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CN119095924A - Water-based resin dispersion, water-based paint and articles coated with water-based paint - Google Patents

Water-based resin dispersion, water-based paint and articles coated with water-based paint Download PDF

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Publication number
CN119095924A
CN119095924A CN202280095469.0A CN202280095469A CN119095924A CN 119095924 A CN119095924 A CN 119095924A CN 202280095469 A CN202280095469 A CN 202280095469A CN 119095924 A CN119095924 A CN 119095924A
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meth
acrylate
mass
aqueous
resin dispersion
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Inventor
松泽博
王世良
吴琼
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DIC Corp
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

An aqueous resin dispersion obtained by radical polymerization of a (meth) acrylate (X) in resin particles dispersed in an aqueous medium, wherein the (meth) acrylate (X) is a product of a reaction of an acrylic polymer (a) having hydroxyl groups and carboxyl groups with a urethane (meth) acrylate (B) having isocyanate groups, is provided. The aqueous resin dispersion is useful for aqueous coating because it provides a cured coating film having excellent appearance, hardness, adhesion, alcohol resistance, hot water resistance and solvent resistance, and the aqueous coating can be applied to various articles.

Description

Aqueous resin dispersion, aqueous coating material, and article coated with aqueous coating material
Technical Field
The present invention relates to an aqueous resin dispersion, an aqueous coating material and an article coated with the aqueous coating material.
Background
In the context of VOC regulations, the use of waterborne coatings is advancing in a variety of applications. However, automotive interior coatings face high hurdles to aqueous coatings due to high performance requirements for coating film appearance, adhesion, chemical resistance, and the like, and solvent-based coatings are the mainstream.
Under such circumstances, an aqueous resin dispersion obtained by copolymerizing a urethane acrylate oligomer and another acrylic monomer has been proposed (see, for example, patent document 1). However, this material has problems such as workability, because it is a two-component curing type using an amino resin as a curing agent.
Therefore, there is a need for a one-component aqueous material that provides a cured coating film having a variety of excellent physical properties such as appearance, hardness, adhesion, alcohol resistance, hot water resistance, and solvent resistance.
Citation enumeration
Patent literature
PTL 1:CN105601832B
Summary of The Invention
Technical problem
The problem to be solved by the present invention is to provide an aqueous resin dispersion which provides a cured coating film having excellent appearance, hardness, adhesion, alcohol resistance, hot water resistance and solvent resistance, an aqueous coating material containing the aqueous dispersion, and an article coated with the coating material.
Solution to the problem
The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the inventors have found that the above-mentioned problems can be solved by obtaining an aqueous resin dispersion by radical polymerization of a specific (meth) acrylate in resin particles dispersed in an aqueous medium, and completed the present invention.
That is, the present invention relates to an aqueous resin dispersion obtained by radical polymerization of (meth) acrylic acid ester (X) in resin particles dispersed in an aqueous medium, wherein the (meth) acrylic acid ester (X) is a reaction product of an acrylic polymer (A) having hydroxyl groups and carboxyl groups and a urethane (meth) acrylic acid ester (B) having isocyanate groups, an aqueous coating material containing the aqueous dispersion, and an article coated with the aqueous coating material.
Advantageous effects of the invention
The aqueous resin dispersion of the present invention is useful for water-based coating materials because it provides a cured coating film having excellent appearance, hardness, adhesion, alcohol resistance, hot water resistance and solvent resistance, and the aqueous coating material can be applied to various articles. Accordingly, the aqueous resin dispersion of the present invention can be suitably used as an aqueous coating material for coating articles such as bodies of household appliances such as refrigerators, televisions and air conditioners, housings of information terminals such as mobile phones, smart phones and personal computers, automotive interiors, cosmetic containers and highly-designed packaging materials.
Description of the embodiments
The aqueous resin dispersion of the present invention is an aqueous resin dispersion obtained by radical polymerization of (meth) acrylate (X) in resin particles dispersed in an aqueous medium, wherein (meth) acrylate (X) is a product of a reaction of an acrylic polymer (a) having hydroxyl groups and carboxyl groups with a urethane (meth) acrylate (B) having isocyanate groups.
First, the acrylic polymer (a) will be described. The acrylic polymer (a) is obtained by copolymerizing an unsaturated monomer (a 1) having a hydroxyl group, an unsaturated monomer (a 2) having a carboxyl group, and another unsaturated monomer (a 3).
Examples of the unsaturated monomer (a 1) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-N-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-N-butyl (meth) acrylate, 3-hydroxy-N-butyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and lactone-modified (meth) acrylate having a terminal hydroxyl group. These unsaturated monomers (a 1) may be used alone, or two or more may be used in combination.
Examples of the unsaturated monomer (a 2) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, β -carboxyethyl (meth) acrylate, ω -carboxyl-polycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl succinate and 2- (meth) acryloyloxyethyl hexahydrophthalic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and half esters of these unsaturated dicarboxylic acids. Among them, (meth) acrylic acid is preferable because of its excellent dispersibility in water. These unsaturated monomers (a 2) may be used singly, or two or more may be used in combination.
Further, examples of the unsaturated monomer (a 3) include aromatic vinyl monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, N-pentyl (meth) acrylate, N-hexyl (meth) acrylate, N-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methacrylamide, N-dimethyl (meth) acrylamide, methacryloyl (meth) acrylonitrile, 3-propyl (meth) acryl, and (meth) acryl (meth) nitrile N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, alpha-methylstyrene, p-methylstyrene and p-methoxystyrene. Among them, from the viewpoint of water dispersibility, (meth) acrylic acid esters having an ethylene oxide chain such as methoxypolyethylene glycol (meth) acrylic acid esters and ethoxypolyethylene glycol (meth) acrylic acid esters are preferable, and (meth) acrylic acid compounds having a carbonyl group such as diacetone (meth) acrylamide are preferable because they can form a crosslink with a dihydrazide compound. These unsaturated monomers (a 3) may be used singly or in combination of two or more.
From the viewpoint of the reaction point with the urethane acrylate (B), the amount of the acrylic monomer (a 1) in the monomer component as the raw material of the acrylic polymer (a) is preferably 3 to 50 mass%, more preferably 5 to 30 mass%.
From the viewpoint of water dispersibility, the amount of the acrylic monomer (a 2) in the monomer component as a raw material of the acrylic polymer (a) is preferably 1 to 20 mass%, more preferably 3 to 10 mass%.
The amount of the acrylic monomer (a 3) used is the balance obtained by subtracting the use ratio of the unsaturated monomers (a 1) and (a 2) from the total 100 mass% of the monomer components as the raw material of the acrylic polymer (a).
Examples of the method for producing the acrylic polymer (a) include a method of copolymerizing the acrylic monomer (a 1) and the unsaturated monomer (a 2) in an organic solvent using a polymerization initiator. The organic solvent used herein is preferably an alcohol compound, a ketone compound, an ester compound, an ether compound, an amide compound, a sulfoxide compound, or a hydrocarbon compound, and specific examples thereof include methanol, ethanol, propanol, N-butanol, isobutanol, t-butanol, 3-methoxybutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, and xylene. Among them, dialkyl glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether are more preferable from the viewpoint of improving the storage stability of the aqueous resin dispersion obtained.
Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3, 5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; a peroxyketal compound of the formula (I), such as 1, 1-di (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-di (t-butylperoxy) cyclohexane, n-butyl-4, 4-di (t-butylperoxy) valerate, 2-di (4, 4-di-t-butylperoxy) cyclohexyl) propane, 2-di (4, 4-di-t-pentylperoxycyclohexyl) propane, 2-di (4, 4-di-t-hexylperoxy cyclohexyl) propane, 2-di (4, 4-di-t-octylperoxy cyclohexyl) propane and 2, 2-di (4, 4-diisopropylperoxy cyclohexyl) propane; hydroperoxides such as cumene hydroperoxide and 2, 5-dimethylhexane-2, 5-dihydroperoxide, dialkyl peroxide compounds such as 1, 3-di (t-butylperoxy-m-isopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, dicumyl peroxide and t-butylcumyl peroxide, diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2, 4-dichlorobenzoyl peroxide, peroxide carbonate compounds such as bis (t-butylcyclohexyl) peroxydicarbonate, organic peroxides such as t-butylperoxy-2-ethylhexanoate, peroxyester compounds and the like, tert-butyl peroxybenzoate and 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, and azo compounds such as 2,2 '-azobisisobutyronitrile and 1,1' -azobis (cyclohexane-1-carbonitrile).
In addition, when the acrylic polymer (A) is produced, chain transfer agents such as dodecyl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid and octylthioglycolic acid may be used as necessary.
From the viewpoint of the reaction point with the urethane (meth) acrylate (B), the hydroxyl value of the acrylic polymer (a) is preferably 10 to 200mgKOH/g, more preferably 20 to 100mgKOH/g.
The acid value of the acrylic polymer (A) is preferably 10 to 150mgKOH/g, more preferably 20 to 80mgKOH/g, from the viewpoint of water dispersibility.
The hydroxyl value and acid value in the present invention are values calculated from the raw materials used.
The weight average molecular weight (Mw) of the acrylic polymer (a) is preferably 3,000 to 200,000, more preferably 5,000 to 150,000, from the viewpoint of further improving the water dispersibility and storage stability of the obtained aqueous resin dispersion. Here, the weight average molecular weight (Mw) is a polystyrene equivalent value measured based on gel permeation chromatography (hereinafter referred to as "GPC").
The urethane (meth) acrylate (B) having an isocyanate group has an isocyanate group and a (meth) acryloyl group.
For example, the urethane (meth) acrylate (B) can be obtained by a urethane reaction between the polyisocyanate (B1) and the (meth) acrylate (B2) having a hydroxyl group.
Examples of the polyisocyanate (b 1) include aromatic diisocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, m-xylene diisocyanate and m-xylylene diisocyanate, and aliphatic or alicyclic diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1, 3-diisocyanatocyclohexane, 2-methyl-1, 5-diisocyanatocyclohexane, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate. Among them, aliphatic or alicyclic diisocyanate compounds are preferable because of their excellent yellowing resistance.
In addition, as the polyisocyanate (b 1), a prepolymer having an isocyanate group obtained by subjecting the above-mentioned diisocyanate compound to an addition reaction with a polyhydric alcohol, a compound having an isocyanate ring obtained by cyclizing trimerization of the above-mentioned diisocyanate compound, a polyisocyanate compound having a urea bond or a biuret bond (burette bond) obtained by reacting the above-mentioned diisocyanate compound with water, homopolymers of acrylic monomers having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl- α, α -dimethylbenzyl isocyanate and (meth) acryloyl isocyanate, and copolymers having an isocyanate group obtained by copolymerizing an acrylic monomer having an isocyanate group with other monomers such as an acrylic monomer, a vinyl ester compound, a vinyl ether compound, an aromatic vinyl monomer and a fluoroolefin can also be used.
The above polyisocyanates (b 1) may be used singly or in combination of two or more.
Examples of the (meth) acrylic acid ester having a hydroxyl group (b 2) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-N-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-N-butyl (meth) acrylate, 3-hydroxy-N-butyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and lactone-modified (meth) acrylic acid esters having a terminal hydroxyl group. These (meth) acrylic acid esters (b 2) having a hydroxyl group may be used alone or in combination of two or more.
In the present invention, the polyurethane reaction may be carried out in the absence of a catalyst, or may be carried out in the presence of a polyurethane-forming catalyst to promote the progress of the reaction. Examples of the polyurethane forming catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, phosphine compounds such as triphenylphosphine and triethylphosphine, organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate and tin octoate, and organometallic compounds such as zinc octoate.
From the viewpoint of the reaction point with the acrylic polymer (a), the content of isocyanate groups in the urethane (meth) acrylate (B) is preferably 3 to 20 mass%.
The polyurethane (meth) acrylate (B) preferably has a weight average molecular weight of 200 to 2,000.
The (meth) acrylate (X) is obtained by a urethane reaction between an acrylic polymer (a) having a hydroxyl group and a urethane (meth) acrylate (B) having an isocyanate group.
From the viewpoint of improving the water dispersibility and improving the storage stability of the resulting aqueous resin dispersion, the mass ratio (a/B) of the acrylic polymer (a) to the urethane (meth) acrylate (B) is preferably in the range of 0.25 to 4, more preferably in the range of 0.5 to 3.
From the viewpoint of improving the water dispersibility and improving the storage stability of the resulting aqueous resin dispersion, the molar ratio (a/B) of the hydroxyl groups of the acrylic polymer (a) to the isocyanate groups of the urethane (meth) acrylate (B) is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
The acid value of the (meth) acrylic acid ester (X) is preferably 10 to 60mgKOH/g from the viewpoint of further improving the water dispersibility.
The (meth) acrylate (X) is a reaction product of an acrylic polymer (a) having a hydroxyl group and a urethane (meth) acrylate (B) having an isocyanate group. However, it is preferable to further use the polymer polyol (P) as a reaction raw material.
Examples of the polymer polyol (P) include polycarbonate diol, polyester diol and polyether diol. These polymer polyols (P) may be used alone or in combination of two or more.
From the viewpoint of water dispersibility, the number average molecular weight of the polymer polyol (P) is preferably 500 to 3000, more preferably 500 to 2000.
The amount of the polymer polyol (P) is preferably 5 to 20 mass%, more preferably 5 to 10 mass%, based on the raw material of the (meth) acrylate (X), from the viewpoint of further improving chemical resistance and coating film hardness.
Examples of the reaction method of the acrylic polymer (A), the urethane (meth) acrylate (B) and the polymer polyol (P) include a method of simultaneously reacting the acrylic polymer (A), the urethane (meth) acrylate (B) and the polymer polyol (P), and a method of reacting the polyisocyanate (B1) and the polymer polyol (P) and then reacting the (meth) acrylate (B2) having a hydroxyl group when the urethane (meth) acrylate (B) is obtained.
Preferred examples of the method of dispersing the (meth) acrylic acid ester (X) as the resin particles in the aqueous medium include a method of neutralizing the carboxyl group of the (meth) acrylic acid ester (X) with a basic compound and then mixing with the aqueous medium.
Examples of the basic compound include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N-dimethylethanolamine, 2-aminoethanol and other monoalkanolamines, diethanolamine, diisopropanolamine and dibutylamine, inorganic basic compounds such as ammonia, sodium hydroxide and potassium hydroxide, and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-N-butylammonium hydroxide and trimethylbenzylammonium hydroxide. Among them, organic amine and ammonia (ammonia water may be used) are preferably used. These basic compounds may be used singly, or two or more kinds may be used in combination.
Further, from the viewpoint of further improving the storage stability of the aqueous resin dispersion, the amount of the basic compound used is preferably such that the neutralization rate of the carboxyl group of the (meth) acrylate (X) is in the range of 50% to 100%.
Examples of aqueous media include water, hydrophilic organic solvents, and mixtures thereof. For the hydrophilic organic solvent, a water-miscible organic solvent that is miscible with water without separation is preferable, and among these solvents, an organic solvent having a solubility in water (the number of grams of the organic solvent dissolved in 100g of water) of 3g or more at 25 ℃ is preferable. Examples of such water-miscible organic solvents include alcohol solvents such as methanol, ethanol, propanol, butanol, 3-methoxybutanol and 3-methyl-3-methoxybutanol, ketone solvents such as acetone and methyl ethyl ketone, and glycol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether and diethylene glycol dimethyl ether. These water-miscible organic solvents may be used alone, or two or more kinds may be used in combination.
Although the aqueous resin dispersion of the present invention is obtained by radical polymerization of the (meth) acrylic acid ester (X) in the resin particles dispersed in the aqueous medium, it can also be obtained by copolymerization of other (meth) acrylic acid monomers (Y).
As the (meth) acrylic monomer (Y), the above-mentioned unsaturated monomers (a 1) to (a 3) can be used as raw materials for the acrylic polymer (a).
When copolymerizing the (meth) acrylic monomer (Y), it is preferable to mix the (meth) acrylic ester (X) with the (meth) acrylic monomer (Y) first and then disperse the (meth) acrylic ester (X) in the aqueous medium.
In addition, in the radical polymerization of the (meth) acrylic ester (X), a water-soluble polymerization initiator such as ammonium persulfate, potassium persulfate, and sodium persulfate is preferably used.
The aqueous resin dispersion of the present invention may contain a dihydrazide compound because it can form a higher density of crosslinks.
The aqueous coating material of the present invention contains the above aqueous resin dispersion. However, as other compounds, additives such as antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, and pigment dispersants may be used.
In addition, the aqueous coating composition of the present invention can be used as a coating composition for coating a variety of articles, and examples of articles that can be coated with the aqueous coating composition of the present invention include bodies of household appliances such as refrigerators, televisions and air conditioners, housings of information terminals such as mobile phones, smart phones and personal computers, automotive upholstery, cosmetic containers and highly engineered packaging materials.
Examples of the method of applying the aqueous coating material of the present invention include a method using a gravure coater, a roll coater, a comma coater, a blade coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a spin coater, dipping, screen printing, spraying, an applicator, a bar coater, or a brush. Further, examples of a method of forming a coating film after coating include a method of drying at room temperature to 120 ℃.
Examples
The present invention will be described in more detail below with specific examples. In addition, the weight average molecular weight (Mw) of the polymer was measured under the following GPC measurement conditions.
[ GPC measurement conditions ]
Measurement apparatus high speed GPC apparatus ("HLC-8220 GPC" produced by Tosoh Corporation) columns the following columns produced by Tosoh Corporation were connected in series and used.
“TSKgel G5000”(7.8mm I.D.×30cm)×1
“TSKgel G4000”(7.8mm I.D.×30cm)×1
“TSKgel G3000”(7.8mm I.D.×30cm)×1
“TSKgel G2000”(7.8mm I.D.×30cm)×1
Detector RI (differential refractometer)
Column temperature of 40 DEG C
Tetrahydrofuran (THF)
Flow rate 1.0mL/min
Sample volume 100. Mu.L (tetrahydrofuran solution, sample concentration 4 mg/mL)
Standard samples calibration curves were created using the following monodisperse polystyrene.
(Monodisperse polystyrene)
"TSKgel Standard polystyrene A-500" manufactured by Tosoh Co "
"TSKgel Standard polystyrene A-1000" manufactured by Tosoh Co "
"TSKgel Standard polystyrene A-2500" manufactured by Tosoh Co "
"TSKgel Standard polystyrene A-55000" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-1" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-2" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-4" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-10" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-20" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-40" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-80" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-128" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-288" manufactured by Tosoh Co "
"TSKgel Standard polystyrene F-550" manufactured by Tosoh Co "
Synthesis example 1 Synthesis of acrylic Polymer (A-1)
In a reactor equipped with stirring, cooling and heating means, 283 parts by mass of diglyme (hereinafter abbreviated as "MDM") was charged, and the mixture was heated to 135 ℃. Then, a monomer mixture of 70 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), 160 parts by mass of n-butyl methacrylate (hereinafter abbreviated as "nBMA"), 70 parts by mass of 2-hydroxyethyl methacrylate (hereinafter abbreviated as "HEMA") and 60 parts by mass of styrene (hereinafter abbreviated as "St"), and a solution prepared by dissolving 20 parts by mass of t-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as "P-O") in 20 parts by mass of MDM were added dropwise at a constant rate over 2 hours. Then, a monomer mixture of 210 parts by mass of MMA, 73 parts by mass of n-butyl acrylate (hereinafter abbreviated as "nBA"), 27 parts by mass of HEMA, 40 parts by mass of St, 40 parts by mass of acrylic acid (hereinafter abbreviated as "AA'), 10 parts by mass of methoxypolyethylene glycol methacrylate (number of oxyethylene repeating units: 23), and 40 parts by mass of diacetone acrylamide (hereinafter abbreviated as" DAAM "), and a solution prepared by dissolving 10 parts by mass of P-O in 10 parts by mass of MDM were added dropwise at a constant rate over 2 hours and 30 minutes. After maintaining the temperature at 135℃for 60 minutes, the mixture was cooled to obtain a solution of the acrylic polymer (A-1) having carboxyl groups and hydroxyl groups. The solid content of the solution was 70.0% by mass, the hydroxyl value was 52, the acid value was 39, and the weight-average molecular weight was 33,000. Synthesis example 2 Synthesis of polyurethane (meth) acrylate (B-1)
In a reactor equipped with stirring, cooling and heating means, 222 parts by mass of isophorone diisocyanate, 0.07 parts by mass of 4-Methoxyphenol (MEHQ) and dibutyltin dilaurate were charged, and stirring was started. Then, the reaction temperature was kept at 25 to 35 ℃, and 139 parts by mass of HEMA was added dropwise over 2 hours. After completion of the dropping for thirty minutes, the reaction temperature was raised to 40 ℃ and maintained until the isocyanate group content became lower than 11% to obtain a urethane (meth) acrylate (B-1) having an isocyanate group and a (meth) acryloyl group. The isocyanate group content of the urethane (meth) acrylate (B-1) was 10.8%.
EXAMPLE 1 Synthesis and evaluation of aqueous resin Dispersion (1)
Into a reactor equipped with stirring, cooling and heating means, 890 parts by mass of the solution of the acrylic polymer (A-1) obtained in Synthesis example 1, 200 parts by mass of the urethane (meth) acrylate (B-1) obtained in Synthesis example 2 and 0.1 part by mass of MEHQ were charged, and the mixture was heated to 80 ℃. The temperature was maintained for about 3 hours until the isocyanate group content became less than 0.2% to obtain (meth) acrylate (X-1). Then, the mixture was cooled to 60 ℃, 80 parts by mass of MMA and 28 parts by mass of Triethylamine (TEA) were added. After holding for about 30 minutes, 1000 parts by mass of deionized water was added and stirred to obtain an aqueous dispersion containing (meth) acrylate (X-1) and MMA in particles. Then, the mixture was heated to 60 ℃, an aqueous solution prepared by dissolving 0.45 parts by mass of ammonium persulfate in 40 parts by mass of deionized water was added, and the mixture was heated to 80 ℃ for 1 hour. Then, the mixture was cooled to 60 ℃, and an aqueous solution prepared by dissolving 12 parts by mass of adipic acid hydrazide (ADH) in 50 parts by mass of deionized water was added over 30 minutes, followed by cooling, to obtain an aqueous resin dispersion (1). The resin solid content of the aqueous resin dispersion (1) was 40.9 mass%.
EXAMPLE 2 Synthesis and evaluation of aqueous resin Dispersion (2)
In a reactor equipped with stirring, cooling and heating means, 860 parts by mass of the solution of the acrylic polymer (A-1) obtained in Synthesis example 1, 150 parts by mass of polycarbonate diol (manufactured by ASAHI KASEI Corporation, "DURANOL T5651"), 280 parts by mass of polyurethane (meth) acrylate (B-1) and 0.1 part by mass of MEHQ were charged, and the mixture was heated to 80 ℃. The temperature was maintained for about 4 hours until the isocyanate group content was less than 0.2%, to obtain (meth) acrylate (X-2). Then, the mixture was cooled to 60 ℃, 27 parts by mass of TEA was added. After holding for about 30 minutes, 1200 parts by mass of deionized water was added and stirred to obtain an aqueous dispersion containing (meth) acrylate (X-2) in the particles. The mixture was then heated to 60 ℃, an aqueous solution prepared by dissolving 0.5 parts by mass of ammonium persulfate in 28 parts by mass of deionized water was added, and the mixture was heated to 80 ℃ for 1 hour. The mixture was then cooled to 60 ℃, and an aqueous solution prepared by dissolving 12 parts by mass of ADH in 70 parts by mass of deionized water was added over 30 minutes, followed by cooling, to obtain an aqueous resin dispersion (2). The resin solid content of the aqueous resin dispersion (2) was 41.1 mass%.
Comparative example 1 Synthesis and evaluation of aqueous resin Dispersion (R1)
In a reactor equipped with stirring, cooling and heating means, 283 parts by mass of MDM was charged and the mixture was heated to 135 ℃. Then, a monomer mixture of 70 parts by mass of MMA, 160 parts by mass of nmma, 70 parts by mass of HEMA, and 60 parts by mass of St, and a solution prepared by dissolving 20 parts by mass of P-O in 20 parts by mass of MDM were added dropwise in two lines at a constant rate over 2 hours. Then, a monomer mixture of 210 parts by mass of MMA,73 parts by mass of nBA,27 parts by mass of HEMA,40 parts by mass of St,40 parts by mass of AA,10 parts by mass of methoxypolyethylene glycol methacrylate and 40 parts by mass of DAAM, and a solution prepared by dissolving 10 parts by mass of P-O in 10 parts by mass of MDM were added dropwise in two lines at a constant rate over 2 hours and 30 minutes. After maintaining the temperature at 135 ℃ for 60 minutes, the mixture was cooled to 60 ℃ and 36 parts by mass of TEA was added. After holding for about 30 minutes, 810 parts by mass of deionized water was added with stirring to obtain an aqueous dispersion of an acrylic polymer having carboxyl groups and hydroxyl groups. The mixture was then cooled to 60 ℃ and an aqueous solution prepared by dissolving 16 parts by mass of ADH in 50 parts by mass of deionized water was added over 30 minutes. The mixture was cooled to obtain an aqueous resin dispersion (R1). The resin solid content in the aqueous resin dispersion (R1) was 40.0 mass%.
[ Preparation of cured coating film for evaluation ]
The aqueous resin dispersion obtained above was sprayed on ABS (acrylonitrile-butadiene-styrene copolymer) boards, PC (polycarbonate) boards and aluminum boards so that the film thickness after drying was 20 μm. After predrying for 30 minutes at 80 ℃ in a dryer, the coating was cured at 25 ℃ for 1 week to give a cured coating film.
[ Evaluation of appearance of coating film ]
The appearance of the coating film of the cured coating film prepared on the ABS sheet was visually observed, and the appearance of the coating film was evaluated according to the following criteria.
And A, no blushing occurs.
Slight blushing was observed.
And C, blushing occurs.
[ Evaluation of hardness of coating film ]
For the cured coating film prepared on the aluminum plate, the hardness of the hardest pencil which does not generate scars was measured as pencil hardness in accordance with JIS K5600-5-4:1999 using a pencil specified in JIS 6006:2007.
[ Evaluation of adhesion of coating film ]
The measurement was carried out according to JIS K-5600 cross-cut test method. On the cured coating film prepared on the PC board, cuts with a width of 1mm were made with a cutter to give a mesh number of 100, and cellophane tape was attached so as to cover all the meshes and peeled off promptly. The determination is made by calculating the number of meshes remaining. The evaluation criteria are as follows.
A, not stripping.
The stripping area is more than 1% and less than 65% of the total grid area.
And C, the stripping area is more than 65% of the total grid area.
[ Evaluation of alcohol resistance ]
After the cured coating film prepared on the ABS panel was reciprocally rubbed 100 times with a felt impregnated with ethanol at a load of 500g, the state of the cured coating film was evaluated by finger touch and visual observation. The evaluation criteria are as follows.
No softening or tarnishing was observed.
A slight softening or tarnishing was observed.
A significant softening or tarnishing was observed.
[ Evaluation of hot Water resistance ]
Immediately after immersing the cured coating film prepared on the ABS sheet in 80 ℃ hot water for 4 hours, visual observation evaluation was performed on the appearance of the cured coating film after being taken out from the hot water according to the following evaluation criteria.
A no blushing or foaming
Blushing or foaming was observed.
Peeling from the substrate was observed.
[ Evaluation of solvent resistance ]
After the cured coating film prepared on the ABS panel was rubbed back and forth 50 times with a felt impregnated with methyl ethyl ketone at a load of 500g, the state of the cured coating film was evaluated by finger touch and visual observation. The evaluation criteria are as follows.
No softening or tarnishing was observed.
A slight softening or tarnishing was observed.
A significant softening or tarnishing was observed.
The evaluation results of examples 1 to 2 and comparative example 1 are shown in table 1.
TABLE 1
The results show that the coating film obtained from the aqueous resin dispersion of the present invention is excellent in appearance, hardness, adhesion, alcohol resistance, hot water resistance and solvent resistance.
It was also found that in comparative example 1, which is an example in which the urethane (meth) acrylate (B) as an essential raw material of the present invention was not used, hardness, adhesion, alcohol resistance, hot water resistance and solvent resistance were insufficient.

Claims (6)

1. An aqueous resin dispersion obtained by radical polymerization of a (meth) acrylate (X) in resin particles dispersed in an aqueous medium, wherein the (meth) acrylate (X) is a product of a reaction of an acrylic polymer (a) having a hydroxyl group and a carboxyl group with a urethane (meth) acrylate (B) having an isocyanate group.
2. The aqueous resin dispersion according to claim 1, wherein the polyurethane (meth) acrylate (B) is a product of a reaction of a polyisocyanate (B1) and a (meth) acrylate (B2) having a hydroxyl group.
3. The aqueous resin dispersion according to claim 1, wherein the radical polymerization is copolymerization of the (meth) acrylate (X) and (meth) acrylic acid monomer (Y).
4. The aqueous resin dispersion according to claim 1, wherein the reaction product contains a polymer polyol (P) as an essential raw material.
5. An aqueous coating material containing the aqueous resin dispersion according to any one of claims 1 to 4.
6. An article coated with the aqueous coating of claim 5.
CN202280095469.0A 2022-08-30 2022-08-30 Water-based resin dispersion, water-based paint and articles coated with water-based paint Pending CN119095924A (en)

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