CN116670194A - Water-dispersible polyisocyanate composition, method for preparing the composition, water-based curable composition, water-based coating and article - Google Patents
Water-dispersible polyisocyanate composition, method for preparing the composition, water-based curable composition, water-based coating and article Download PDFInfo
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- 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
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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Abstract
A water-dispersible polyisocyanate composition is provided which contains a hydrophobic polyisocyanate (A) and an acrylic polymer (B) containing an alkoxy-terminated polyoxyalkylene group and an isocyanate group. The acrylic polymer (B) is the reaction product of an acrylic polymer (B) and a hydrophobic polyisocyanate. The acrylic polymer (b) contains a polymer (b 1) and a polymer (b 2). The polymer (b 1) is derived from a monomer raw material containing 11 mol% or more and 35 mol% or less of an acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group. The polymer (b 2) is derived from a monomer raw material containing 2 mol% or more and less than 11 mol% of an acrylic monomer (x). The water-dispersible polyisocyanate composition provides a long pot life in the form of a two-component coating as well as an excellent appearance for a coating film to be formed, and thus can be suitably used for various coating applications.
Description
Technical Field
Embodiments of the present invention relate to water-dispersible polyisocyanate compositions, methods for preparing the compositions, water-based curable compositions, water-based coatings and articles.
Background
With respect to room temperature crosslinkable two-component urethane coating compositions used as solvent-borne coatings, water-based coatings have recently been desired from the standpoint of environmental protection. However, the polyisocyanates used as curing agents in the two-component urethane coating compositions are not readily dispersible in water and readily react with water to produce carbon dioxide. In order to solve this problem, polyisocyanates which have emulsifying properties even in a water-dispersed state and inhibit the reaction between isocyanate groups and water have been reported (for example, see patent documents 1 and 2).
Patent documents 1 and 2 disclose water-dispersible polyisocyanate compositions containing a polyisocyanate and a nonionic group-containing vinyl polymer. However, even these isocyanate compositions disadvantageously have a short pot life as two-component urethane coatings.
[ quotation list ]
[ patent literature ]
[PTL 1]
Japanese unexamined patent application publication No. 2002-194237
[PTL 2]
Japanese unexamined patent application publication No. 2006-009029
Disclosure of Invention
[ technical problem ]
It is an object of the present invention to provide a water-dispersible polyisocyanate composition which has excellent water dispersibility and provides a long pot life and an excellent appearance to a coating film to be formed in the form of a two-component coating, a method for producing the composition, and a water-based coating material containing the composition.
[ solution to the problem ]
The inventors have conducted intensive studies in order to solve the above-mentioned problems, and have found that a water-dispersible polyisocyanate composition containing a hydrophobic polyisocyanate and a specific acrylic polymer provides a long pot life after mixing the two components and an excellent appearance for a coating film to be formed. These findings have led to the completion of the present invention.
An aspect of the present invention is to provide a water-dispersible polyisocyanate composition comprising a hydrophobic polyisocyanate (a) and an acrylic polymer (B) containing an alkoxy-terminated polyoxyalkylene group and an isocyanate group, wherein the acrylic polymer (B) is a reaction product of an acrylic polymer (B) and a hydrophobic polyisocyanate, the acrylic polymer (B) comprises an acrylic polymer (B1) and an acrylic polymer (B2), the acrylic polymer (B1) is derived from a monomer raw material containing 11 mol% or more and 35 mol% or less of an acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group, and the acrylic polymer (B2) is derived from a monomer raw material containing 2 mol% or more and less than 11 mol% of an acrylic monomer (x).
[ advantageous effects of the invention ]
The water-dispersible polyisocyanate composition according to one embodiment of the present invention provides a long pot life after mixing the two components and provides excellent appearance to a coating film to be formed, and thus can be suitably used for various coatings, for example, for interior and exterior of automobiles, automobile maintenance, plastics, industrial machinery, building materials, and wood processing.
Detailed Description
The water-dispersible polyisocyanate composition according to one embodiment of the present invention contains a hydrophobic polyisocyanate (a) and an acrylic polymer (B) containing an alkoxy-terminated polyoxyalkylene group and an isocyanate group, wherein the acrylic polymer (B) is a reaction product of the acrylic polymer (B) and the hydrophobic polyisocyanate, the acrylic polymer (B) contains an acrylic polymer (B1) and an acrylic polymer (B2), the acrylic polymer (B1) is derived from a monomer raw material containing 11 mol% or more and 35 mol% or less of an acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group, and the acrylic polymer (B2) is derived from a monomer raw material containing 2 mol% or more and less than 11 mol% of the acrylic monomer (x).
The hydrophobic polyisocyanate (a) has no hydrophilic group. Examples of the hydrophobic polyisocyanate (A) include aliphatic diisocyanates such as 1, 4-tetramethylene diisocyanate, ethyl 2, 6-diisocyanatohexanoate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, and 2, 4-or 2, 4-trimethylhexamethylene diisocyanate; aliphatic triisocyanates such as 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4- (isocyanatomethyl) octane and 2-isocyanatoethyl (2, 6-diisocyanato) hexanoate; alicyclic diisocyanates such as 1, 3-bis (isocyanatomethyl cyclohexane), 1, 4-bis (isocyanatomethyl cyclohexane), 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 3, 5-trimethyl (3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane 4,4' -diisocyanate, 2, 5-diisocyanatomethyl norbornane and 2, 6-diisocyanatomethyl norbornane; alicyclic triisocyanates such as 2, 5-diisocyanalmethyl-2-isocyanatopropyl norbornane and 2, 6-diisocyanalmethyl-2-isocyanatopropyl norbornane; aralkylene diisocyanates such as m-xylylene diisocyanate, α, α, α ', α' -tetramethyl-m-xylylene diisocyanate; aromatic diisocyanates such as meta-or para-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, diphenylmethane-4, 4 '-diisocyanate, naphthalene-1, 5-diisocyanate, diphenyl-4, 4' -diisocyanate, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 3-methyldiphenylmethane-4, 4 '-diisocyanate and diphenyl ether-4, 4' -diisocyanate; aromatic triisocyanates such as triphenylmethane triisocyanate and tris (isocyanatophenyl) thiophosphate; polyisocyanates having a uretdione structure formed by the cyclopolymerization of the above-mentioned diisocyanates or triisocyanates; polyisocyanates having an isocyanurate structure formed by the cyclotrimerization of the isocyanate groups of the above-mentioned di-or triisocyanates; polyisocyanates having a biuret structure formed by the reaction of the above-mentioned diisocyanates or triisocyanates with water; polyisocyanates having an oxadiazinetrione structure formed by the reaction of the above-mentioned di-or triisocyanates with carbon dioxide; and polyisocyanates having allophanate structures. These hydrophobic polyisocyanates (A) may be used alone or in combination of two or more.
Among these hydrophobic polyisocyanates (a), aliphatic or alicyclic di-or triisocyanates, aralkylene diisocyanates and polyisocyanates derived therefrom are preferable in view of the stability of isocyanate groups in water and the weather resistance of a coating film formed from a coating material containing the water-dispersible polyisocyanate composition. Among these polyisocyanates, in order to prepare a water-based curable composition excellent in weather resistance and durability, polyisocyanates having three or more functionalities such as isocyanurate type polyisocyanates, polyisocyanates having a biuret structure, polyisocyanates having a uretdione structure, polyisocyanates having an allophanate structure, and polyisocyanates formed by the reaction of diisocyanates with a ternary or higher polyol are preferable. The hydrophilic group-containing polyisocyanate may be used in combination with the hydrophobic polyisocyanate (a) as long as the stability of the water-dispersible polyisocyanate composition according to the embodiment of the present invention is not impaired.
The acrylic polymer (B) has an alkoxy-terminated polyoxyalkylene group. The polyoxyalkylene group can be easily introduced by using the acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group as a monomer raw material for the acrylic polymer (b).
Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a polyoxyalkylene group formed by random or block copolymerization of different alkylene oxides, and a polyoxyalkylene group formed by ring-opening polymerization of dioxolane. Among these polyoxyalkylene groups, those containing an ethylene oxide unit as an essential structural unit are preferable because water dispersibility is further improved.
The polyoxyalkylene group preferably has 12 to 30 oxyalkylene repeating units because water dispersibility and pot life are further improved.
Preferred examples of the terminal alkoxy group include lower alkoxy groups such as methoxy, ethoxy and butoxy.
The acrylic polymer (b) contains an acrylic polymer (b 1) and an acrylic polymer (b 2). This provides excellent pot life after mixing the two components.
The monomer raw material for the acrylic polymer (b 1) contains 11 mol% or more and 35 mol% or less, preferably 12 mol% or more and 24 mol% or less of the acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group because a longer pot life is achieved.
The monomer raw material for the acrylic polymer (b 2) contains 2 mol% or more and less than 11 mol%, preferably 5 mol% or more and 10 mol% or less of the acrylic monomer (x) because a longer pot life is achieved.
Examples of the acrylic monomer (x) include methoxy poly (ethylene glycol) (meth) acrylate, (ethoxy poly (ethylene glycol) meth) acrylate, propoxy poly (ethylene glycol) (meth) acrylate, butoxy poly (ethylene glycol) (meth) acrylate, phenoxy poly (ethylene glycol) (meth) acrylate, methoxy poly (propylene glycol) (meth) acrylate, ethoxy poly (propylene glycol) (meth) acrylate, propoxy poly (propylene glycol) (meth) acrylate, butoxy poly (propylene glycol) (meth) acrylate, phenoxy poly (propylene glycol) (meth) acrylate, methoxy poly (butylene glycol) (meth) acrylate, ethoxy poly (butylene glycol) (meth) acrylate, propoxy poly (butylene glycol) (meth) acrylate, butoxy poly (butylene glycol) (meth) acrylate, phenoxy poly (butylene glycol) (meth) acrylate, methoxy poly (ethylene glycol) -poly (propylene glycol) (meth) acrylate, phenoxy poly (ethylene glycol) -poly (propylene glycol) (meth) acrylate, methoxy poly (ethylene glycol) -poly (butylene glycol) (meth) acrylate and phenoxy poly (ethylene glycol) -poly (butylene glycol) (meth) acrylate. Among these, the polyoxyethylene group-containing acrylic monomer (x) is preferable because satisfactory water dispersibility is provided. These acrylic monomers (x) may be used alone or in combination of two or more.
The term "(meth) acrylate" as described in the present specification means one or both of methacrylate and acrylate.
The acrylic polymer (B) is a reaction product of the acrylic polymer (B) and a hydrophobic polyisocyanate, and is easily prepared by introducing an active hydrogen-containing group into the acrylic polymer (B1) and/or the acrylic polymer (B2) and reacting the acrylic polymer (B1) and/or the acrylic polymer (B2) with a hydrophobic polyisocyanate.
The active hydrogen-containing group can be easily introduced into the acrylic polymer by using an unsaturated monomer having an active hydrogen-containing group as a monomer raw material for the acrylic polymer (b 1) and/or the acrylic polymer (b 2).
Examples of the unsaturated monomer having an active hydrogen group include hydroxyl group-containing unsaturated monomers, carboxyl group-containing unsaturated monomers, amino group-containing unsaturated monomers, and active methylene group-containing unsaturated monomers. Hydroxyl group-containing unsaturated monomers are preferred. These unsaturated monomers having an active hydrogen-containing group may be used singly or in combination of two or more.
Examples of such hydroxyl group-containing unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, poly (ethylene glycol) mono (meth) acrylate, poly (propylene glycol) mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate 2-hydroxyethyl and lactone-modified (meth) acrylates having terminal hydroxyl groups. These hydroxyl group-containing unsaturated monomers may be used alone or in combination of two or more.
For the monomer raw materials for the acrylic polymers (b 1) and (b 2), unsaturated monomers containing a hydrophobic group having 4 or more carbon atoms are preferably used because water dispersibility and pot life are further improved.
Examples of the unsaturated monomer having a hydrophobic group having 4 or more carbon atoms include (meth) acrylic esters each having an alkyl group having 4 to 22 carbon atoms, such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; cycloalkyl alkyl (meth) acrylates such as cyclopentyl methyl (meth) acrylate, cyclohexyl methyl (meth) acrylate and 2-cyclohexyl ethyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate; aromatic vinyl monomers such as styrene, p-t-butylstyrene, alpha-methylstyrene and vinyltoluene; vinyl esters of carboxylic acids having 5 or more carbon atoms such as vinyl pivalate, vinyl versatate, and vinyl benzoate; crotonates having an alkyl group having 4 to 22 carbon atoms, such as n-butyl crotonate and 2-ethylhexyl crotonate; diesters of unsaturated dibasic acids containing at least one alkyl group having 4 to 22 carbon atoms, such as di-n-butyl maleate, di-n-butyl fumarate, and di-n-butyl itaconate; alkyl vinyl ethers having an alkyl group having 4 to 22 carbon atoms, such as n-butyl vinyl ether and n-hexyl vinyl ether; and cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, and 4-methylcyclohexyl vinyl ether.
For the acrylic polymers (b 1) and (b 2), known and commonly used monomers such as alkyl (meth) acrylates having 3 or less carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate or n-propyl (meth) acrylate, may be used in combination with the above-mentioned monomers.
The monomer raw material for the acrylic polymer (b 1) preferably contains 11 mol% or more and 35 mol% or less of the acrylic monomer (x) because the water dispersibility and pot life are further improved.
The monomer raw material for the acrylic polymer (b 2) preferably contains 2 mol% or more and less than 11 mol% of the acrylic monomer (x) because the water dispersibility and pot life are further improved.
The monomer raw material for each of the acrylic polymers (b 1) and (b 2) preferably contains 1 to 10 mass% of a monomer having an active hydrogen-containing group, because the water dispersibility and pot life are further improved.
Each of the acrylic polymers (b 1) and (b 2) preferably has a hydroxyl value of 5 to 50mgKOH/g, because water dispersibility and pot life are further improved.
The hydroxyl number according to one embodiment of the invention is defined as the calculated value determined by the raw materials used.
For the formation of the acrylic polymers (b 1) and (b 2), various known and commonly used polymerization methods may be employed. The radical solution polymerization method in an organic solvent is convenient and preferable.
When a radical solution polymerization method is employed, various known and commonly used polymerization initiators may be used. Examples thereof include azo compounds such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylbutyronitrile), and 2,2' -azobis (2-methylbutyronitrile); and peroxides such as t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, cumene hydroperoxide and diisopropyl peroxycarbonate. These polymerization initiators may be used alone or in combination of two or more.
As the organic solvent, any compound that does not react with isocyanate groups may be used. Examples thereof include aliphatic or alicyclic hydrocarbon compounds such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic hydrocarbon compounds such as toluene, xylene and ethylbenzene; ester compounds such as ethyl acetate, n-butyl acetate, n-pentyl acetate and ethylene glycol monomethyl ether acetate; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; poly (alkylene glycol) dialkyl ether compounds such as diglyme, diethylene glycol diethyl ether and diethylene glycol dibutyl ether; ether compounds such as 1, 2-dimethoxyethane, tetrahydrofuran and dioxane; n-methylpyrrolidone, dimethylformamide, dimethylacetamide and ethylene carbonate. These organic solvents may be used alone or in combination of two or more.
The acrylic polymer (b) contains acrylic polymers (b 1) and (b 2). As a method for producing the acrylic polymer (b), a method in which a monomer raw material for the acrylic polymer (b 2) is polymerized in the presence of the acrylic polymer (b 1) is preferable because water dispersibility and pot life are further improved.
Each of the acrylic polymers (b 1) and (b 2) preferably has a weight average molecular weight of 5,000 to 100,000 because water dispersibility and pot life are further improved.
The acrylic polymer (b) preferably has a hydroxyl value of 5 to 50mgKOH/g, because the water dispersibility and pot life are further improved.
Regarding the method for producing the acrylic polymer (B), it is preferable to react the isocyanate group-containing hydrophobic polyisocyanate (a) with the acrylic polymer (B) in an excess of the equivalent weight of the active hydrogen group-containing groups of the acrylic polymer (B). The equivalent ratio of isocyanate groups to active hydrogen-containing groups is preferably in the range of 10 to 80.
The water-dispersible polyisocyanate composition according to one embodiment of the present invention contains a hydrophobic polyisocyanate (a) and an acrylic polymer (B), and is easily obtained by the above-described method for producing the acrylic polymer (B). The mass ratio (A/b) of the hydrophobic polyisocyanate (A) to the acrylic polymer (b) is in the range of 0.8 to 6.3 because of further improvement in water dispersibility and pot life.
The water-dispersible polyisocyanate composition according to one embodiment of the present invention contains a hydrophobic polyisocyanate (a) and an acrylic polymer (B). The mass ratio (A/B) of the hydrophobic polyisocyanate (A) to the acrylic polymer (B) is preferably in the range of 0.5 to 6 because of further improvement in water dispersibility and pot life.
The water-based curable composition according to one embodiment of the present invention contains a water-dispersible polyisocyanate composition and a water-based resin (C) having active hydrogen-containing groups reactive with isocyanate groups.
Examples of the active hydrogen-containing groups of the water-based resin (C) include hydroxyl groups, carboxyl groups, amino groups, amide groups, and active methylene group-containing groups such as acetoacetyl groups. Of these, hydroxyl groups and carboxyl groups are preferable. Examples of the form of the water-based resin (C) include known and commonly used forms such as water-soluble forms and water-dispersible forms, for example, colloidal dispersions and emulsions.
Examples of the water-based resin (C) include vinyl polymers such as vinyl acetate-based resins, styrene-butadiene-based resins, styrene-acrylonitrile resins, acrylic resins, fluoroolefin resins, silicone-modified vinyl polymers, and poly (vinyl alcohol); synthetic resins other than vinyl polymers, such as polyester resins, polyurethane resins, phenolic resins, melamine resins, epoxy resins, alkyd resins, polyamide resins, polyether resins, and silicone resins; and naturally occurring polymers such as animal proteins, starches, cellulose derivatives, dextrins and gum arabic. Among these, vinyl polymers and various other synthetic resins other than vinyl polymers are preferable. These water-based resins (C) may be used alone or in combination of two or more.
In view of curability of the water-based curable composition according to one embodiment of the present invention and water resistance of a cured article to be formed, the amount of active hydrogen-containing groups contained in the water-based resin (C) is preferably in the range of 0.1 to 6 moles, more preferably 0.2 to 4 moles, even more preferably 0.4 to 3 moles per 1,000g of solid content of the water-based resin.
Regarding the preferable mixing ratio of the water-dispersible polyisocyanate composition according to one embodiment of the present invention to the water-based resin (C), the ratio of the molar amount of isocyanate groups (1) in the polyisocyanate composition to the total molar amount of active hydrogen-containing groups (2) contained in the water-based resin (C) and the NCO group-containing vinyl polymer (B) (i.e., (1)/(2)) is preferably in the range of 0.1 to 5, more preferably 0.3 to 3, even more preferably 0.5 to 2, in view of curability of the curable composition and performance of a cured article formed from the composition.
The water-based curable composition according to one embodiment of the present invention may be used as a pigment-free transparent composition. Alternatively, the water-based curable composition according to an embodiment of the present invention may further contain various known and commonly used organic or inorganic pigments, and thus may be used as a coloring composition.
The water-based curable composition thus prepared can be used in various applications such as paints, adhesives, inks, waterproof materials, sealants, impregnating treatments for various fibers such as natural fibers, synthetic fibers and glass fibers and paper, and surface treatments for various fibers such as natural fibers, synthetic fibers and glass fibers and paper. In particular, the water-based curable composition is preferably used for water-based coating materials.
The water-based paint according to one embodiment of the present invention has a long pot life and provides a cured coating film excellent in appearance and the like.
The water-based paint according to one embodiment of the present invention may further contain various additives known and commonly used, which are suitable for various applications, as other components such as fillers, leveling agents, thickeners, defoamers, organic solvents, ultraviolet absorbers, antioxidants and pigment dispersants, in addition to the aforementioned water-based curable composition according to one embodiment of the present invention, as needed.
Examples of the substrate on which the water-based paint according to one embodiment of the present invention is applied include various metal substrates, inorganic substrates, plastic substrates, inorganic fibers such as paper, synthetic fibers, natural fibers and glass fibers, cloth, synthetic leather, natural leather, and wood substrates.
Examples of the metal substrate include metals such as iron, nickel, aluminum, chromium, zinc, tin, copper, and lead; alloys of the above metals, such as stainless steel and brass; and various surface-treated metals and alloys in which the foregoing various metals and alloys have been subjected to surface treatment such as plating or chemical conversion treatment.
Examples of the inorganic substrate include hardened articles prepared from calcium compounds such as calcium silicate, calcium aluminate, calcium sulfate and calcium oxide; ceramic materials prepared by sintering metal oxides such as alumina, silica and zirconia; ceramic tiles prepared by sintering various clay minerals; and various glasses. Typical examples of hardened products prepared from calcium compounds include hardened products of cement compositions such as concrete and mortar, asbestos cement boards and plates, hardened products of Autoclaved Lightweight Concrete (ALC), hardened products of dolomite mortar, hardened products of gypsum plaster, and calcium silicate boards.
Examples of the plastic substrate include molded articles of thermoplastic resins such as polystyrene, polycarbonate, poly (methyl methacrylate), acrylonitrile-butadiene-styrene (ABS) resin, poly (phenylene ether), polyurethane, polyethylene, poly (vinyl chloride), polypropylene, poly (butylene terephthalate), and poly (ethylene terephthalate); and molded articles of various thermosetting resins such as unsaturated polyester resins, phenolic resins, crosslinked polyurethanes, crosslinked acrylic resins, and crosslinked saturated polyester resins.
A coated substrate in which various substrates as described above have been coated can be used. In addition, a coated substrate in which deterioration of the coated portion has progressed can also be used.
These various substrates are used in various shapes such as a plate shape, a sphere shape, a film shape, a sheet shape, a large-sized structure, and a complex-shaped assembly, depending on the application without particular limitation.
The water-based paint according to one embodiment of the present invention is applied to such a substrate by a known and commonly used coating method such as brushing, rolling, spraying, dipping, coating with a flow coater, coating with a roll coater, and then allowed to stand at room temperature for about 1 to about 10 days or heated in a temperature range of 40 to 250 ℃ for about 30 seconds to about 2 hours, whereby a cured coating film excellent in appearance and the like can be formed.
Examples (example)
The present invention will be described in detail using examples and comparative examples.
Synthesis example 1 Synthesis of acrylic Polymer (b-1)
First, 1,730 parts by mass of propylene glycol monomethyl ether acetate (hereinafter simply referred to as "PMA") was charged into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet, and heated to 110 ℃ under a nitrogen stream. Then, a mixture of 564 parts by mass of methoxypoly (ethylene glycol) methacrylate (containing 23 ethylene oxide units per molecule on average; hereinafter referred to as "MPEGA-1"), 219 parts by mass of butyl acrylate (hereinafter referred to as "BA"), 41 parts by mass of 2-hydroxyethyl methacrylate (hereinafter referred to as "2-HEMA") and 50 parts by mass of t-butyl peroxy-2-ethylhexanoate (hereinafter referred to as "P-O") was added dropwise thereto over a period of 2.5 hours. The resulting mixture was kept at 110℃for 1 hour. To this was added a mixture of 403 parts by mass of "MPEGA-1", 378 parts by mass of BA, 41 parts by mass of 2-HEMA and 50 parts by mass of P-O dropwise over a period of 2.5 hours. After the completion of the dropwise addition, the resulting mixture was reacted at 110℃for 9 hours to prepare a solution containing the acrylic polymer (b 1-1) and the acrylic polymer (b 2-1) and having a nonvolatile content of 50% by mass. The hydroxyl value of the acrylic polymer (b-1) was 21.5mgKOH/g.
( Synthesis examples 2 to 4: synthesis of acrylic polymers (b-2) to (b-4) )
Solutions of the acrylic polymers (b-2) to (b-4) having a nonvolatile content of 50 mass% were prepared as in Synthesis example 1, except that the monomer components were changed as given in Table 1. The hydroxyl value of each of the acrylic polymers (b-2) to (b-4) was 21.5mgKOH/g.
( Synthesis examples 5 and 6: synthesis of acrylic polymers (Rb-1) and (Rb-2) )
With the exception of changing the monomer components as given in Table 2, solutions of the acrylic polymers (Rb-1) and (Rb-2) having a nonvolatile content of 50% by mass were prepared as in Synthesis example 1. The hydroxyl value of each of the acrylic polymers (Rb-1) and (Rb-2) was 21.5mgKOH/g.
Synthesis example 7 Synthesis of acrylic Polymer (Rb-3)
First, 1,730 parts by mass of PMA was charged into a four-necked flask equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet, and heated to 110 ℃ under a nitrogen flow. Then, a mixture of 851 parts by mass of "MPEGA-1", 715 parts by mass of BA, 82 parts by mass of 2-HEMA and 100 parts by mass of P-O was added dropwise thereto over a period of 5 hours. After the completion of the dropwise addition, the resulting mixture was reacted at 110℃for 9 hours to prepare a solution of an acrylic polymer (Rb-3) having a nonvolatile content of 50% by mass. The hydroxyl value of the acrylic polymer (Rb-3) was 21.5mgKOH/g.
Table 1 shows the monomer compositions used for preparing the acrylic polymers (b-1) to (b-4) in Synthesis examples 1 to 4.
TABLE 1
Abbreviations in the tables are as follows.
"MPEGA-1": methoxy poly (ethylene glycol) acrylate (containing an average of 13 ethylene oxide units per molecule)
"MPEGMA-2": methoxy poly (ethylene glycol) methacrylate (containing an average of 9 ethylene oxide units per molecule)
Table 2 shows the monomer compositions used for preparing the acrylic polymers (Rb-1) to (Rb-3) in Synthesis examples 5 to 7.
TABLE 2
( Example 1: synthesis of Water-dispersible polyisocyanate composition (1) )
First, 185 parts by mass of a hydrophobic polyisocyanate ("Burdock DN-980S", available from DIC Corporation), an isocyanurate type polyisocyanate based on Hexamethylene Diisocyanate (HDI), an isocyanate group content (hereinafter referred to as "NCO group content"): 21% by mass, a nonvolatile content: 100% by mass, hereinafter referred to as "hydrophobic polyisocyanate (A-1)") and 100 parts by mass of a solution (solid content: 50 parts by mass) of the acrylic polymer (b-1) prepared in Synthesis example 1 were charged into the same reaction vessel as that used in Synthesis example 1. The mixture was heated to 100℃under a nitrogen stream and then allowed to react at the same temperature under stirring for 6 hours, to obtain a water-dispersible polyisocyanate composition (1) having a nonvolatile content of 82.5% by mass and an NCO group content of 13.3% by mass.
( Examples 2 to 8: synthesis of Water-dispersible polyisocyanate compositions (2) to (8) )
Water-dispersible polyisocyanate compositions (2) to (8) were prepared as in example 1, except that the hydrophobic polyisocyanate (A-1) and the acrylic polymer (b-1) used in example 1 were changed as given in tables 3 and 4.
( Comparative examples 1 to 3: synthesis of Water-dispersible polyisocyanate compositions (R1) to (R3) )
Water-dispersible polyisocyanate compositions (R1) to (R3) were prepared as in example 1, except that the hydrophobic polyisocyanate (A-1) and the acrylic polymer (b-1) used in example 1 were changed as given in Table 5.
Tables 3 and 4 present the compositions of the polyisocyanate compositions (1) to (8) prepared in examples 1 to 8.
TABLE 3
TABLE 4
Table 5 presents the compositions of the polyisocyanate compositions (R1) to (R3) prepared in comparative examples 1 to 3.
TABLE 5
( Example 9: preparation and evaluation of Water-based curable composition (1) )
The water-dispersible polyisocyanate composition (1) prepared in example 1 was mixed with a water-based resin ("Burdock WD-551", available from DIC Corporation, nonvolatile content: 44% by mass, hydroxyl value of solid: 100 mgKOH/g) in such a manner that the molar ratio of isocyanate groups in the water-dispersible polyisocyanate composition (1) to hydroxyl groups in the water-based resin (i.e., (NCO/OH)) was 1.2/1. The mixture was diluted with water to have a viscosity of 500 mPa-s or less (Brookfield-type viscometer, 25 ℃, no. 2 spindle, 30 rpm). Thus, a water-based curable composition (1) was prepared.
[ evaluation of pot life ]
The viscosity of the water-based curable composition (1) was measured immediately after the preparation and once every one hour after the preparation. Pot life was determined by subtracting 1 hour from the time at which the viscosity exceeded 2,000 mpa-s. Pot life was evaluated according to the following evaluation criteria.
Excellent: for more than 6 hours
Good: 5 hours
The difference is: for less than 4 hours
[ evaluation of appearance of coating film ]
Immediately after the preparation of the water-based curable composition (1), the water-based curable composition (1) was applied to a glass plate with an applicator to a dry thickness of 30 μm and dried at 60℃for 2 hours to prepare a cured coating film. The appearance of the obtained cured coating film was evaluated according to the following evaluation criteria.
Good: no turbidity
Generally: slightly turbid
The difference is: very turbid
( Examples 10 to 16: preparation and evaluation of Water-based curable compositions (2) to (8) )
Water-based curable compositions (2) to (8) were prepared in the same manner as in example 9 except that the water-dispersible polyisocyanate composition (1) used in example 9 was changed to water-dispersible polyisocyanate compositions (2) to (8), and then evaluated similarly.
( Comparative examples 4 to 6: preparation and evaluation of Water-based curable compositions (R-1) to (R-3) )
Water-based curable compositions (R-1) to (R-3) were prepared in the same manner as in example 9 except that the water-dispersible polyisocyanate composition (1) used in example 9 was changed to water-dispersible polyisocyanate compositions (R1) to (R3), and then evaluated similarly.
Tables 6 to 8 present the evaluation results of examples 9 to 16 and comparative examples 4 to 6.
TABLE 6
TABLE 7
TABLE 8
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The results show that the water-based curable compositions prepared by using the water-dispersible polyisocyanate compositions of examples 1 to 8 have a long pot life and provide excellent appearance of the resulting coating films.
The water-dispersible polyisocyanate composition of comparative example 1 is one example of a water-dispersible polyisocyanate composition prepared without using the acrylic polymer (b 2) as an essential raw material of one embodiment of the present invention. The results show that the water-based curable composition prepared by using the water-dispersible polyisocyanate composition of comparative example 1 provided a coating film having poor appearance.
The water-dispersible polyisocyanate composition of comparative example 2 is one example of a water-dispersible polyisocyanate composition prepared without using the acrylic polymer (b 1) as an essential raw material of one embodiment of the present invention. The results show that the water-based curable composition prepared by using the water-dispersible polyisocyanate composition of comparative example 2 provided a coating film having poor appearance.
The water-dispersible polyisocyanate composition of comparative example 3 is one example of a water-dispersible polyisocyanate composition prepared by using only one type of acrylic polymer as a raw material. The results show that the water-based curable composition prepared by using the water-dispersible polyisocyanate composition of comparative example 3 has a poor pot life.
Claims (7)
1. A water-dispersible polyisocyanate composition comprising:
hydrophobic polyisocyanates (a); and
an acrylic polymer (B) containing an alkoxy-terminated polyoxyalkylene group and an isocyanate group,
wherein the acrylic polymer (B) is the reaction product of an acrylic polymer (B) and a hydrophobic polyisocyanate,
the acrylic polymer (b) contains an acrylic polymer (b 1) and an acrylic polymer (b 2),
the acrylic polymer (b 1) is derived from a monomer raw material containing 11 mol% or more and 35 mol% or less of an acrylic monomer (x) having an alkoxy-terminated polyoxyalkylene group, and
the acrylic polymer (b 2) is derived from a monomer raw material containing 2 mol% or more and less than 11 mol% of the acrylic monomer (x).
2. The water-dispersible polyisocyanate composition according to claim 1, wherein the acrylic polymer (B) has 12 to 30 oxyalkylene repeat units in the alkoxy-terminated polyoxyalkylene group.
3. The water-dispersible polyisocyanate composition according to claim 1 or 2, wherein the mass ratio (a/b) of the hydrophobic polyisocyanate (a) to the acrylic polymer (b) is in the range of 0.8 to 6.3.
4. A water-based curable composition comprising:
a water-dispersible polyisocyanate composition according to any one of claims 1 to 3; and
an active hydrogen group-containing water-based resin (C) having an active hydrogen group reactive with an isocyanate group.
5. A water-based coating, the water-based coating comprising:
the water-based curable composition according to claim 4.
6. An article coated with the water-based coating of claim 5.
7. A process for preparing the water-dispersible polyisocyanate composition according to any one of claims 1 to 3, the process comprising:
polymerizing a monomer raw material for the acrylic polymer (b 2) in the presence of the acrylic polymer (b 1) to form the acrylic polymer (b).
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| PCT/CN2021/074798 WO2022165622A1 (en) | 2021-02-02 | 2021-02-02 | Water-dispersible polyisocyanate composition, method for producing composition, water-based curable composition, water-based paint, and article |
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| JP (1) | JP2023532141A (en) |
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| JP3775578B2 (en) * | 2000-10-19 | 2006-05-17 | 大日本インキ化学工業株式会社 | Water-dispersible polyisocyanate composition, production method thereof, aqueous curable composition and application thereof |
| JP3956664B2 (en) * | 2000-10-19 | 2007-08-08 | 大日本インキ化学工業株式会社 | Water dispersible polyisocyanate composition, aqueous curable composition and application thereof |
| JP5150994B2 (en) * | 2001-08-30 | 2013-02-27 | Ｄｉｃ株式会社 | Water-dispersible polyisocyanate composition, aqueous curable composition, aqueous paint and aqueous adhesive containing aqueous curable composition |
| JP4251273B2 (en) * | 2003-03-31 | 2009-04-08 | Ｄｉｃ株式会社 | Water-dispersible polyisocyanate composition and aqueous curable composition containing the composition |
| US8153708B2 (en) * | 2010-04-01 | 2012-04-10 | Ppg Industries Ohio, Inc | Process for forming a waterborne composite polyurethane/acrylic polymer dispersion |
| JP6247492B2 (en) * | 2012-11-06 | 2017-12-13 | ダウ グローバル テクノロジーズ エルエルシー | Aqueous leather coating composition and method for coating leather |
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