimer acid K salt), and potassium salt of trimer acid (trimer acid K salt), iodine value (solid) are shown in table 1.
[ monomer composition ]
Monomer compositions 1 to 16 were prepared, each containing styrene, methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, cyclohexyl methacrylate, a fatty acid-modified monomer, diacetone acrylamide and methacrylic acid in the amounts indicated in table 2.
Examples 1 to 25 and comparative examples 1 to 7
(production of resin composition for Water-based paint)
Emulsifiers having compositions (mass%) shown in tables 3 to 5 were prepared. Half of the emulsifier and 91.5 parts by mass of distilled water were supplied to the reaction vessel in the specified supply amounts shown in tables 3 to 5. The reaction vessel was stirred while nitrogen gas was supplied to the reaction vessel for nitrogen gas replacement, and water containing an emulsifier in the reaction vessel was heated to 90 ℃ and held.
Then, 55.2 parts by mass of distilled water and 0.74 parts by mass of ammonium persulfate were added to a mixture of 100 parts by mass of the monomer composition shown in tables 3 to 5 and the remaining half of the emulsifier, and the mixture was stirred at a high speed using a high-speed disperser to emulsify the mixture, thereby preparing a monomer emulsion.
It took 3 hours to add the monomer emulsion dropwise to the reaction vessel. The reaction solution in the reaction vessel was maintained at 90 ℃ for 2 hours to conduct radical polymerization, thereby synthesizing a copolymer. After that, the reaction solution in the reaction vessel was cooled to 40 ℃ or lower, and then the reaction solution was adjusted to pH9 with 28 mass% aqueous ammonia to obtain a resin composition for an aqueous coating material having a solid content (copolymer) concentration of 40 mass%.
The content (% by mass) and the amount (parts by mass) of the emulsifier shown in tables 3 to 5 represent the amount of the solid content.
(production of Water-based paint)
8.55 parts by mass of water, 17.09 parts by mass of a pigment (titanium oxide), 0.70 parts by mass of a pigment dispersant (product name "DISPERBYK-190" manufactured by BYK Chemie) and 0.09 parts by mass of an antifoaming agent (product name "SN Defoamer 777" manufactured by San Nopco) were uniformly mixed to prepare a coating material liquid.
26.43 parts by mass of the above-mentioned coating material liquid, 1.81 parts by mass of an emulsifier (trade name "Newcol 707-SF" manufactured by Nippon emulsifier Co., Ltd.), 27.00 parts by mass (solid content) of a resin composition for a water-based coating material, 40.50 parts by mass of water, 2.20 parts by mass of a film forming aid (diethylene glycol butyl ether), 0.10 parts by mass of an antifoaming agent (trade name "SN Defoamer 777" manufactured by San Nopco Co., Ltd.), 0.40 parts by mass of a thickener (trade name "Primat RM-12W" manufactured by Dow Chemical Japan Co., Ltd.), 1.46 parts by mass of a metal drier (trade name "NATE 3111 TL" manufactured by DIC Co., Ltd.), and 0.10 parts by mass of an auxiliary agent (adipic dihydrazide) were uniformly mixed to prepare a water-based coating material. The amount of the resin composition for aqueous coating material is the amount of solid content.
The following points were used as evaluation criteria for the initial gloss and initial water resistance of the obtained water-based paint, and the gloss retention was measured, and the results are shown in tables 3 to 5. The aqueous coating material of comparative example 4 was gelled and could not be evaluated.
(initial gloss)
An aqueous coating material was applied to a stainless steel plate (150 mm in length x 70mm in width x 0.8mm in thickness) (manufactured by Taiyou machine Co., Ltd.) by using a film applicator (trade name "AP 100" manufactured by Taiyou machine Co., Ltd.) to form a coating layer.
The coating layer on the stainless steel plate was dried in a room at 23 ℃ and a relative humidity of 50% for 16 hours, and water contained in the coating layer was evaporated and removed to form a coating film. The 20 ° specular reflectance (20 ° G) of the obtained coating film was measured, and the measured value was converted into specular gloss in accordance with JIS Z8741. The obtained specular gloss was defined as "initial specular gloss", and this was used as a standard for evaluation of initial gloss.
(initial Water resistance)
The coating film was formed in the same manner as the initial gloss, and the initial specular gloss of the coating film was measured in the manner described above.
A polyvinyl chloride pipe having an inner diameter of 43mm was prepared, and silicone grease was applied to the entire surface of the end face of the first opening in the pipe. So that the pipeline is tightly attached to the coating film. The treatment is performed so that the coated surface of the silicone grease of the pipe is closely adhered to the coating film over the entire surface.
After 15g of distilled water was supplied into the tube, the second opening of the tube was closed with a synthetic resin film to prevent evaporation of the distilled water in the tube. The test piece was left standing for 24 hours in a room at 23 ℃ and a relative humidity of 50%.
Then, after removing distilled water from the inside of the duct, the duct was taken out from the coating film, and after sufficiently wiping off water on the coating film, the duct was left standing for 1 hour in a room at 23 ℃ and a relative humidity of 50%.
The specular gloss of the coating film after the water resistance test (specular gloss after the water resistance test) was measured in the same manner as the initial specular gloss. The gloss retention was calculated based on the following formula. The higher gloss retention means the better initial water resistance.
Gloss retention (%) of 100 × specular gloss after Water resistance test/initial specular gloss
Industrial applicability
The aqueous coating material formed from the resin composition for aqueous coating materials of the present invention can form a coating film having excellent initial gloss and initial water resistance on the surface of a coating object such as a building material, and can coat the surface of the coating object.
(cross-reference to related applications)
The present application claims priority based on japanese patent application No. 2019-51959, filed on 3/19/2019, the entire disclosure of which is incorporated by reference into the present specification.
Claims (7)
1. A resin composition for aqueous coating materials, comprising:
comprises a styrene monomer unit, an acrylic monomer unit and an unsaturated fatty acid salt unit, and has a glass transition temperature of-4 to 40 ℃.
2. The resin composition for aqueous coating material according to claim 1, wherein,
the unsaturated fatty acid salt comprises a polymerized fatty acid salt and/or an oleate salt.
3. The resin composition for aqueous coating according to claim 2, wherein,
the polymerized fatty acid salt comprises a dimer acid salt.
4. The resin composition for aqueous coating material according to any one of claims 1 to 3, wherein,
the unsaturated fatty acid salt contains potassium salt.
5. The resin composition for aqueous coating material according to any one of claims 1 to 4, wherein,
the copolymer is an emulsion polymer of a monomer composition comprising a styrenic monomer, an acrylic monomer, and an unsaturated fatty acid salt as a reactive emulsifier.
6. The resin composition for aqueous coating material according to claim 5, wherein,
the monomer composition is an emulsion polymer of a monomer composition comprising a styrenic monomer, an acrylic monomer, and a reactive emulsifier comprising an unsaturated fatty acid salt and a compound other than the unsaturated fatty acid salt.
7. A coating film which is a cured product of a coating layer formed by applying the resin composition for an aqueous coating material according to any one of claims 1 to 6 to an object to be coated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-051959 | 2019-03-19 | ||
| JP2019051959 | 2019-03-19 | ||
| PCT/JP2020/011949 WO2020189714A1 (en) | 2019-03-19 | 2020-03-18 | Resin composition for aqueous coating materials, and coating film |
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| Publication Number | Publication Date |
|---|---|
| CN113597454A true CN113597454A (en) | 2021-11-02 |
| CN113597454B CN113597454B (en) | 2023-07-25 |
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| CN202080022181.1A Active CN113597454B (en) | 2019-03-19 | 2020-03-18 | Resin composition for aqueous coating material and coating film |
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|---|---|
| JP (1) | JP7341222B2 (en) |
| CN (1) | CN113597454B (en) |
| AU (1) | AU2020240710A1 (en) |
| MY (1) | MY196253A (en) |
| SG (1) | SG11202109832PA (en) |
| WO (1) | WO2020189714A1 (en) |
Citations (6)
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|---|---|---|---|---|
| DE3731760A1 (en) * | 1987-09-22 | 1989-03-30 | Texaco Ag | WAESSED PLASTIC DISPERSION |
| US5538760A (en) * | 1995-05-22 | 1996-07-23 | Eastman Chemical Company | Alkyd/acrylic latexes for cleaning and protecting hard surfaces |
| CN1272854A (en) * | 1997-08-12 | 2000-11-08 | 伊斯曼化学公司 | Acrylic modified waterborne sulfonated alkyd dispersions |
| WO2007042684A1 (en) * | 2005-10-14 | 2007-04-19 | Rhodia Recherches Et Technologies | Method for preparing a grafted copolymer by polyunsaturated fatty acids, copolymer grafted by polyunsaturated fatty acids obtainable by said method and uses thereof |
| CN101981066A (en) * | 2008-03-31 | 2011-02-23 | 帝斯曼知识产权资产管理有限公司 | Coating composition comprising autoxidisable component |
| JP2018521145A (en) * | 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 | Aqueous dispersion |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50161581A (en) * | 1974-06-21 | 1975-12-27 | ||
| KR20100100887A (en) * | 2007-11-21 | 2010-09-15 | 바스프 에스이 | New polymers by emulsion polymerization |
| CN109438635B (en) * | 2018-10-24 | 2021-08-17 | 北京金汇利应用化工制品有限公司 | Waterborne epoxy ester modified petroleum resin |
-
2020
- 2020-03-18 MY MYPI2021005419A patent/MY196253A/en unknown
- 2020-03-18 WO PCT/JP2020/011949 patent/WO2020189714A1/en active Application Filing
- 2020-03-18 JP JP2021507393A patent/JP7341222B2/en active Active
- 2020-03-18 AU AU2020240710A patent/AU2020240710A1/en active Pending
- 2020-03-18 SG SG11202109832P patent/SG11202109832PA/en unknown
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3731760A1 (en) * | 1987-09-22 | 1989-03-30 | Texaco Ag | WAESSED PLASTIC DISPERSION |
| US5538760A (en) * | 1995-05-22 | 1996-07-23 | Eastman Chemical Company | Alkyd/acrylic latexes for cleaning and protecting hard surfaces |
| CN1272854A (en) * | 1997-08-12 | 2000-11-08 | 伊斯曼化学公司 | Acrylic modified waterborne sulfonated alkyd dispersions |
| WO2007042684A1 (en) * | 2005-10-14 | 2007-04-19 | Rhodia Recherches Et Technologies | Method for preparing a grafted copolymer by polyunsaturated fatty acids, copolymer grafted by polyunsaturated fatty acids obtainable by said method and uses thereof |
| FR2892122A1 (en) * | 2005-10-14 | 2007-04-20 | Rhodia Recherches & Tech | PROCESS FOR PREPARING A POLYUNSATURATED FATTY ACID COPOLYMER, POLYUNSATURATED FATTY ACID COPOLYMER CAPABLE OF OBTAINING THE SAME, AND USES THEREOF |
| CN101981066A (en) * | 2008-03-31 | 2011-02-23 | 帝斯曼知识产权资产管理有限公司 | Coating composition comprising autoxidisable component |
| JP2018521145A (en) * | 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 | Aqueous dispersion |
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| Publication number | Publication date |
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| JP7341222B2 (en) | 2023-09-08 |
| CN113597454B (en) | 2023-07-25 |
| MY196253A (en) | 2023-03-24 |
| SG11202109832PA (en) | 2021-10-28 |
| JPWO2020189714A1 (en) | 2020-09-24 |
| WO2020189714A1 (en) | 2020-09-24 |
| AU2020240710A1 (en) | 2021-09-30 |
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