WO2015005054A1 - 水性コーティング剤及びそれを用いた物品 - Google Patents
水性コーティング剤及びそれを用いた物品 Download PDFInfo
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- WO2015005054A1 WO2015005054A1 PCT/JP2014/065575 JP2014065575W WO2015005054A1 WO 2015005054 A1 WO2015005054 A1 WO 2015005054A1 JP 2014065575 W JP2014065575 W JP 2014065575W WO 2015005054 A1 WO2015005054 A1 WO 2015005054A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
- B05D1/305—Curtain coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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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
Definitions
- the present invention relates to, for example, an aqueous coating agent capable of forming a coating film on the surface of a plastic substrate or a metal substrate and an article using the same.
- the coating agent is generally required to be able to form a coating film that can prevent deterioration of the substrate surface.
- a coating agent that can form a coating film with a level of chemical resistance that can prevent deterioration of the substrate due to adhesion of chemicals such as cleaning agents and acid rain is generally required to be able to form a coating film that can prevent deterioration of the substrate surface.
- a coating agent that can form a coating film with a level of chemical resistance that can prevent deterioration of the substrate due to adhesion of chemicals such as cleaning agents and acid rain there is a demand from industry.
- the coating agent having the above-mentioned characteristics is often required especially for the surface protection of a plastic substrate that is easily deteriorated due to adhesion of chemicals or the like, or a metal substrate that is liable to generate rust.
- Examples of the coating agent that can be used for protecting the surface of the plastic substrate include polymer particles, a polyfunctional epoxy compound, and an aqueous medium, and the polymer particles are composed of at least two types of layers.
- a curable polymer aqueous dispersion in which the phase is composed of a carboxyl group-containing polymer and the B phase is an ethylenic polymer having a basic nitrogen atom-containing group is known (for example, see Patent Document 1).
- the coating film formed using the aqueous dispersion of the curable polymer can prevent deterioration of the plastic substrate and the metal substrate over a long period of time in terms of hot water resistance, corrosion resistance, and chemical resistance. It wasn't a step further. In particular, there were cases where it was not practically sufficient to prevent the occurrence of rust on the metal substrate.
- aqueous coating agent those containing various emulsifiers are known in order to impart excellent storage stability and blending stability.
- the storage stability may not be improved even when an emulsifier is used.
- the storage stability of the aqueous coating agent can be improved by using the emulsifier, there is a problem that the adhesion of the coating film to the substrate, hot water resistance, corrosion resistance, chemical resistance, and the like are lowered.
- the problems to be solved by the present invention are excellent in adhesion, warm water resistance, corrosion resistance and chemical resistance, can form a coating film that can prevent deterioration of various substrates, and is excellent in storage stability and blending stability.
- An aqueous coating agent is provided.
- the coating film of the water-based coating agent containing the present invention has been found to be excellent in adhesion to the substrate, hot water resistance, corrosion resistance and chemical resistance, and can form a coating film that can prevent the deterioration of various substrates. Completed.
- the present invention comprises an aqueous coating agent comprising a vinyl polymer (A) having a basic nitrogen atom-containing group and a carboxyl group, a quaternary ammonium salt (B), and an aqueous medium (C), and
- A vinyl polymer
- B quaternary ammonium salt
- C aqueous medium
- the aqueous coating agent of the present invention can form a coating film having excellent adhesion to a substrate, hot water resistance, corrosion resistance and chemical resistance, it is a surface protective coating agent for plastic substrates, metal substrates, etc.
- plastic base material to which the aqueous coating agent of the present invention can be applied include acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), A polymethacrylic acid resin (PMMA resin) etc. are mentioned. Since the aqueous coating agent of the present invention can be applied to these plastic substrates, it can be suitably used for various articles such as mobile phones, home appliances, OA equipment, and automobile interior materials.
- the metal substrate to which the aqueous coating agent of the present invention can be applied examples include galvanized steel sheets and plated steel sheets of aluminum-zinc alloy steel sheets, aluminum sheets, aluminum alloy sheets, electromagnetic steel sheets, copper sheets, and stainless steel sheets. It is done. Since the water-based coating agent of the present invention can form a coating film excellent in corrosion resistance capable of preventing the occurrence of rust and the like of these metal base materials, such as building members such as outer walls and roofs, guardrails, soundproof walls, drainage grooves, etc. It can be suitably used for various articles such as civil engineering members, home appliances, industrial machines, and automobile exterior materials.
- the coating agent of the present invention contains a vinyl polymer (A) having a basic nitrogen atom-containing group and a carboxyl group, a quaternary ammonium salt (B), and an aqueous medium (C).
- A vinyl polymer having a basic nitrogen atom-containing group and a carboxyl group
- B quaternary ammonium salt
- C aqueous medium
- vinyl polymer (A) those having a basic nitrogen atom-containing group and a carboxyl group are used.
- Examples of the basic nitrogen atom-containing group include N, N-dimethylaminoethyl group, N, N-dimethylaminopropyl group, N, N-diethylaminoethyl group, N, N-dimethylaminopropyl group, N, N -A diethylaminopropyl group, a pyridinyl group, an amino group and the like can be mentioned, and an N, N-dimethylaminoethyl group is preferable.
- the content of the basic nitrogen atom-containing group in the vinyl polymer (A) is preferably in the range of 30 to 700 mmol / kg because the chemical resistance of the coating film of the aqueous coating agent of the present invention can be further improved.
- the range of 50 to 600 mmol / kg is more preferable, and the range of 80 to 400 mmol / kg is more preferable.
- the carboxyl group of the vinyl polymer (A) imparts good water dispersion stability to the vinyl polymer (A).
- the content of the carboxyl group in the vinyl polymer (A) is preferably in the range of 50 to 1,200 mmol / kg because it can further improve the adhesion with the base material of the aqueous coating agent of the present invention.
- the range of 80 to 1,000 mmol / kg is more preferable, and the range of 100 to 650 mmol / kg is more preferable.
- the said vinyl polymer (A) is a thing of the range of content of said basic nitrogen atom containing group, and that whose content of a carboxyl group is these ranges is preferable.
- the molar ratio of the basic nitrogen atom-containing group to the carboxyl group [basic nitrogen atom-containing group / carboxyl group] in the vinyl polymer (A) is the chemical resistance of the coating film of the aqueous coating agent of the present invention.
- the range of 0.1 to 3 is preferable, and the range of 0.3 to 2.8 is more preferable because adhesion to the substrate can be further improved.
- the vinyl polymer (A) can be produced, for example, by polymerizing a vinyl monomer mixture in the presence of a polymerization initiator and an aqueous medium (C).
- the vinyl polymer (A) comprises a vinyl monomer having a basic nitrogen atom-containing group, a vinyl monomer having a carboxyl group, and other vinyl monomers as necessary.
- the vinyl monomer mixture can be produced by radical polymerization.
- Examples of the vinyl monomer having a basic nitrogen atom-containing group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meta) ) Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxy Ethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine Vinyl monomers having
- N, N-dimethylaminoethyl (meth) acrylate is more preferred.
- the “(meth) acrylate” refers to one or both of acrylate and methacrylate.
- vinyl monomer having a basic nitrogen atom-containing group for example, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide and the like can be used.
- Examples of the vinyl monomer having a basic nitrogen atom-containing group include (meth) acrylamide, diethyl (meth) acrylamide, N-vinylpyrrolidone, N, N-dimethyl (meth) acrylamide, N, N— Diethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide and the like can also be used.
- vinyl monomer having a basic nitrogen atom-containing group for example, (meth) acrylonitrile can be suitably used.
- the vinyl monomers having a basic nitrogen atom-containing group may be partially or completely neutralized beforehand with an acidic compound or the like, and after radical polymerization of them to produce a vinyl polymer (A) If necessary, it may be neutralized.
- an inorganic acid or an organic acid can be used as the acidic compound that can be used for the neutralization.
- the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.
- the organic acid include formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, malic acid and the like.
- the total amount of the monomer mixture is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass.
- vinyl monomer having a carboxyl group examples include (meth) acrylic monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, or half esters or salts thereof. Is mentioned. Among the (meth) acrylic monomers, (meth) acrylic acid is preferable. These vinyl monomers can be used alone or in combination of two or more.
- the vinyl monomer having a carboxyl group may be partially or completely neutralized with a basic compound or the like in advance, and is necessary after radical polymerization of them to produce a vinyl polymer (A). It may be neutralized accordingly.
- Examples of basic compounds that can be used for neutralization include ammonia, triethylamine, morpholine, organic amines such as monoethanolamine and diethylethanolamine having a boiling point of 100 ° C. or higher; sodium hydroxide, potassium hydroxide, lithium hydroxide A metal hydroxide such as can be used.
- the use amount of the vinyl monomer having a carboxyl group can further improve physical properties such as adhesion to the base material of the coating film of the aqueous coating agent of the present invention, warm water resistance, chemical resistance (alkali resistance), and the like. Therefore, the total amount of the vinyl monomer mixture used for the production of the vinyl polymer (A) is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.3 to 8 parts by mass. .
- vinyl monomer that can be used for the production of the vinyl polymer (A) other vinyl monomers can be used as necessary in addition to the above-described ones.
- Examples of the other vinyl monomers include N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, and N- [2- (meth) acryloyl.
- Oxyethyl] morpholine 2-vinylpyridine, vinyl monomers having a pyridinyl group such as 4-vinylpyridine; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meta ) Acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate , N-decyl (meth) ac Alkyl (meta) such as acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, n-
- Examples of the other vinyl monomers include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl laurate, styrene, chlorostyrene, chloromethylstyrene, Also included are ⁇ -methylstyrene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.
- methyl (meth) acrylate, ethyl (meth) acrylate, or n-butyl (meth) acrylate is used because the coating performance of the aqueous coating agent of the present invention can be further improved. Is preferred.
- the total amount of the vinyl monomer mixture used in the production of the vinyl polymer (A) is 100 parts by mass. , Preferably 0.5 to 97 parts by mass, more preferably 50 to 97 parts by mass, and still more preferably 80 to 95 parts by mass.
- the polymerization of the vinyl monomer mixture may be carried out by supplying the vinyl monomer mixture and the polymerization initiator separately in the aqueous medium (C) or by supplying the mixture in a lump or divided. it can.
- Examples of the polymerization initiator that can be used in producing the vinyl polymer (A) include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide; 4,4′-azobis (4 And azo initiators such as -cyanovaleric acid) and 2,2'-azobis (2-amidinopropane) dihydrochloride.
- the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent described later.
- persulfate examples include potassium persulfate, sodium persulfate, and ammonium persulfate.
- organic peroxide examples include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and the like. Diacyl peroxide, t-butylcumyl peroxide, dialkyl peroxide such as dicumyl peroxide, peroxyesters such as t-butylperoxylaurate and t-butylperoxybenzoate, cumene hydroperoxide, paramentane hydro Hydroperoxides such as peroxide and t-butyl hydroperoxide can be used.
- reducing agent examples include ascorbic acid and its salt, erythorbic acid and its salt, tartaric acid and its salt, citric acid and its salt, metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, chloride Ferric iron or the like can be used.
- a nonionic emulsifier (D) is preferably used for the purpose of stabilizing the polymerization reaction.
- nonionic emulsifier (D) examples include polyoxyalkylene alkyl ethers such as polyoxyalkylene branched decyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene diphenyl ether, polyoxyethylene-polyoxy Examples thereof include a propylene block copolymer and an acetylenic diol surfactant.
- nonionic emulsifiers include “Neugen XL-series”, “Neugen TDS-series”, and “Neugen TDX-series” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
- polyoxyalkylene alkyl ethers are preferred because the storage stability and blending stability of the aqueous coating agent of the present invention can be further improved. More specifically, polyoxyalkylene branched decyl ethers are preferred. Is preferred. Examples of commercially available polyoxyalkylene branched decyl ethers include “Neugen XL-series” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- the usage-amount of the said nonionic emulsifier (D) since the storage stability and mixing
- the range of ⁇ 10 parts by mass is preferable, and the range of 0.5 to 7.5 parts by mass is more preferable.
- the content ratio of the vinyl polymer (A) in the aqueous coating agent of the present invention is preferably in the range of 3 to 70% by mass.
- the aqueous coating agent of the present invention contains a quaternary ammonium salt (B) together with the vinyl polymer (A).
- the quaternary ammonium salt (B) is generally used as an emulsifier, but when combined with the vinyl polymer (A), the physical properties of the coating such as adhesion to the substrate are not deteriorated. The storage stability and blending stability can be remarkably improved.
- the quaternary ammonium salt (B) is preferably a compound represented by the following general formula (1).
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group.
- R 1 in the formula is an alkyl group having 10 to 20 carbon atoms. More preferably, R 2 to R 4 are each independently an alkyl group having 1 to 3 carbon atoms.
- Examples of commercially available products of the quaternary ammonium salt (B) include “Katiogen Series” (Daiichi Kogyo Co., Ltd.), “Cotamine Series” (Kao Co., Ltd.), and the like.
- the quaternary ammonium salt (B) can further improve the storage stability and compounding stability of the aqueous coating agent of the present invention, 0.1 to 10 parts per 100 parts by mass of the vinyl polymer (A). It is preferably used in the range of parts by mass, and more preferably in the range of 0.3 to 7 parts by mass.
- the quaternary ammonium salt (B) may be mixed with the aqueous dispersion after producing the aqueous dispersion of the vinyl polymer (A), but the vinyl used for the production of the vinyl polymer (A). For the purpose of stabilizing the polymerization reaction of the monomer mixture, it may be used during the production of the vinyl polymer (A).
- Examples of the aqueous medium (C) used in the aqueous coating agent of the present invention include water, organic solvents miscible with water, and mixtures thereof.
- Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ether solvents; lactam solvents such as N-methyl-2-pyrrolidone, and the like.
- only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
- water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
- the aqueous medium (C) can suppress a sudden increase in viscosity during the production of the aqueous coating agent of the present invention, and can improve the productivity of the aqueous coating agent, its coating property, drying property, etc.
- the aqueous coating agent of the invention is preferably contained in the range of 5 to 80% by mass.
- the aqueous coating agent of the present invention contains an aqueous dispersion in which the vinyl polymer (A) is dispersed in an aqueous medium (C) and the quaternary ammonium salt (B), and other additives as necessary. Can be manufactured.
- a film-forming aid, a dispersion stabilizer, and a leveling agent may be used. However, it is preferable not to use the additive as much as possible because the hot water resistance of the coating film of the aqueous coating agent of the present invention can be improved.
- the amount used is preferably 0.5 parts by mass or less with respect to 100 parts by mass of the solid content in the aqueous coating agent of the present invention.
- the film forming aid examples include N-methylpyrrolidone, butyl carbitol acetate, dibutyl diglycol, methyl cellosolve, and butyl cellosolve. When using these film-forming aids, it is preferable to use them within a range that does not impair the effects of the present invention.
- the aqueous coating agent of the present invention can be used for coating various articles for the purpose of protecting the surface of various articles and imparting design properties.
- the article of the present invention has a coating film of the aqueous coating agent of the present invention.
- the material of the article include various plastics, metals, glass, paper, and wood.
- the aqueous coating agent of the present invention when used for various plastic substrates, it has excellent warm water resistance, corrosion resistance, and chemical resistance, even if a coating film is formed in a relatively low temperature drying process, and plastic. A coating film having excellent adhesion to the substrate can be obtained.
- plastic articles in which the aqueous coating agent of the present invention can be used include, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), Examples include molded products made of plastics such as polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, and polyethylene resin.
- ABS resin acrylonitrile-butadiene-styrene resin
- PC resin polycarbonate resin
- PS resin polystyrene resin
- PMMA resin polymethyl methacrylate resin
- acrylic resin polypropylene resin
- polyethylene resin polyethylene resin
- Specific examples of the article include a mobile phone, a home appliance, an OA device, and an automobile interior / exterior material.
- the aqueous coating agent of the present invention can also be used for various film substrates.
- the film substrate include a polyethylene terephthalate film, a polyester film, a polyethylene film, a polypropylene film, a TAC (triacetyl cellulose) film, a polycarbonate film, and a polyvinyl chloride film.
- the aqueous coating agent of the present invention can form a densely formed crosslinked coating film that can suppress corrosion of the metal substrate, it can also be suitably used for a metal substrate.
- the metal substrate include galvanized steel sheets used for applications such as automobiles, home appliances, and building materials, plated steel sheets such as aluminum-zinc alloy steel sheets, aluminum sheets, aluminum alloy sheets, electromagnetic steel sheets, copper sheets, and stainless steel sheets.
- Examples of specific articles based on metals include building members such as outer walls and roofs, guard rails, soundproof walls, civil engineering members such as drainage grooves, home appliances, industrial machinery, and automobile exterior materials. .
- the aqueous coating agent of the present invention can provide a coating film with excellent corrosion resistance, chemical resistance such as acid resistance and alkali resistance, even if the coating film has a thickness of about 1 ⁇ m. Accordingly, the aqueous coating agent of the present invention is extremely useful as a coating agent (metal surface treatment agent) for metal substrates because it can be used for metal substrates to prevent corrosion of metal substrates and improve chemical resistance. It is.
- the aqueous coating agent of the present invention can be applied on a substrate, dried and cured to form a coating film.
- Examples of the method for applying the aqueous coating agent of the present invention to the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
- the drying conditions when the aqueous coating agent of the present invention is used as a coating film may be natural drying at room temperature, or may be heat-dried. When drying by heating, it is usually preferable to carry out in a temperature range of 40 to 250 ° C. for a time of about 1 to 600 seconds.
- the above drying temperature is preferably 80 ° C. or less.
- the aqueous coating agent of the present invention has excellent warm water resistance since the crosslinking reaction of the coating proceeds at low temperature (normal temperature) after heat drying even when it is dried at a low temperature of 80 ° C. or lower for a few seconds. A coating film having good properties, corrosion resistance and chemical resistance is obtained.
- Example 1 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 49 parts by weight of n-butyl acrylate, 48 parts of methyl methacrylate 135 parts by weight of monomer pre-emulsion (X-1) was prepared by sequentially feeding 1 part by weight, 2 parts by weight of dimethylaminoethyl methacrylate, and 1 part by weight of methacrylic acid.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- the remaining monomer pre-emulsion (X-1) was added dropwise over 180 minutes.
- the monomer pre-emulsion (X-1) was added dropwise and cooled to obtain an aqueous coating agent (1) comprising an aqueous dispersion of a vinyl polymer.
- Example 2 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 46.3 parts by weight of n-butyl acrylate, methyl By supplying 48 parts by weight of methacrylate, 4 parts by weight of dimethylaminoethyl methacrylate, and 1.7 parts by weight of acrylic acid in this order and stirring, 135 parts by weight of monomer pre-emulsion (X-2) was prepared. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (2) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 3 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 45 parts by weight of n-butyl acrylate, 44 parts of methyl methacrylate 135 parts by weight of monomer pre-emulsion (X-3) was prepared by sequentially feeding and stirring parts by weight, 9 parts by weight of dimethylaminoethyl methacrylate, and 2 parts by weight of acrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (3) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 4 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 43 parts by weight of n-butyl acrylate, 42 parts of methyl methacrylate 135 parts by weight of monomer pre-emulsion (X-4) was prepared by sequentially feeding and stirring parts by weight, 8 parts by weight of dimethylaminoethyl methacrylate, and 7 parts by weight of acrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (4) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 5 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 48 parts by weight of n-butyl acrylate, 47 parts of methyl methacrylate 135 parts by weight of monomer pre-emulsion (X-5) was prepared by sequentially feeding and stirring parts by weight, 2 parts by weight of dimethylaminoethyl methacrylate, and 3 parts by weight of acrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (5) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 6 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 48 parts by weight of n-butyl acrylate and 49 parts by weight of methyl methacrylate. 135 parts by mass of monomer pre-emulsion (X-6) was prepared by sequentially feeding and agitating 1.5 parts by mass of dimethylaminoethyl methacrylate and 1.5 parts by mass of methacrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (6) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 7 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 48 parts by weight of n-butyl acrylate and 48 parts of methyl methacrylate 135 parts by weight of a monomer pre-emulsion (X-7) was prepared by sequentially feeding and stirring parts by weight, 3 parts by weight of dimethylaminoethyl methacrylate, and 1 part by weight of methacrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (7) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 8 In a container containing 30 parts by weight of deionized water and 5 parts by weight of Neugen XL-400 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether), 47 parts by weight of n-butyl acrylate, 46 parts of methyl methacrylate 135 parts by mass of monomer pre-emulsion (X-8) was prepared by sequentially feeding and agitating 6 parts by mass of dimethylaminoethyl methacrylate and 1 part by mass of acrylic acid. Subsequent operations were performed in the same manner as in Example 1 to obtain an aqueous coating agent (8) comprising an aqueous dispersion of a vinyl polymer.
- Neugen XL-400 Densiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether
- Example 9 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel, 110 parts by mass of deionized water and Cathogen TML (Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride, 30% by mass aqueous solution) ) 20 parts by mass was supplied, and the temperature in the reaction vessel was adjusted to 70 ° C. while blowing nitrogen gas.
- Cathogen TML Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride, 30% by mass aqueous solution
- the remaining monomer pre-emulsion (X-1) was added dropwise over 180 minutes.
- the monomer pre-emulsion (X-1) was added dropwise and cooled to obtain an aqueous coating agent (9) comprising an aqueous dispersion of a vinyl polymer.
- Example 10 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 110 parts by mass of deionized water and Cathogen TMS (Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride, 25% by mass aqueous solution) ) 8 parts by mass was supplied, and the temperature in the reaction vessel was adjusted to 70 ° C. while blowing nitrogen gas.
- Cathogen TMS Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride, 25% by mass aqueous solution
- the remaining monomer pre-emulsion (X-1) was added dropwise over 180 minutes.
- the monomer pre-emulsion (X-1) was added dropwise and cooled to obtain an aqueous coating agent (10) comprising an aqueous dispersion of a vinyl polymer.
- Example 11 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 110 parts by mass of deionized water and Catiogen BC-50 (Daiichi Kogyo Seiyaku Co., Ltd., alkyldimethylbenzylammonium chloride, 50 (Mass% aqueous solution) 4 parts by mass was supplied, and the temperature in the reaction vessel was adjusted to 70 ° C. while blowing nitrogen gas.
- Catiogen BC-50 Daiichi Kogyo Seiyaku Co., Ltd., alkyldimethylbenzylammonium chloride, 50 (Mass% aqueous solution) 4 parts by mass
- the remaining monomer pre-emulsion (X-1) was added dropwise over 180 minutes.
- the monomer pre-emulsion (X-1) was added dropwise and cooled to obtain an aqueous coating agent (11) comprising an aqueous dispersion of a vinyl polymer.
- Example 12 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel, 110 parts by mass of deionized water, Cathogen ES-L (Daiichi Kogyo Seiyaku Co., Ltd., alkyldimethylethylammonium ethyl sulfate, (50 mass% aqueous solution) 4 parts by mass was supplied, and the temperature in the reaction vessel was adjusted to 70 ° C. while blowing nitrogen gas.
- Cathogen ES-L Daiichi Kogyo Seiyaku Co., Ltd., alkyldimethylethylammonium ethyl sulfate, (50 mass% aqueous solution) 4 parts by mass was supplied, and the temperature in the reaction vessel was adjusted to 70 ° C. while blowing nitrogen gas.
- the remaining monomer pre-emulsion (X-1) was added dropwise over 180 minutes.
- the monomer pre-emulsion (X-1) was dropped and then cooled to obtain an aqueous coating agent (12) comprising an aqueous dispersion of a vinyl polymer.
- Example 13 In a container containing 30 parts by weight of deionized water and 6.7 parts by weight of Cathogen TML (Daiichi Kogyo Seiyaku Co., Ltd., alkyltrimethylammonium chloride, 30% by weight aqueous solution), 49 parts by weight of n-butyl acrylate, By supplying 48 parts by weight of methyl methacrylate, 2 parts by weight of dimethylaminoethyl methacrylate, and 1 part by weight of methacrylic acid in this order and stirring, 136.7 parts by weight of monomer pre-emulsion (X-9) was prepared.
- the aqueous coating agent obtained in the examples and comparative examples was coated on a 55% by mass aluminum-zinc alloy plated steel sheet degreased with acetone so that the film thickness after drying was about 5 ⁇ m using a bar coater. Then, it was put in a dryer having an atmospheric temperature of 100 ° C. for 60 seconds and dried to prepare a coating film. Thereafter, the test piece was cured at room temperature for 3 days. The said test piece was immersed in 50 degreeC warm water, the deterioration state of the coating film 100 minutes after was observed visually, and warm water resistance was evaluated according to the following reference
- A There was no change in the coating film.
- B Although a slight discoloration was observed on a very small part of the coating film surface, it was at a level causing no practical problem.
- C Swelling etc. were seen in the whole coating film.
- D The coating film was peeled off and the substrate was exposed.
- the aqueous coating agent obtained in the examples and comparative examples was coated on a 55% by mass aluminum-zinc alloy plated steel sheet degreased with acetone so that the film thickness after drying was about 5 ⁇ m using a bar coater. Then, it was put in a dryer having an atmospheric temperature of 100 ° C. for 60 seconds and dried to prepare a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. Place 1N hydrochloric acid on the coating film constituting the test piece as a spot, visually observe the deterioration state of the coating film after standing for 100 minutes, and evaluate chemical resistance (acid resistance) according to the following criteria. did.
- A There was no change on the surface of the coating film.
- B Slight yellowing was observed on the surface of the coating film, but it was at a level causing no practical problem.
- C The surface of the coating film was remarkably discolored.
- D The coating film was dissolved and the substrate was exposed.
- the aqueous coating agent obtained in the examples and comparative examples was coated on a 55% by mass aluminum-zinc alloy plated steel sheet degreased with acetone so that the film thickness after drying was about 5 ⁇ m using a bar coater. Then, it was put in a dryer having an atmospheric temperature of 100 ° C. for 60 seconds and dried to prepare a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. A 5% by mass aqueous sodium hydroxide solution is placed on the coating film constituting the test piece with a spot, and the deterioration state of the coating film after standing for 60 minutes is visually observed, and the chemical resistance ( Alkali resistance) was evaluated.
- A There was no change on the surface of the coating film.
- B Although a slight discoloration was observed on a part of the surface of the coating film, it was at a level causing no practical problem.
- C Discoloration was observed on the surface of the coating film.
- D The coating film was dissolved and the substrate was exposed.
- ABS resin acrylonitrile-butadiene-styrene resin
- PC resin polycarbonate resin
- a base material made of a polymer alloy (ABS / PC resin) of acrylonitrile-butadiene-styrene resin and polycarbonate resin hereinafter abbreviated as “ABS / PC”.
- a base material made of polymethyl methacrylate resin (PMMA resin) hereinafter abbreviated as “PMMA”)
- A The number of grids not peeled was 90 or more.
- B The number of grids not peeled was 60 or more and less than 90.
- C The number of grids not peeled was 40 or more and less than 60.
- D The number of grids not peeled was less than 40.
- a coating film was prepared in the same manner as the above adhesiveness (primary adhesiveness) to prepare a test piece.
- the test piece was immersed in warm water at 50 ° C. for 100 minutes, then taken out, wiped off the surface water, and then contacted with the above.
- the peel test was conducted in the same manner as the property (primary adhesion), and the adhesion to the plastic substrate (warm water adhesion) was evaluated according to the above criteria.
- the aqueous coating agent obtained in the examples and comparative examples was coated on a 55% by mass aluminum-zinc alloy plated steel sheet degreased with acetone so that the film thickness after drying was about 5 ⁇ m using a bar coater. Then, it was put in a dryer having an atmospheric temperature of 100 ° C. for 60 seconds and dried to prepare a coating film. Then, what was cured at room temperature for 3 days was used as a test piece.
- the coating surface of the test piece prepared above was scratched with a cutter knife to the depth reaching the substrate (cross cut part), and the salt spray test was performed using a salt spray tester manufactured by Suga Test Instruments Co., Ltd.
- the rust generation area after 240 hours was obtained visually, and corrosion resistance was evaluated according to the following criteria. In addition, evaluation of corrosion resistance was performed separately for the flat portion not scratched by the cutter knife and the periphery of the cross-cut portion.
- ⁇ Cross-cut area> A: Generation
- A Aggregates and precipitates were not confirmed at the bottom of the glass bottle.
- B Aggregates and precipitates were confirmed at 0 to 10% of the bottom of the glass bottle.
- C Aggregates and precipitates were confirmed at 10 to 50% of the bottom surface at the bottom of the glass bottle.
- D Aggregates and precipitates were confirmed at 50 to 100% of the bottom of the glass bottle.
- A Aggregates and precipitates were not confirmed at the bottom of the glass bottle.
- B Aggregates and precipitates were confirmed at 0 to 10% of the bottom of the glass bottle.
- C Aggregates and precipitates were confirmed at 10 to 50% of the bottom surface at the bottom of the glass bottle.
- D Aggregates and precipitates were confirmed at 50 to 100% of the bottom of the glass bottle.
- Tables 1 to 3 show the compositions and evaluation results of the aqueous coating agents obtained in the above Examples and Comparative Examples.
- the aqueous coating agent of the present invention is excellent in adhesion, hot water resistance, corrosion resistance, and chemical resistance, and can form a coating film that can prevent deterioration of various substrates. It was confirmed that the storage stability and blending stability were also excellent.
- Comparative Example 1 is an example of an aqueous coating agent that does not contain a quaternary ammonium salt (B).
- the coating film of the aqueous coating agent of Comparative Example 1 was remarkably inferior in hot water resistance, and was confirmed to have insufficient chemical resistance (acid resistance and alkali resistance), corrosion resistance, and hot water adhesion to a polycarbonate substrate. .
- water-based coating agent of this comparative example 1 was inadequate in the storage stability after one month, and the mixing
- Comparative Example 2 is an example of an aqueous coating agent using a vinyl polymer having no basic nitrogen atom-containing group. It can be confirmed that the coating film of the aqueous coating agent of Comparative Example 2 is extremely inferior in chemical resistance (acid resistance and alkali resistance), adhesion to the ABS resin base material, corrosion resistance, etc., and insufficient in hot water resistance. It was. Moreover, it has confirmed that the aqueous
- Comparative Example 3 is an example of an aqueous coating agent using a vinyl polymer having no carboxyl group.
- the coating film of the aqueous coating agent of Comparative Example 3 was remarkably inferior in chemical resistance (acid resistance and alkali resistance), corrosion resistance and the like, and it was confirmed that the hot water adhesion to the plastic substrate was insufficient. Further, it was confirmed that the aqueous coating agent of Comparative Example 3 was remarkably inferior in storage stability after 1 month and blending stability with an acidic aqueous solution.
- Comparative Example 4 is an example of an aqueous coating agent using a cationic emulsifier instead of a quaternary ammonium salt. It can be confirmed that the coating film of the aqueous coating agent of Comparative Example 4 is remarkably inferior in hot water resistance and the like, and has insufficient chemical resistance (acid resistance and alkali resistance), primary adhesion to a plastic substrate and corrosion resistance. It was. Moreover, it was confirmed that the aqueous coating agent of Comparative Example 4 was insufficient in storage stability after 1 month and blending stability with respect to the acidic aqueous solution.
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Abstract
Description
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート49質量部、メチルメタクリレート48質量部、ジメチルアミノエチルメタクリレート2質量部、及び、メタクリル酸1質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-1)を135質量部調製した。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート46.3質量部、メチルメタクリレート48質量部、ジメチルアミノエチルメタクリレート4質量部、及び、アクリル酸1.7質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-2)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(2)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート45質量部、メチルメタクリレート44質量部、ジメチルアミノエチルメタクリレート9質量部、及び、アクリル酸2質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-3)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(3)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート43質量部、メチルメタクリレート42質量部、ジメチルアミノエチルメタクリレート8質量部、及び、アクリル酸7質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-4)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(4)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート48質量部、メチルメタクリレート47質量部、ジメチルアミノエチルメタクリレート2質量部、及び、アクリル酸3質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-5)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(5)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート48質量部、メチルメタクリレート49質量部、ジメチルアミノエチルメタクリレート1.5質量部、及び、メタクリル酸1.5質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-6)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(6)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート48質量部、メチルメタクリレート48質量部、ジメチルアミノエチルメタクリレート3質量部、及び、メタクリル酸1質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-7)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(7)を得た。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート47質量部、メチルメタクリレート46質量部、ジメチルアミノエチルメタクリレート6質量部、及び、アクリル酸1質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-8)を135質量部調製した。それ以降の操作を実施例1と同様の方法で行い、ビニル重合体の水分散液からなる水性コーティング剤(8)を得た。
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、脱イオン水110質量部と、カチオーゲンTML(第一工業製薬株式会社製、アルキルトリメチルアンモニウムクロライド、30質量%水溶液)20質量部を供給し、窒素ガスを吹き込みながら前記反応容器内の温度を70℃に調整した。続いて、前記反応容器に、撹拌下、2’,2-アゾビス(2-アミジノプロパン)0.04質量部を脱イオン水2質量で希釈した溶液を供給した後、実施例1と同様の方法で得られた単量体プレエマルジョン(X-1)135質量部の一部(5.4質量部)を供給し、前記反応容器内の温度を70±2℃に保った状態で45分間反応させた。
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、脱イオン水110質量部と、カチオーゲンTMS(第一工業製薬株式会社製、アルキルトリメチルアンモニウムクロライド、25質量%水溶液)8質量部を供給し、窒素ガスを吹き込みながら前記反応容器内の温度を70℃に調整した。続いて、前記反応容器に、撹拌下、2’,2-アゾビス(2-アミジノプロパン)0.04質量部を脱イオン水2質量で希釈した溶液を供給した後、実施例1と同様の方法で得られた単量体プレエマルジョン(X-1)135質量部の一部(5.4質量部)を供給し、前記反応容器内の温度を70±2℃に保った状態で45分間反応させた。
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、脱イオン水110質量部と、カチオーゲンBC-50(第一工業製薬株式会社製、アルキルジメチルベンジルアンモニウムクロライド、50質量%水溶液)4質量部を供給し、窒素ガスを吹き込みながら前記反応容器内の温度を70℃に調整した。続いて、前記反応容器に、撹拌下、2’,2-アゾビス(2-アミジノプロパン)0.04質量部を脱イオン水2質量で希釈した溶液を供給した後、実施例1と同様の方法で得られた単量体プレエマルジョン(X-1)135質量部の一部(5.4質量部)を供給し、前記反応容器内の温度を70±2℃に保った状態で45分間反応させた。
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、脱イオン水110質量部と、カチオーゲンES-L(第一工業製薬株式会社製、アルキルジメチルエチルアンモニウムエチルサルフェート、50質量%水溶液)4質量部を供給し、窒素ガスを吹き込みながら前記反応容器内の温度を70℃に調整した。続いて、前記反応容器に、撹拌下、2’,2-アゾビス(2-アミジノプロパン)0.04質量部を脱イオン水2質量で希釈した溶液を供給した後、実施例1と同様の方法で得られた単量体プレエマルジョン(X-1)135質量部の一部(5.4質量部)を供給し、前記反応容器内の温度を70±2℃に保った状態で45分間反応させた。
次いで、前記反応容器に、70±2℃を維持した状態で、2’,2-アゾビス(2-アミジノプロパン)0.12質量部を脱イオン水6質量部で希釈した溶液とを、240分かけて滴下するとともに、前記単量体プレエマルジョン(X-1)の残りを180分かけて滴下した。前記単量体プレエマルジョン(X-1)を滴下後、冷却することで、ビニル重合体の水分散液からなる水性コーティング剤(12)を得た。
脱イオン水30質量部と、カチオーゲンTML(第一工業製薬株式会社製、アルキルトリメチルアンモニウムクロライド、30質量%水溶液)6.7質量部とを含有する容器内に、n-ブチルアクリレート49質量部、メチルメタクリレート48質量部、ジメチルアミノエチルメタクリレート2質量部、及び、メタクリル酸1質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-9)を136.7質量部調製した。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)6.5質量部とを含有する容器内に、n-ブチルアクリレート49質量部、メチルメタクリレート48質量部、ジメチルアミノエチルメタクリレート2質量部、及び、メタクリル酸1質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-10)を136.5質量部調製した。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート48質量部、メチルメタクリレート48質量部、及び、ジメチルアミノエチルメタクリレート4質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-11)を135質量部調製した。
脱イオン水30質量部と、ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)5質量部とを含有する容器内に、n-ブチルアクリレート50質量部、メチルメタクリレート48質量部、及び、アクリル酸2質量部を順に供給し、撹拌することによって、単量体プレエマルジョン(X-12)を135質量部調製した。
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、脱イオン水110質量部と、アセタミン24(花王株式会社製、アルキルアミン塩)2質量部を供給し、窒素ガスを吹き込みながら前記反応容器内の温度を70℃に調整した。前記反応容器に、撹拌下、2’,2-アゾビス(2-アミジノプロパン)0.04質量部を脱イオン水2質量で希釈した溶液を供給した後、実施例1と同様の方法で得られた単量体プレエマルジョン(X-1)135質量部の一部(5.4質量部)を供給し、前記反応容器内の温度を70±2℃に保った状態で45分間反応させた。
実施例及び比較例で得た水性コーティング剤を、バーコーターを使用して乾燥後の膜厚が約5μmになるように、アセトンで脱脂した55質量%アルミニウム-亜鉛系合金メッキ鋼板に塗工し、雰囲気温度100℃の乾燥機に60秒間入れて乾燥し、塗膜を作製した。その後、室温で3日間養生して試験片とした。前記試験片を50℃の温水に浸漬し、100分後の塗膜の劣化状態を目視で観察し、下記の基準にしたがって、耐温水性を評価した。
B:塗膜表面のごく一部に若干の変色が見られたが実用上問題ないレベルであった。
C:塗膜全体に膨れ等が見られた。
D:塗膜が剥離し、基材が露出した。
実施例及び比較例で得た水性コーティング剤を、バーコーターを使用して乾燥後の膜厚が約5μmになるように、アセトンで脱脂した55質量%アルミニウム-亜鉛系合金メッキ鋼板に塗工し、雰囲気温度100℃の乾燥機に60秒間入れて乾燥し、塗膜を作製した。その後、室温で3日間養生したものを試験片とした。前記試験片を構成する塗膜の上に1N塩酸をスポットで置き、100分間静置後の塗膜の劣化状態を目視で観察し、下記の基準にしたがって、耐薬品性(耐酸性)を評価した。
B:塗膜の表面に若干の黄変が見られたが実用上問題ないレベルであった。
C:塗膜の表面が著しく変色した。
D:塗膜が溶解し、基材が露出した。
実施例及び比較例で得た水性コーティング剤を、バーコーターを使用して乾燥後の膜厚が約5μmになるように、アセトンで脱脂した55質量%アルミニウム-亜鉛系合金メッキ鋼板に塗工し、雰囲気温度100℃の乾燥機に60秒間入れて乾燥し、塗膜を作製した。その後、室温で3日間養生したものを試験片とした。前記試験片を構成する塗膜の上に5質量%水酸化ナトリウム水溶液をスポットで置き、60分間静置後の塗膜の劣化状態を目視で観察し、下記の基準にしたがって、耐薬品性(耐アルカリ性)を評価した。
B:塗膜の表面の一部に若干の変色が見られたが実用上問題ないレベルであった。
C:塗膜の表面に変色が見られた。
D:塗膜が溶解し、基材が露出した。
実施例及び比較例で得た水性コーティング剤を、下記の4種類のプラスチック基材上に3mil(0.0762mm)のアプリケーターを用いて塗工し、60℃で30分間乾燥後、25℃で2日間養生した塗膜を作製した。得られた塗膜の表面に、JIS K-5400に準じて、1mm角100個の碁盤目のセロテープ(登録商標)剥離試験を実施した。剥離しない碁盤目数を計測し、下記の基準にしたがって、プラスチック基材に対する密着性(一次密着性)を評価した。
・アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)からなる基材(以下、「ABS」と略記する。)
・ポリカーボネート樹脂(PC樹脂)からなる基材(以下、「PC」と略記する。)
・アクリロニトリル-ブタジエン-スチレン樹脂とポリカーボネート樹脂とのポリマーアロイ(ABS/PC樹脂)からなる基材(以下、「ABS/PC」と略記する。)
・ポリメチルメタクリレート樹脂(PMMA樹脂)からなる基材(以下、「PMMA」と略記する。)
B:剥離しない碁盤目数が60以上90未満であった。
C:剥離しない碁盤目数が40以上60未満であった。
D:剥離しない碁盤目数が40未満であった。
上記の密着性(一次密着性)と同様に塗膜を作製して試験片とし、試験片を50℃の温水に100分間浸漬させた後、取り出し、表面の水を拭き取った後、上記の密着性(一次密着性)と同様に剥離試験を実施し、上記の基準にしたがって、プラスチック基材に対する密着性(温水密着性)を評価した。
実施例及び比較例で得た水性コーティング剤を、バーコーターを使用して乾燥後の膜厚が約5μmになるように、アセトンで脱脂した55質量%アルミニウム-亜鉛系合金メッキ鋼板に塗工し、雰囲気温度100℃の乾燥機に60秒間入れて乾燥し、塗膜を作製した。その後、室温で3日間養生したものを試験片とした。
A:錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して5%未満であった。
B:錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して5%以上30%未満であった。
C:錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して30%以上60%未満であった。
D:錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して60%以上であった。
A:クロスカット部の周辺に錆の発生は見られず、錆に起因した塗膜の剥離等も見られなかった。
B:クロスカット部の周辺にわずかに錆の発生が見られたが、それに起因した塗膜の剥離や膨れは見られなかった。
C:クロスカット部の周辺に広く錆の発生が見られ、それに起因した塗膜の剥離や膨れが見られたものの、流れ錆は見られなかった。
D:クロスカット部の周辺に広く錆の発生と、それに起因した塗膜の剥離や膨れが見られ、さらに流れ錆による塗膜の汚染が見られた。
実施例及び比較例で得た水性コーティング剤80mLを、100mLのガラス瓶に入れ、雰囲気温度40℃の乾燥機内に保存し、1週間保存後と1か月保存後の水性コーティング剤の外観を目視で観察し、下記の基準にしたがって、保存安定性を評価した。
B:ガラス瓶の底に凝集物や沈殿が底面の0~10%に確認された。
C:ガラス瓶の底に凝集物や沈殿が底面の10~50%に確認された。
D:ガラス瓶の底に凝集物や沈殿が底面の50~100%に確認された。
実施例及び比較例で得た水性コーティング剤30mLを、100mLのガラス瓶に入れ、0.1Mのクエン酸39.5mL及び0.2Mのリン酸水素二ナトリウム溶液14.1mLを混合して得られたクエン酸-リン酸緩衝液(pH=3.4)3mLを加えて均一に混合した後、得られた液の外観を目視で観察し、下記の基準にしたがって、酸性水溶液に対する配合安定性を評価した。
B:ガラス瓶の底に凝集物や沈殿が底面の0~10%に確認された。
C:ガラス瓶の底に凝集物や沈殿が底面の10~50%に確認された。
D:ガラス瓶の底に凝集物や沈殿が底面の50~100%に確認された。
実施例及び比較例で得た水性コーティング剤30mLを、100mLのガラス瓶に入れ、0.2Mのリン酸二水素ナトリウム溶液5.3mL及び0.2Mのリン酸水素二ナトリウム溶液94.7mLを混合して得られたリン酸緩衝液(pH=8.0)3mLを加えて均一に混合した後、得られた液の外観を目視で観察し、上記の基準にしたがって、アルカリ性水溶液に対する配合安定性を評価した。
BA:n-ブチルアクリレート
MMA:メチルメタクリレート
DM:N,N-ジメチルアミノエチルメタクリレート
MAA:メタクリル酸
AA:アクリル酸
TML:カチオーゲンTML(第一工業製薬株式会社製、アルキルトリメチルアンモニウムクロライド、30質量%水溶液)
BC-50:カチオーゲンBC-50(第一工業製薬株式会社製、アルキルジメチルベンジルアンモニウムクロライド、50質量%水溶液)
ES-L:カチオーゲンES-L(第一工業製薬株式会社製、アルキルジメチルエチルアンモニウムエチルサルフェート、50質量%水溶液)
アセタミン:アセタミン24(花王株式会社製、アルキルアミン塩)
XL-400:ノイゲンXL-400(第一工業製薬株式会社製、ポリオキシアルキレン分岐デシルエーテル)
Claims (9)
- 塩基性窒素原子含有基とカルボキシル基とを有するビニル重合体(A)、4級アンモニウム塩(B)及び水性媒体(C)を含有することを特徴とする水性コーティング剤。
- 前記4級アンモニウム塩(B)が、前記ビニル重合体(A)100質量部に対して、0.1~10質量部の範囲で含まれるものである請求項1又は2記載の水性コーティング剤。
- 前記ビニル重合体(A)が、30~700mmol/kgの塩基性窒素原子含有基を有し、かつ、50~1,200mmol/kgのカルボキシル基を有するものである請求項1~3のいずれか1項記載の水性コーティング剤。
- 前記ビニル重合体(A)中の塩基性窒素原子含有基とカルボキシル基とのモル比[塩基性窒素原子含有基/カルボキシル基]が、0.1~3の範囲である請求項1~4のいずれか1項記載の水性コーティング剤。
- さらに、ノニオン性乳化剤(D)を含有する請求項1~5のいずれか1項記載の水性コーティング剤。
- 前記ノニオン性乳化剤(D)が、前記ビニル重合体(A)100質量部に対して、0.1~10質量部の範囲で含まれるものである請求項6項記載の水性コーティング剤。
- 請求項1~7のいずれか1項記載の水性コーティング剤の塗膜を有することを特徴とする物品。
- 請求項1~7のいずれか1項記載の水性コーティング剤の塗膜を有することを特徴とする金属物品。
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US14/901,905 US9803087B2 (en) | 2013-07-09 | 2014-06-12 | Aqueous coating agent and article using same |
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US20160369106A1 (en) | 2016-12-22 |
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EP3020772A4 (en) | 2017-01-04 |
JP5831671B2 (ja) | 2015-12-09 |
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CN105378007A (zh) | 2016-03-02 |
US9803087B2 (en) | 2017-10-31 |
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