WO2020026743A1 - Composition de revêtement à base d'eau - Google Patents

Composition de revêtement à base d'eau Download PDF

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Publication number
WO2020026743A1
WO2020026743A1 PCT/JP2019/027452 JP2019027452W WO2020026743A1 WO 2020026743 A1 WO2020026743 A1 WO 2020026743A1 JP 2019027452 W JP2019027452 W JP 2019027452W WO 2020026743 A1 WO2020026743 A1 WO 2020026743A1
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Prior art keywords
resin particles
acrylic resin
meth
mass
coating composition
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PCT/JP2019/027452
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English (en)
Japanese (ja)
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岳 富森
睦 小笠原
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関西ペイント株式会社
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Priority to CN201980045082.2A priority Critical patent/CN112384580B/zh
Priority to JP2020534150A priority patent/JP7339257B2/ja
Publication of WO2020026743A1 publication Critical patent/WO2020026743A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the present invention relates to an aqueous coating composition having excellent corrosion resistance, adhesion and water resistance.
  • the present invention also relates to a coated article having a cured coating film of the aqueous coating composition.
  • Patent Document 1 the storage stability is good, rust prevention, and as a coating composition capable of forming a coating film having excellent water adhesion to the top coat, as a latex comprising a specific vinylidene chloride-based copolymer resin, An aqueous rust preventive coating composition using a specific silane coupling agent is disclosed.
  • Patent Document 2 discloses, as a dried coating film excellent in water resistance, adhesion and lifting resistance, and an aqueous coating material excellent in storage stability for application to buildings, civil engineering structures, and the like, (A A) an aqueous dispersion of a copolymer resin having a weight average molecular weight of 30,000 to 300,000, comprising (B) a silane coupling agent, wherein component (B) is added to component (A) in a solids ratio of 0.05. There is disclosed an aqueous dispersion composition of a copolymer resin, which is characterized by being about 10% by weight.
  • Patent Documents 1 and 2 silane coupling agents are widely known as a technique for improving adhesion.
  • both of the aqueous compositions of Patent Documents 1 and 2 have insufficient adhesion after water resistance load and the like, and improvement has been desired.
  • the present invention has been made in view of the above circumstances, and has as its object to provide an aqueous coating composition having excellent corrosion resistance, adhesion, and water resistance.
  • the present invention includes the following embodiments.
  • the acrylic resin particles (A) have a polymerizable unsaturated monomer having an acid value of 10 to 100 mgKOH / g, 80% by weight or more of all copolymer components, and a solubility parameter value of 9.5 or less;
  • a water-based paint wherein the rust inhibitor (B) comprises an aminosilane (b1), an azole compound (b2), and at least one compound (b3) selected from the group consisting of fatty acids, aromatic acids and aliphatic amines Composition.
  • a coated article having a substrate and a cured coating film of the aqueous coating composition according to any one of (1) to (4) on the substrate.
  • the aqueous coating composition of the present invention having the above characteristics can form a coating film having excellent corrosion resistance, adhesion and water resistance.
  • the aqueous coating composition according to the present invention is an acrylic resin which is a polymerizable unsaturated monomer having an acid value of 10 to 100 mgKOH / g, at least 80% by mass of all copolymer components, and a solubility parameter value of 9.5 or less.
  • the acrylic resin particles (A) may be prepared, for example, by polymerizing a polymerizable unsaturated monomer by a known method, for example, a solution polymerization method in an organic solvent and then dispersing it in water to form resin particles, or an emulsion weight in water. It can be obtained by polymerizing by a method such as a legal method.
  • a so-called core / shell polymerization method in which a mixture of polymerizable unsaturated monomers is fed in multiple stages, and a power feed method in which the composition of the polymerizable unsaturated monomers fed during polymerization is gradually changed can be adopted. Further, two or more kinds of acrylic resin particles produced by the above method can be used in combination.
  • core-shell type acrylic resin particles (A) can be obtained.
  • the core-shell type acrylic resin particles (A) are usually a copolymer (I) containing a polymerizable unsaturated monomer as a copolymer component and a copolymer containing a polymerizable unsaturated monomer as a copolymer component (A).
  • Acrylic resin particles comprising a shell portion as II).
  • the ratio of the copolymer (I) / the copolymer (II) is preferably about 10/90 to 90/10, and more preferably 15/85 to 85/15, in terms of solid content mass ratio, from the viewpoint of achieving both corrosion resistance and hardness. Degree is more preferable, and about 20/80 to 80/20 is further preferable.
  • the “shell portion” of the core-shell type acrylic resin particles (A) means the polymer layer present in the outermost layer of the resin particles, and the “core portion” is the weight of the resin particle inner layer excluding the shell portion.
  • the term “core-shell type structure” means a structure having the above-mentioned core portion and shell portion.
  • the core-shell structure generally has a layer structure in which the core portion is completely covered with the shell portion, but depending on the mass ratio of the core portion and the shell portion, the amount of monomer in the shell portion forms the layer structure. In some cases, it may not be enough. In such a case, it is not necessary to have a complete layer structure as described above, and a structure in which a shell part covers a part of the core part may be used. Further, the concept of the multilayer structure in the core-shell type structure is similarly applied to the case where the core portion of the core-shell type acrylic resin particles (A) has a multilayer structure.
  • acrylic resin particles (A) having a gradient polymer layer can be obtained.
  • the gradient polymer layer means a polymer layer having a layer structure in which the composition changes continuously (has a composition gradient).
  • it means a polymer layer having a composition gradient in which the monomer (or monomer mixture) composition continuously changes from, for example, monomer A (or monomer mixture A) to monomer B (or monomer mixture B). It is.
  • the power feed method is a known polymerization method. Specifically, for example, when a polymerization reaction of two types of monomer A (monomer mixture A) and monomer B (monomer mixture B) is performed, monomer B (monomer mixture B) is used. ) Is dropped into a container containing the monomer A (monomer mixture A), and the polymerization reaction is performed by introducing the monomer A (monomer mixture A) into the reaction vessel.
  • the synthesis conditions timing of the start of mixing of monomer A (monomer mixture A) and monomer B (monomer mixture B), container containing monomer B (monomer mixture A) in monomer B (monomer mixture B)
  • a gradient polymer layer having a desired composition gradient can be obtained by, for example, setting the rate at which the monomer A (monomer mixture A) is introduced into the reaction vessel and the rate at which the monomer A (monomer mixture A) is introduced into the reaction vessel.
  • the acrylic resin particles (A) can have at least one gradient polymer layer as needed.
  • the gradient polymer layer is It can be any layer.
  • a polymerizable unsaturated monomer is a monomer having a polymerizable unsaturated group.
  • the polymerizable unsaturated group means an unsaturated group capable of undergoing radical polymerization.
  • examples of the polymerizable unsaturated group include a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group.
  • (meth) acrylate means “acrylate or methacrylate”.
  • (Meth) acrylic acid means “acrylic acid or methacrylic acid”.
  • (meth) acryloyl means “acryloyl or methacryloyl”.
  • (Meth) acrylamide” means “acrylamide or methacrylamide”.
  • polymerizable unsaturated monomer examples include a polymerizable unsaturated monomer having one polymerizable unsaturated group in one molecule and a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule. it can.
  • Examples of the polymerizable unsaturated monomer having one polymerizable unsaturated group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate , N-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl (me
  • These monomers can be used alone or in combination of two or more, depending on the performance required for the acrylic resin particles (A).
  • Examples of the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol.
  • the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule has a function of imparting a crosslinked structure to the copolymer.
  • the proportion of the polymerizable unsaturated monomer can be appropriately determined according to the degree of crosslinking of the copolymer.
  • the method of preparing the acrylic resin particles (A) by emulsion polymerization can be performed by a conventionally known method. For example, it can be carried out by emulsion-polymerizing a polymerizable unsaturated monomer mixture using a polymerization initiator in the presence of an emulsifier.
  • an emulsifier an anionic emulsifier and a nonionic emulsifier can be suitably used.
  • anionic emulsifier examples include sodium salts and ammonium salts of alkylsulfonic acid, alkylbenzenesulfonic acid, alkylphosphoric acid and the like.
  • nonionic emulsifiers include, for example, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene nonyl phenyl ether.
  • Ethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, etc. be able to.
  • Examples of the reactive anionic emulsifier include a sodium salt of a sulfonic acid compound having a radical polymerizable unsaturated group such as an allyl group, a methallyl group, a (meth) acryloyl group, a propenyl group, and a butenyl group, and an ammonium salt of the sulfonic acid compound. And the like.
  • the amount of the emulsifier used is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and 15% by mass, based on the total amount of all the monomers used. Is preferably 10% by mass or less, more preferably 5% by mass or less.
  • polymerization initiator examples include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, tert-butylperoxylaurate, and tert-butylperoxy.
  • Organic peroxides such as isopropyl carbonate, tert-butylperoxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropionnitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydridene) Azo compounds such as xyethyl) -propionamide] and azobis ⁇ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide ⁇ ; persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; Can be mentioned.
  • persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate
  • polymerization initiators can be used alone or in combination of two or more. Further, if necessary, a reducing agent such as sugar, sodium formaldehyde sulfoxylate, iron complex or the like may be used in combination with the polymerization initiator to form a redox initiator.
  • a reducing agent such as sugar, sodium formaldehyde sulfoxylate, iron complex or the like may be used in combination with the polymerization initiator to form a redox initiator.
  • the amount of the polymerization initiator used is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less, based on the total amount of all the monomers used. It is more preferably at most 3% by mass.
  • the method of adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount of the polymerization initiator. For example, it can be previously contained in a monomer mixture or an aqueous medium, can be added at a time during polymerization, or can be added dropwise.
  • the polymerizable unsaturated monomer mixture is emulsion-polymerized to obtain an emulsion of the core copolymer (I), and then the polymerizable unsaturated monomer is added to the emulsion. It can be obtained by adding a mixture and further performing emulsion polymerization to prepare a shell copolymer (II).
  • Emulsion polymerization for preparing an emulsion of the core copolymer (I) can be carried out by a conventionally known method. For example, it can be carried out by emulsion polymerization of a polymerizable unsaturated monomer mixture using a polymerization initiator in the presence of an emulsifier in the same manner as described above.
  • the core-shell type acrylic resin particles (A) are obtained by adding a polymerizable unsaturated monomer mixture to the emulsion of the core copolymer (I) obtained above and further polymerizing to form a shell copolymer (II). Can be obtained.
  • the monomer mixture forming the shell copolymer (II) may appropriately contain components such as the polymerization initiator, the chain transfer agent, the reducing agent, and the emulsifier, if necessary. Further, the monomer mixture can be dropped as it is, but it is preferable to drop the monomer mixture as a monomer emulsion obtained by dispersing the monomer mixture in an aqueous medium. In this case, the particle size of the monomer emulsion is not particularly limited.
  • the monomer mixture or an emulsion thereof is dropped at once or gradually, and an emulsion of the core copolymer (I) is obtained. And heating the mixture to an appropriate temperature with stirring.
  • the core-shell type acrylic resin particles (A) thus obtained have a multilayer structure having the copolymer (I) as a core and the copolymer (II) as a shell.
  • the core-shell type acrylic resin particles (A) are polymerizable to form another resin layer between the step of obtaining the core copolymer (I) and the step of obtaining the shell copolymer (II).
  • a step of supplying an unsaturated monomer (one or a mixture of two or more) to carry out emulsion polymerization core-shell type acrylic resin particles comprising three or more layers can be obtained.
  • the acrylic resin particles (A) can have at least one gradient polymer layer as needed.
  • the gradient polymer layer is It can be any layer.
  • the resin layer used as the gradient polymer layer can be prepared by the above-described power feed polymerization or the like.
  • the acrylic resin particles (A) have an acid value in the range of 10 to 100 mgKOH / g, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, and 80 mgKOH / g from the viewpoints of adhesion and water resistance. g or less, and more preferably 70 mgKOH / g or less.
  • a monomer for imparting an acid value to the acrylic resin particles (A) from the viewpoint that a neutralizing agent is volatilized, hydrophilicity is greatly reduced after forming a film, and water resistance and corrosion resistance are advantageous. It is preferable to contain a group-containing polymerizable unsaturated monomer.
  • Acrylic acid and / or methacrylic acid can be particularly preferably used as the carboxyl group-containing polymerizable unsaturated monomer.
  • the acid value (mgKOH / g) is represented by mg of potassium hydroxide when the amount of acid groups contained in 1 g of a sample (1 g of solid content in the case of resin) is converted into potassium hydroxide. It is.
  • the molecular weight of potassium hydroxide is 56.1.
  • Acid value (mgKOH / g) 56.1 ⁇ V ⁇ C / m V: titration (ml), C: concentration of titrant (mol / l), m: solid weight of sample (g)
  • the acrylic resin particles (A) 80% by mass or more of the total copolymer components are polymerizable unsaturated monomers having a solubility parameter value (SP value) of 9.5 or less, and the hydrophilicity of the coating film is high. It is preferable from the viewpoint of water resistance and corrosion resistance without becoming too much.
  • the polymerizable unsaturated monomer having a solubility parameter value (SP value) of 9.5 or less is preferably at least 85% by mass of all copolymerized components, more preferably at least 90% by mass.
  • solubility parameter value is as defined in Polymer ⁇ Engineering and ⁇ Science, 14, No. 2, p. 147 (1974), calculated by the following Fedors equation.
  • SP ⁇ ( ⁇ e1) / ⁇ ( ⁇ v1) ⁇ (In the formula, ⁇ e1 represents the aggregation energy per unit functional group, and ⁇ v1 represents the molecular volume per unit functional group.)
  • the SP value of a copolymer or a blend of a mixture of two or more resins is as follows: , And a value obtained by multiplying the SP value of each component of the monomer unit or the blend by the mass fraction.
  • the glass transition temperature (Tg) of the acrylic resin particles (A) is preferably ⁇ 10 ° C. or higher, more preferably 0 ° C. or higher, and even more preferably 10 ° C. or higher, from the viewpoints of hardness and corrosion resistance.
  • Tg glass transition temperature
  • the glass transition temperature (Tg, ° C) of the copolymer can be calculated by the following equation.
  • n the number of types of monomers used (natural number)
  • W1 to Wn are the weight percentages of the n monomers used in the copolymerization
  • T1 to Tn are the weights of the n monomers.
  • T1 to Tn the values described in Polymer Hand Book (Second Edition, edited by J. Brandup, EH Immergut), pages III-139 to 179, can be used.
  • the glass transition temperature (° C.) when the Tg of the homopolymer of the monomer is not clear can also be obtained as a static glass transition temperature by actual measurement.
  • a sample is taken in a measurement cup, and the solvent is completely removed by vacuum suction.
  • the calorie change is measured at a temperature rate in the range of ⁇ 20 ° C. to + 200 ° C., and the first baseline change point on the low temperature side is defined as a static glass transition temperature.
  • the acrylic resin particles (A) preferably have a weight average molecular weight of more than 75,000, more preferably 90,000 or more, and still more preferably 100,000 or more, from the viewpoint of corrosion resistance and water resistance.
  • the weight average molecular weight is a value obtained by converting the retention time measured using a gel permeation chromatograph into the molecular weight of polystyrene by the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. .
  • HEC-8120GPC (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and one “TSKgel @ G4000HXL” and two “TSKgel @ G3000HXL” are used as columns.
  • TSKgel @ G2000HXL (trade name, all manufactured by Tosoh Corporation) using a differential refractometer as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C.
  • the weight average molecular weight can be determined by measuring the flow rate under the condition of 1 mL / min.
  • the average particle size of the acrylic resin particles (A) is preferably 50 nm or more, more preferably 60 nm or more, still more preferably 70 nm or more, and preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the average particle diameter can be measured using a general measuring means such as laser light scattering.
  • the average particle size of the resin particles is a value measured at 20 ° C. after dilution with deionized water by a conventional method using a submicron particle size distribution analyzer.
  • the submicron particle size distribution measuring device for example, “COULTER N4 type” (trade name, manufactured by Beckman Coulter, Inc.) can be used.
  • an acid group such as a carboxyl group of the acrylic resin particles can be neutralized with a neutralizing agent.
  • the neutralizing agent is not particularly limited as long as it can neutralize an acid group. Examples thereof include sodium hydroxide, potassium hydroxide, trimethylamine, 2- (dimethylamino) ethanol, and 2-amino-2-methyl- Examples thereof include 1-propanol, triethylamine, and aqueous ammonia. These neutralizing agents can be suitably used in such an amount that the pH of the aqueous dispersion of the acrylic resin particles (A) after neutralization is about 6.5 to 9.0.
  • the rust preventive (B) is an aminosilane (b1), an azole compound (b2), and at least one compound (b3) selected from the group consisting of a fatty acid, an aromatic acid, and an aliphatic amine (hereinafter, each referred to as “b1 ), “(B2) component”, and “(b3) component”), which have the effect of improving the corrosion protection and adhesion of the aqueous coating composition. .
  • Aminosilane (b1) is a silane compound having an amino group, specifically, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyl Diethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, N-phenyl- Aminosilanes such as ⁇ -aminopropyltrimethoxysilane, N-benzyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltrimethoxysilane, and bis (trimethoxysilylpropyl)
  • aminosilane (b1) ⁇ -aminopropyltriethoxysilane can be suitably used from the viewpoint of stability at the time of preparing a paint.
  • the azole compound (b2) is a 5-membered heterocyclic compound containing one or more nitrogen atoms.
  • a cyclic compound having one nitrogen atom such as pyrrole, pyrazole, imidazole, triazole, tetrazole and pentazole
  • a cyclic compound having two or more nitrogen atoms a cyclic compound having one nitrogen atom and one oxygen atom such as oxazole and isoxazole, and one nitrogen atom such as thiazole and isothiazole.
  • a cyclic compound having two sulfur atoms is a 5-membered heterocyclic compound containing one or more nitrogen atoms.
  • a cyclic compound having one nitrogen atom such as pyrrole, pyrazole, imidazole, triazole, tetrazole and pentazole
  • a cyclic compound having two or more nitrogen atoms a cyclic compound having one nitrogen atom and one oxygen atom such as oxazo
  • azole compound (b2) triazole and thiazole can be suitably used from the viewpoint of the interaction point with metal and the acting force.
  • the azole compound (b2) includes benzotriazole, mercaptobenzothiazole, aminotriazole, mercaptobenzoxazole, mercaptobenzimidazole and the like.
  • benzotriazole and mercaptobenzothiazole can be particularly preferably used.
  • the fatty acids are long-chain hydrocarbon monovalent carboxylic acids.
  • a saturated or unsaturated alkyl carboxylic acid having 8 to 22 carbon atoms, preferably 14 to 22 carbon atoms can be suitably used from the viewpoint of improving water resistance.
  • fatty acid specifically, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, arachidic acid, behenic acid, coconut oil fatty acid, Palm oil fatty acids, beef tallow fatty acids and the like can be mentioned.
  • the aromatic acid is a carboxylic acid of an aromatic compound.
  • the aromatic acid include benzoic acid, 4-t-butylbenzoic acid, aminobenzoic acid, toluic acid, ethylbenzoic acid, n-propylbenzoic acid, n-butylbenzoic acid and the like.
  • the aliphatic amine is a linear hydrocarbon having an amino group, and specifically, monomethylamine, dimethylamine, monoethylamine, diethylamine, triethylamine, octylamine, dodecylamine, tridecyl Alkylamines such as amine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine and docosylamine; N-methylaminoethanol, N, N-dimethylaminoethanol, N, N Hydroxylamines such as -diethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine or triethanolamine; ethylenediamine, diethylenetriamine, N-octadecylpropane-1,3 Polyvalent amines such as diamine, and the
  • monovalent amines having a long-chain alkyl group having 8 or more carbon atoms such as octylamine and octadecylamine, can be suitably used among the above aliphatic amines.
  • the rust preventive (B) is preferably at least 0.3% by volume, more preferably at least 0.4% by volume, based on the total solid content of all components of the aqueous coating composition, from the viewpoint of corrosion resistance and water resistance. , 0.5 vol% or more, more preferably 6.0 vol% or less, more preferably 5.0 vol% or less, even more preferably 4.0 vol% or less.
  • each component (component (b1), component (b2) and component (b3)) of the rust preventive (B) is expressed as solid content based on the total solid content of the rust preventive (B).
  • the component b1) is preferably at least 20% by mass, more preferably at least 30% by mass, still more preferably at least 40% by mass, and preferably at most 80% by mass, more preferably at most 70% by mass, further preferably at most 60% by mass. preferable.
  • the component (b2) is preferably at least 10% by mass, more preferably at least 15% by mass, even more preferably at least 20% by mass, and more preferably 70% by mass, based on the total solids of the rust preventive (B).
  • the component (b3) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and more preferably 70% by mass, based on the total solid content of the rust preventive (B). %, Preferably 60% by mass or less, more preferably 50% by mass or less. These are all preferable from the viewpoint of anticorrosion and adhesion.
  • the acrylic resin particles (C) are resins that act as a film-forming aid. In the drying process after coating, the acrylic resin particles (C) diffuse along with the phase transition, and the acrylic resin particles (A) serving as the base resin are removed. The voids are filled, and the formation of voids in the coating film during the drying process is suppressed. This makes it possible to improve the low-temperature film-forming property even when the film-forming aid such as a solvent is not contained at all or is contained or contained in a small amount.
  • the acrylic resin particles (C) can be obtained by using the same polymerization method as the acrylic resin particles (A) and appropriately changing the polymerization conditions.
  • the acrylic resin particles (C) produced by a method of polymerizing in an organic solvent by a solution polymerization method and then dispersing in water to obtain resin particles.
  • the weight average molecular weight of the acrylic resin particles (C) is 7500 to 75,000, preferably 8000 or more, more preferably 8500 or more, and preferably 30,000 or less, more preferably 20,000 or less.
  • the acid value of the acrylic resin particles (C) is 10 to 90 mgKOH / g, preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g. g or less.
  • the glass transition temperature (Tg) of the acrylic resin particles (C) is preferably 0 ° C or higher, more preferably 10 ° C or higher, even more preferably 20 ° C or higher. By setting the glass transition temperature (Tg) to 0 ° C. or higher, the hardness of the obtained coating film is improved.
  • the SP value (solubility parameter value) of the acrylic resin particles (C) is preferably 9.3 or less, more preferably 9.0 or less. By setting the SP value to 9.3 or less, good water resistance is obtained and the corrosion resistance is excellent.
  • the SP value difference between the shell portion (outermost layer (outermost surface layer portion)) of the acrylic resin particles (A) and the acrylic resin particles (C) is preferably within 0.4, more preferably within 0.3, Within 0.2 is even more preferred, and within 0.1 is even more preferred.
  • the total solid content of the acrylic resin particles (A) is 35% by mass based on the total solid content of the acrylic resin particles (A) and the acrylic resin particles (C). % Or more, and the acrylic resin particles (C) are preferably 65% by mass or less, the acrylic resin particles (A) are more preferably 40% by mass or more, and the acrylic resin particles (C) are more preferably 60% by mass or less. Is more preferably 45% by mass or more and the acrylic resin particles (C) are 55% by mass or less.
  • the total solid content is preferably 90% by mass or less for the acrylic resin particles (A), 10% by mass or more for the acrylic resin particles (C), 80% by mass or less for the acrylic resin particles (A), and 90% by mass or less. ) Is more preferably 20% by mass or more, the acrylic resin particles (A) are more preferably 70% by mass or less, and the acrylic resin particles (C) are more preferably 30% by mass or more. All of these are preferable from the viewpoint of corrosion protection and water resistance.
  • the aqueous coating composition contains the acrylic resin particles (C)
  • the method of mixing the acrylic resin particles (A) and the acrylic resin particles (C) there is no limitation on the method of mixing the acrylic resin particles (A) and the acrylic resin particles (C). That is, both a method of adding the acrylic resin particles (C) to the acrylic resin particles (A) and a method of adding the acrylic resin particles (C) to the acrylic resin particles (A) can be adopted.
  • Resin particles other than the acrylic resin particles (A) and the acrylic resin particles (C) can be used in the water-based coating composition as needed.
  • the resin particles may be resin particles after a plurality of resins are blended, or may be a blend of a plurality of types of resin particles. These resin particles can be usually incorporated into the composition of the present invention in the form of an emulsion.
  • the aqueous paint composition preferably has a pH of 5.0 or more, more preferably 6.0 or more, and preferably 10.0 or less, more preferably 9.0 or less.
  • the aqueous coating composition may contain a crosslinking agent, a curing catalyst, a pigment such as a coloring pigment, a filler, an aggregate, a dispersant, a wetting agent, a thickener, a rheology control agent, a surface conditioning agent, It can also contain foaming agents, preservatives, fungicides, pH adjusters, rust inhibitors, anti-settling agents, anti-freezing agents, anti-skinning agents, ultraviolet absorbers, antioxidants, organic solvents and the like.
  • the water-based coating composition is a cured coating film which is applied and cured on various substrates, preferably a metal substrate, as required.
  • the coating film can be formed directly or twice or more by a conventionally known method, for example, a method such as roller coating, spray coating, brush coating, curtain coating, shower coating, dip coating, etc. to form a coating film.
  • the aqueous coating composition according to the present embodiment is applied on the metal base material, and cured to form a cured coating film. An excellent coated article can be obtained.
  • the coating film of the water-soluble coating composition is preferably cured at normal temperature from the viewpoint of energy saving and the like.
  • forced drying or heat curing can also be performed.
  • the thickness of the cured coating film obtained by coating and curing the aqueous coating composition is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, from the viewpoints of corrosion resistance, water resistance and hardness of the formed cured coating film. Preferably, it is 25 ⁇ m or more, more preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 60 ⁇ m or less.
  • Component (A2), component (B1) ) Component and (B2) component), and an aqueous solution of initiator 1 (in Table 1, VA-057 is a trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 2-2'-azobis [N- ( 2-carboxyethyl) -2-methylpropiondiamine] tetrahydrate was added dropwise over 3 hours to polymerize. After the completion of the dropwise addition, the reaction was carried out at 82 ° C. for 0.5 hour, and the initiator 2 aqueous solution was added dropwise over 0.5 hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C. for 1.5 hours, and then cooled to 25 ° C.
  • VA-057 is a trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 2-2'-azobis [N- ( 2-carboxyethyl) -2-methylpropiondiamine] tetrahydrate was added dropwise over 3 hours to poly
  • the dropping of the (A1) component emulsion was completed, the dropping of the (B1) component emulsion shown in Table 1 was started, and was dropped at about 146.0 parts / hour.
  • the reaction was carried out at 82 ° C. for 0.5 hour, and an aqueous solution of initiator 2 was added dropwise at about 3.3 parts / hour.
  • the reaction was carried out at 82 ° C. for 1.5 hours, and then cooled to 25 ° C.
  • the dropping rate was about 146.0 parts / hour for the component (A1) emulsion and about 6.6 parts / hour for the aqueous initiator 1 solution.
  • the dropping of the (A1) component emulsion was completed.
  • the dropping of the (A2) component emulsion shown in Table 1 was started.
  • the component (B1) emulsion shown in Table 1 was dropped into the component (A2) emulsion.
  • the dropping rate of the component (B1) emulsion was set to a rate at which the dropping was completed simultaneously with the dropping of the component (A2) emulsion, that is, about 73.0 parts / hour in this example. Thereafter, the component (B2) emulsion was dropped at about 146.0 parts / hour.
  • reaction was carried out at 82 ° C. for 0.5 hour, and an aqueous solution of initiator 2 was added dropwise at about 3.3 parts / hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C. for 1.5 hours, and then cooled to 25 ° C.
  • Acrylic resin particles (A-5), (A-6) and (A-7) are acrylic resin particles for a comparative example.
  • Table 1 shows the acid value of each acrylic resin particle (A), the SP value of 9.5 or less, the monomer ratio (% by mass) and the weight average molecular weight, the pH of the emulsion of each acrylic resin particle (A) (measured with a pH meter), The viscosity (measured with a B-type viscometer, measured at 60 rpm and 20 ° C.) and the average particle size are also shown.
  • Example 8 A beaker was charged with 186 parts of ethylene glycol monobutyl ether, 50 parts of KBE-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., ⁇ -aminopropyltriethoxysilane, solid content 100%), 30 parts of benzotriazole, and 20 parts of palmitic acid were added. The solution was added, stirred and dissolved to obtain a rust preventive (B-1) solution having a solid content of 35% by mass.
  • KBE-903 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., ⁇ -aminopropyltriethoxysilane, solid content 100%
  • a solution of each of the rust preventive agents (B-2) to (B-13) having a solid content of 35% by mass was prepared in the same manner as in Preparation Example 8 except that the composition was as shown in Table 2. Obtained.
  • the rust preventives (B-2) to (B-5) were stirred and dissolved, and then heated at 80 ° C. for 8 hours.
  • the rust preventives (B-8) to (B-13) are for comparative examples.
  • the component (b-1) is aminosilane (b1)
  • the component (b-2) is an azole compound (b2)
  • the component (b-3) is fatty acids, aromatic acids and aliphatic amines.
  • Aqueous ammonia (solid content: 25%) was added to the obtained acrylic resin to neutralize it by an equivalent amount, and then deionized water was added with stirring to disperse the resin. Thereafter, propylene glycol monomethyl ether was removed by desolvation under reduced pressure, and deionized water was added again to obtain a dispersion of acrylic resin particles (C-1) having a solid content of 30% by mass.
  • the obtained acrylic resin particles (C-1) had a weight average molecular weight of 20,000, an acid value of 45 mgKOH / g, an SP value of 8.98, and an average particle size of 160 nm.
  • Example 1 DISPERBYK (registered trademark) -190 (trade name, manufactured by BYK, pigment dispersant, solid content: 40%) 3 parts (solid content: 1.2 parts), BYK (registered trademark) -024 (trade name, manufactured by BYK, 0.4 parts of antifoaming agent, solid content 100%), 35 parts of JR-603 (trade name, manufactured by Teika, titanium oxide, solid content 100%), Super SS (trade name, manufactured by Maruo Calcium Co., calcium carbonate, 15 parts of solid content 100%), 25 parts of deionized water and 2 parts of dipropylene glycol monomethyl ether were mixed, and after adding glass beads, the mixture was dispersed with a paint shaker for 60 minutes to obtain a pigment dispersion (P1) (solid content 64.2%). %).
  • P1 solid content 64.2%
  • Example 2 to 15 and Comparative Examples 1 to 9 each water-based coating composition No. was changed in the same manner as in Example 1 except that the composition was changed to those shown in Tables 3 and 4. 2 to No. 24 was obtained.
  • Tables 3 and 4 also show the SP value difference between the shell part (SP value difference between the shell part of the acrylic resin particles (A) and the acrylic resin particles (C)) and the rust preventive (B) concentration (% by volume). Also shown.
  • each aqueous coating composition No. obtained in the above Examples 1 to 15 and Comparative Examples 1 to 9 was coated. 1 to No. 24 were each coated by air spray so that the thickness of the cured coating film was 40 ⁇ m.
  • each test plate having a cured coating film formed on a steel plate was obtained by being left at 23 ° C. and 65% RH for 7 days.
  • Corrosion protection With respect to each test plate, the coating film was cross-cut with a knife so as to reach the base material, and 240 hours in accordance with JIS K 5600-7-1 (1999) "neutral salt spray resistance" A salt spray test was performed. Evaluation was made according to the following criteria based on the width of rust and blisters from knife scratches. The smaller the maximum width of rust and blisters, the better the anticorrosion. If the rating is A to C, the anticorrosion is good.
  • A Good and no problem. :: Some gloss is observed, but it is at a practical level. ⁇ : Either blister or gloss was observed. ⁇ : Either blisters or glossiness are remarkably observed.
  • ⁇ 100 cross-cut coatings remained, and the edge of the cut by the cutter was smooth. Good: 100 cross-cut coating films remained, but small peeling of the coating film occurred at the intersection of cuts of the cutter. ⁇ : 99 to 81 cross-cut coating films remained. ⁇ : The number of remaining cross-cut coating films is 80 or less.
  • an aqueous coating composition which is excellent in all of anticorrosion properties, adhesion properties and water resistance.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Dispersion Chemistry (AREA)
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Abstract

Le but de la présente invention est de fournir une composition de revêtement à base d'eau qui possède des propriétés anti-corrosion supérieures, une adhérence supérieure et une résistance à l'eau supérieure. La présente invention concerne une composition de revêtement à base d'eau contenant : des particules de résine acrylique (A) ayant une valeur acide de 10 à 100 mg KOH/g inclus, au moins 80 % en poids de tous les composants de copolymère étant constitués par des monomères insaturés polymérisables ayant une valeur SP de 9,5 ou moins ; et un inhibiteur de rouille (B) qui contient un aminosilane (b1), un composé azole (b2), et au moins un type de composé (b3) choisi dans le groupe constitué des acides gras, des acides aromatiques et des amines aliphatiques.
PCT/JP2019/027452 2018-08-02 2019-07-11 Composition de revêtement à base d'eau WO2020026743A1 (fr)

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CN117779030A (zh) * 2024-01-10 2024-03-29 开平和盟环保科技有限公司 一种硅晶槽液及环保金属表面处理工艺

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