WO2015015827A1 - Composition de revêtement aqueuse - Google Patents

Composition de revêtement aqueuse Download PDF

Info

Publication number
WO2015015827A1
WO2015015827A1 PCT/JP2014/057360 JP2014057360W WO2015015827A1 WO 2015015827 A1 WO2015015827 A1 WO 2015015827A1 JP 2014057360 W JP2014057360 W JP 2014057360W WO 2015015827 A1 WO2015015827 A1 WO 2015015827A1
Authority
WO
WIPO (PCT)
Prior art keywords
core
meth
aqueous
acrylic resin
acrylate
Prior art date
Application number
PCT/JP2014/057360
Other languages
English (en)
Japanese (ja)
Inventor
日高　貴弘
片岡　泰之
勇也 平本
Original Assignee
関西ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to JP2014543375A priority Critical patent/JP5649763B1/ja
Publication of WO2015015827A1 publication Critical patent/WO2015015827A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to an aqueous coating composition for can coating, which is capable of forming a coating film excellent in storage stability of paint and excellent in water resistance, corrosion resistance and processability.
  • organic solvent-type paints containing bisphenol A type epoxy resins and phenolic resin curing agents have been generally used as paints for the inner surface of cans.
  • organic solvent-type paints containing bisphenol A type epoxy resins and phenolic resin curing agents have been generally used as paints for the inner surface of cans.
  • the paint for the inner surface of the can is being replaced by a water-based paint from an organic solvent-type paint.
  • water-based paint for example, a water-based paint containing an epoxy-modified acrylic resin obtained by reacting an epoxy resin and a carboxyl group-containing acrylic resin has been proposed (see Patent Document 1).
  • an epoxy resin manufactured using a raw material containing bisphenol A is generally used in order to obtain good coating workability and coating film performance.
  • bisphenol A is suspected to be an exogenous endocrine disrupting chemical
  • an aqueous paint for can inner surfaces that does not contain a resin produced using a raw material containing bisphenol A is desired.
  • a coating composition using a resin not containing bisphenol A as a raw material for example, a polymerizable unsaturated monomer containing a carboxyl group-containing polymerizable unsaturated monomer is graft-polymerized to a polyester having a radical reactive unsaturated group.
  • aqueous coating composition for inner surfaces of cans containing an acrylic-modified polyester resin and a cross-linked product of a resol type phenol resin see Patent Document 2.
  • the film obtained from such a composition may have poor retort whitening resistance.
  • a can inner surface aqueous coating composition containing an acrylic resin emulsion obtained by an emulsion polymerization method using a surfactant contains a surfactant in the cured coating film, and this surfactant is cured.
  • Patent Documents 3 to 5 disclose aqueous coating compositions for inner surfaces of cans using an acrylic resin emulsion produced by soap-free polymerization without using a surfactant.
  • Patent Document 3 discloses that an aqueous dispersion obtained by dispersing a mixture of ethylenically unsaturated monomers in an aqueous medium using an aqueous acrylic polymer is present in an aqueous resin different from the aqueous acrylic polymer.
  • An aqueous resin composition for can-making coatings containing a dispersion of a thermosetting aqueous resin obtained by radical polymerization under pressure is disclosed.
  • Patent Document 4 discloses an ethylenically unsaturated monomer in the presence of an aqueous solution or emulsion of a carboxyl group-containing component containing an acrylic copolymer having a carboxyl group, a basic compound, and water.
  • An aqueous coating composition for can inner surface coating containing an emulsion of a composite polymer obtained by radical polymerization of an emulsified component to be contained is disclosed.
  • Patent Document 5 discloses ethylenic unsaturation in the presence of an aqueous solution or emulsion of a polymer containing a carboxyl group-containing component containing a carboxyl group-containing acrylic copolymer, a basic compound, and water.
  • An aqueous paint comprising a polymer emulsion obtained by radical polymerization of a component to be emulsified containing a monomer using a nonionic water-soluble radical initiator is disclosed.
  • water-based paint compositions disclosed in Patent Documents 3 to 5 may be expensive due to complicated manufacturing processes.
  • water-based paint compositions using these acrylic resin-based emulsions may have poor storage stability, and coating films obtained from these water-based paint compositions have water resistance, corrosion resistance, and processability.
  • the coating film obtained from the epoxy-modified acrylic resin-based water-based paint disclosed in Patent Document 1 may be inferior.
  • An object of the present invention is an aqueous coating composition for can coating that does not contain a resin produced using bisphenol A or a raw material containing bisphenol A, and has excellent storage stability of the coating, water resistance, corrosion resistance, and workability. It is to provide an aqueous coating composition for can coating that can form a coating film excellent in, and a coated can coated with the coating composition.
  • the present inventors are an aqueous coating composition for can coating comprising core-shell type acrylic resin particles (A) comprising a shell part and a crosslinked core part,
  • the glass transition temperature of the acrylic resin constituting the shell portion is in the range of 35 to 105 ° C.
  • the glass transition temperature of the acrylic resin constituting the core portion is in the range of ⁇ 10 to 25 ° C.
  • the aqueous coating composition for can coating in which the mass of the core-shell type acrylic resin particles (A) has an acid group is in the range of 10 to 90% by mass based on the total mass of the core part and the shell part It was found that the coating film obtained from the water-based coating composition was excellent in water resistance, corrosion resistance, and processability, and thus completed the present invention.
  • the aqueous coating composition of the present invention is excellent in storage stability, and can form a coating film excellent in water resistance, corrosion resistance, and workability. Moreover, the core-shell type acrylic resin particles having a crosslinked core part used in the aqueous coating composition of the present invention can be produced at low cost.
  • the water-based coating composition for can coating of the present invention includes core-shell type acrylic resin particles (A) (hereinafter simply referred to as “core-shell”) having a shell part and a crosslinked core part.
  • core-shell type acrylic resin particles (A) ”) and a glass transition temperature of the acrylic resin constituting the shell portion (hereinafter referred to as“ shell Tg ”).
  • shell Tg glass transition temperature of the acrylic resin constituting the shell portion
  • core Tg glass transition temperature of the acrylic resin constituting the core portion
  • the mass of the core part is in the range of 10 to 90% by mass based on the total mass of the core part and the shell part, and the core-shell type acrylic resin particles (A) have an acid group. .
  • Core-shell type acrylic resin particles (A) The core-shell type acrylic resin particles (A) can be obtained by conventionally known multistage emulsion polymerization using a radically polymerizable unsaturated monomer.
  • the core-shell type acrylic resin particles (A) have a radically polymerizable unsaturated monomer (hereinafter sometimes referred to as “polyvinyl monomer”) having two or more radically polymerizable unsaturated groups in one molecule.
  • a monomer mixture containing a radically polymerizable unsaturated monomer having a functional group other than an unsaturated group capable of reacting in a complementary manner to form a chemical bond (hereinafter referred to as “core monomer mixture (a1)”)
  • the first step of emulsion polymerization is carried out in the presence of water to obtain an aqueous dispersion of crosslinked core particles, and then a radical polymerizable property for forming a shell portion in the aqueous dispersion. It can be obtained by adding a monomer mixture (a2) of unsaturated monomers (hereinafter sometimes referred to as “shell monomer mixture (a2)”) and performing emulsion polymerization in the second stage.
  • the polyvinyl monomer can be used in an amount in the range of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the mass of the core monomer mixture (a1).
  • radical polymerizable unsaturated monomer having a functional group other than the unsaturated group capable of forming a chemical bond by complementary reaction examples include, for example, N-alkoxymethyl (meth) acrylamide, ⁇ - (meth)
  • functional groups such as acryloyloxypropyltrimethoxysilane which can react with each other in a complementary manner to form a chemical bond, or glycidyl group and carboxylic acid in the combination of (meth) acrylic acid glycidyl ester and (meth) acrylic acid And the like, in which two different functional groups can react complementary to form a chemical bond such as an ester bond.
  • the cross-linking reaction in the core particle may be performed, for example, while forming the core particle in the emulsion polymerization in the first stage, or by adding an appropriate catalyst after forming the core particle, or forming a shell part. An appropriate catalyst may be added later.
  • radical polymerizable unsaturated monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
  • (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.
  • seed particles are obtained by emulsion polymerization using a small portion of the core monomer mixture (a1), and then the remaining core monomer mixture (a1) is emulsified in the presence of the seed particles.
  • An aqueous dispersion of core particles may be obtained by polymerization.
  • the core-shell type acrylic resin particles (A) can be obtained by adding the shell monomer mixture (a2) to the aqueous dispersion of the core particles and performing the second stage emulsion polymerization. At that time, the core-shell type acrylic resin particles (A) having two or more shell portions may be obtained by performing the second stage emulsion polymerization for forming the shell portion in two or more steps. At this time, the blending amount and monomer composition of the shell monomer mixture (a2) may be different at each stage.
  • the means for adding the core monomer mixture (a1) or the shell monomer mixture (a2) to the polymerization reaction tank there is no particular limitation on the means for adding the core monomer mixture (a1) or the shell monomer mixture (a2) to the polymerization reaction tank.
  • the core monomer mixture (a1) may be added all at once, continuously, or intermittently.
  • the shell monomer mixture (a2) may be added all at once, continuously, or intermittently.
  • the core-shell type acrylic resin particles (A) in the present invention have a shell Tg in the range of 35 to 105 ° C. and a core Tg in the range of ⁇ 10 to 25 ° C.
  • the shell Tg is lower than 35 ° C
  • the corrosion resistance of the obtained coating film may be inferior
  • the shell Tg is higher than 105 ° C
  • the workability of the obtained coating film may be inferior
  • the core Tg is lower than ⁇ 10 ° C.
  • the corrosion resistance of the obtained coating film may be inferior
  • the core Tg is higher than 25 ° C.
  • the workability of the obtained coating film may be inferior.
  • the glass transition temperature (Tg) can be calculated using the following formulas (1) and (2).
  • W1, W2,... represent the mass% of each monomer used in the copolymerization
  • T1, T2,... represent the Tg (° K) of the monomer homopolymer, respectively.
  • T1, T2,... are values according to Polymer Hand Book (Second Edition, edited by J. Brandup, E. H. Immergut).
  • the glass transition temperature of a homopolymer based on a monomer not described in this handbook is an actual measurement value for a homopolymer having a weight average molecular weight of about 20,000 to 50,000.
  • This measured value is obtained by vacuum suctioning a sample taken in a measuring cup to remove volatile components such as a solvent, and then using a differential scanning thermal analysis “DSC-50Q type” (trade name, manufactured by Shimadzu Corporation). Measure the amount of heat change in the range of -50 ° C to + 150 ° C at a rate of temperature increase of 3 ° C / min, and use the first baseline change point on the low temperature side.
  • DSC-50Q type trade name, manufactured by Shimadzu Corporation
  • the shell Tg is based on the composition of all the monomers used in the shell monomer mixture (a2). , Values calculated by the above formulas.
  • the core Tg is based on a composition in which the polyvinyl monomer is excluded from the core monomer mixture (a1). It is a value calculated by each of the above formulas.
  • the mass of the core part in the core-shell type acrylic resin particles (A) is 10 to 90% by mass, preferably 20 to 70% by mass, more preferably 30 to 60% by mass based on the total mass of the core part and the shell part. Within range. When the mass of the core part is less than 10% by mass, the processability of the obtained coating film may be inferior, and when it is more than 90% by mass, the corrosion resistance of the obtained coating film may be deteriorated.
  • the core-shell type acrylic resin particles (A) of the aqueous coating composition of the present invention preferably have an acid group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group from the viewpoint of storage stability.
  • the acid value derived from these acid groups is in the range of 0.5 to 100 mgKOH / g, preferably 20 to 90 mgKOH / g, more preferably 40 to 80 mgKOH / g. When the acid value is larger than 100 mgKOH / g, the water resistance of the resulting coating film may be lowered.
  • radical polymerization initiator examples include known compounds such as dibenzoyl peroxide, dioctanoyl peroxide, and dilauroyl.
  • Peroxide distearoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate , Organic peroxides such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis 2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), 2,2′-azobis [2 -(2-imidazolin-2-yl) propane] hydrochloride or sulfate, 2,2'-azobis [2-methylpropionamidine] hydrochloride, 2,2'-
  • the peroxide-based polymerization initiator may optionally be organic acids such as ascorbic acid, erythorbic acid, tartaric acid, citric acid, salts of these organic acids, tertiary amines, saccharides, mercaptans, pyro-suboxides.
  • organic acids such as ascorbic acid, erythorbic acid, tartaric acid, citric acid, salts of these organic acids, tertiary amines, saccharides, mercaptans, pyro-suboxides.
  • One or more known reducing agents such as ferrous iron, Rongalite, and thiourea dioxide may be added and used as a redox initiator.
  • the radical polymerization initiator can be used in an amount in the range of 0.01 to 5% by mass, preferably 0.1 to 1% by mass, based on the total mass of the radical polymerizable unsaturated monomers used in the emulsion polymerization. .
  • the method for adding the radical polymerization initiator is not particularly limited, and can be appropriately selected depending on the type, mass, etc. For example, it may be added to the monomer mixture or water in advance, and added at the same time during polymerization. Alternatively, it may be dropped.
  • Surfactants that can be used in the emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants having both anionic and cationic properties. Conventionally known compounds such as these can be employed.
  • surfactant examples include anionic surfactants such as sodium salts and ammonium salts of acids such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylphosphoric acid, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, Oxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene mono Nonionic boundaries such as oleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate Active agent, dimethyl alkyl betaines, dimethyl alkyl lauryl betaines, mention may be made of zwitterionic surfactants such as alkyl glycine.
  • a reactive anionic surfactant having a polymerizable unsaturated group can also be used.
  • the reactive anionic surfactant include sodium salts and ammonium salts of sulfonic acid compounds having a radical reactive unsaturated group such as an allyl group, a (meth) acryloyl group, a propenyl group, and a butenyl group.
  • the surfactant is used in an amount of 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of radically polymerizable unsaturated monomers used for emulsion polymerization. It is preferable in terms of water resistance.
  • the average particle diameter of the core-shell type acrylic resin particles (A) of the aqueous coating composition of the present invention is preferably from 80 to 500 nm, more preferably from 150 to 300 nm, from the viewpoint of storage stability.
  • the average particle size was measured using a submicron particle analyzer N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring device) diluted with deionized water to a concentration suitable for measurement. (Measured at about 20 ° C.)
  • the emulsion polymerization after the first stage and the second stage can be carried out in the presence of water at a polymerization temperature of 40 ° C. to 98 ° C. for a polymerization time of about 1 to 20 hours.
  • the core-shell type acrylic resin particles (A) in addition to the above-described components such as water, a mixture of radically polymerizable unsaturated monomers, a radical polymerization initiator, and a surfactant, a reducing agent, if desired, Organic solvents, polymer compounds, chain transfer agents and the like may be used.
  • the aqueous coating composition of the present invention may further contain a water-soluble or water-dispersible aqueous resin (B).
  • a water-soluble or water-dispersible aqueous resin (B) a known resin that is water-soluble or water-dispersible and does not use bisphenol A as a raw material can be used.
  • an acrylic resin, an acrylic resin-modified polyester resin, a polyester resin, Urethane resins, olefin resins, polyoxyalkylene resins and resins obtained by modifying these resins by a known method can be used alone or in combination of two or more.
  • the aqueous resin (B) is 0 to 20% by mass, preferably 1 to 15% by mass, based on the solid content of the core-shell type acrylic resin particles (A). Preferably, it can be used in an amount in the range of 2 to 10% by mass.
  • the water-based coating composition of the present invention contains the water-based resin (B), it is possible to adjust to improve performance such as water resistance, corrosion resistance, and workability of the obtained coating film.
  • the weight average molecular weight of the aqueous resin (B) of the aqueous coating composition of the present invention is from 3,000 to 200,000, preferably from 5,000 to 150,000, more preferably from 8,000 to 120,000 from the viewpoint of storage stability and corrosion resistance of the resulting coating film. Those within range can be used.
  • the weight average molecular weight or number average molecular weight is the weight average molecular weight or number average molecular weight measured by gel permeation chromatography (“HLC8120GPC” manufactured by Tosoh Corporation), and the polystyrene weight average molecular weight or number. It is a value converted based on the average molecular weight.
  • Measurements are “TSKgel G-4000H ⁇ L”, “TSKgel G-3000H ⁇ L”, “TSKgel G-2500H ⁇ L”, “TSKgel G-2000H ⁇ L” (both manufactured by Tosoh Corporation, trade name)
  • the measurement is carried out under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
  • the aqueous resin (B) has a glass transition temperature of ⁇ 20 ° C. or higher, preferably ⁇ 10 to 130 ° C., more preferably 0 to 80 ° C., from the viewpoint of processability of the resulting coating film. Can be used.
  • the glass transition temperature was measured by vacuum suctioning a sample taken in a measuring cup and removing the solvent, and then using a differential scanning thermal analysis “DSC-50Q type” (trade name, manufactured by Shimadzu Corporation). Measure the heat change in the range of ⁇ 60 ° C. to + 150 ° C. at a rate of temperature increase of 3 ° C./min and use the first baseline change point on the low temperature side.
  • the aqueous resin (B) in the aqueous coating composition of the present invention is preferably a carboxyl group-containing resin from the viewpoint of storage stability.
  • the acid value of the aqueous resin (B) is in the range of 20 to 250 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 to 150 mgKOH / g, from the viewpoint of water resistance of the resulting coating film.
  • Some or all of the carboxyl groups of the aqueous resin (B) may be neutralized in advance with a base compound such as an amine before blending the paint, or include a base compound such as an amine when blending the paint. You may neutralize by mixing with another coating-material component.
  • the acrylic resin is a resin that does not substantially have a crosslinked structure, and is conventionally known, for example, solution polymerization, dispersion polymerization, emulsion polymerization, bulk polymerization, etc. It can be produced by radical polymerization.
  • the radically polymerizable unsaturated monomer that can be used for the production of the acrylic resin includes, as appropriate, a plurality of radically polymerizable unsaturated monomers that can be used for the production of the core-shell type acrylic resin particles (A). These monomers can be selected and used.
  • the radical polymerization initiator that can be used for the production of the acrylic resin is appropriately selected from those exemplified above as the radical polymerization initiator that can be used for the production of the core-shell type acrylic resin particles (A). Can be used.
  • solvents examples include known organic solvents such as water, toluene, butanol, and butyl cellosolve. These solvents can be used alone or in combination of two or more. can do.
  • the polymerization conditions in the solution polymerization are usually that the reaction temperature is room temperature to about 200 ° C., and the reaction time is about 2 to 10 hours.
  • the aqueous resin (B) preferably has crosslinking reactivity from the viewpoint of water resistance of the resulting coating film.
  • the aqueous resin (B) includes a crosslinking reaction between the aqueous resins (B), a crosslinking reaction between the aqueous resin (B) and the core-shell type acrylic resin particles (A), an aqueous resin (B) and a resol type phenolic resin (C1 described later). ) And / or crosslinking reaction with any crosslinking reaction such as crosslinking reaction with amino resin (C2).
  • the acrylic resin (B) is an acrylic resin
  • examples of the acrylic resin having crosslinking reactivity include N-alkoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxy It can be obtained by copolymerizing a radical polymerizable unsaturated monomer having a crosslinkable functional group such as ethyl (meth) acrylate with another radical polymerizable unsaturated monomer.
  • the aqueous coating composition of the present invention may further contain a resol type phenol resin (C1) and / or an amino resin (C2) as a curing agent.
  • a resol type phenol resin (C1) and / or amino resin (C2) as a curing agent.
  • Examples of the resol type phenol resin (C1) include a phenol resin in which a methylol group is introduced by a condensation reaction of a phenol compound such as phenol or bisphenol A and formaldehyde in the presence of a reaction catalyst; Some of them are alkyl etherified with an alcohol having 1 to 6 carbon atoms.
  • phenol compound examples include bifunctional phenol compounds such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol; coalic acid, m-cresol, Trifunctional phenolic compounds such as m-ethylphenol, 3,5-xylenol, m-methoxyphenol; tetrafunctional phenolic compounds such as bisphenol A and bisphenol F; Can be used.
  • bifunctional phenol compounds such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol
  • coalic acid m-cresol
  • Trifunctional phenolic compounds such as m-ethylphenol, 3,5-xylenol, m-methoxyphenol
  • tetrafunctional phenolic compounds such as bisphenol A
  • formaldehydes examples include formaldehyde, paraformaldehyde or trioxane, and these can be used alone or in combination of two or more.
  • the alcohol used for alkyl etherifying a part of the methylol group of the methylolated phenol resin a monohydric alcohol having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, can be suitably used. Suitable monohydric alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.
  • the resol type phenol resin (C1) has a number average molecular weight of 200 to 2000, preferably 300 to 1200, and an average number of methylol groups per nucleus of the benzene nucleus of 0.3 to 3.0. Preferably, it is within the range of 0.5 to 3.0.
  • a coating film exhibiting good corrosion resistance can be obtained even in a portion where the carboxylic acid formaldehyde resin obtained by condensation reaction of carboxylic acid and formaldehyde has undergone impact processing.
  • amino resin (C2) methylol obtained by reaction of an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like with an aldehyde component such as formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc.
  • an amino acid resin is mentioned.
  • Those obtained by etherifying the methylol group of this methylolated amino resin with a lower alcohol having 1 to 6 carbon atoms are also included in the amino resin (C2).
  • the amino resin (C2) is preferably a lower alkyl etherified melamine resin or a lower alkyl etherified benzoguanamine resin obtained by etherifying a part or all of the methylol group of a methylol melamine resin or a methylol benzoguanamine resin with a lower alcohol.
  • the lower alcohol used in the etherification is preferably methyl alcohol, ethyl alcohol, isobutyl alcohol, or n-butyl alcohol. These alcohols may be used alone or in combination of two or more. Can do.
  • the melamine resin include, for example, Yuban 20SE, 225 (all manufactured by Mitsui Toatsu Co., Ltd.), Super Becamine J820-60, L-117-60, L-109-65, Butyl etherified melamine resins such as 47-508-60, L-118-60, G821-60 (all manufactured by Dainippon Ink & Chemicals, Inc.); Cymel 300, 303, 325, 327, 350, 730, 736, 738 (all manufactured by Mitsui Cytec Co., Ltd.), Melan 522, 523 (all manufactured by Hitachi Chemical Co., Ltd.), Nicarak MS001, MX430, MX650 (all manufactured by Sanwa) Chemical Co., Ltd.), Sumimar M-55, M-100, M-40S (all manufactured by Sumitomo Chemical Co., Ltd.), Resimin 740, 747 (Izu) Monsanto Co., Ltd.) and other methyl etherified melamine resins; Cymel
  • benzoguanamine resin examples include Cymel 1123 (mixed etherified benzoguanamine resin of methyl ether and ethyl ether), Cymel 1123-10 (mixed etherified benzoguanamine resin of methyl ether and butyl ether), Cymel 1128 (butyl etherified benzoguanamine). Resin), Mycoat 102 (methyl etherified benzoguanamine resin) (all manufactured by Mitsui Cytec Co., Ltd.), and the like.
  • the aqueous coating composition of the present invention includes the core-shell type acrylic resin particles (A), and may further include an aqueous resin (B), a resol type phenolic resin (C1), an amino resin (C2) and the like as necessary. Good.
  • the water dispersible resin (B) is in the range of 0 to 20% by mass, preferably 2 to 15% by mass, more preferably 3 to 10% by mass, based on the solid content mass of the core-shell type acrylic resin particles (A). Can be used in quantity. When there is more usage-amount of water-dispersible resin (B) than 20 mass%, the water resistance of the coating film obtained may fall.
  • the resol type phenol resin (C1) and the amino resin (C2) have a total mass of (C1) and (C2) of 0 to 20% by mass based on the solid content mass of the core-shell type acrylic resin particles (A), preferably It can be used in an amount in the range of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. If the total use amount of the resol type phenolic resin (C1) and the amino resin (C2) is more than 20% by mass, the resulting coating film may have poor water resistance and workability.
  • the aqueous coating composition of the present invention may be prepared by neutralizing a part or all of the carboxyl groups in the core-shell type acrylic resin particles (A) with a basic compound, and then further using an aqueous resin (You may add raw materials, such as B), a resol type phenol resin (C1), and an amino resin (C2). Moreover, when aqueous resin (B) has acid groups, such as a carboxyl group and a sulfonic acid group, you may use, after neutralizing a part or all of the said acid group with a basic compound.
  • any of ordinary inorganic bases and organic bases can be used.
  • the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
  • examples of the organic base include alkylamines such as ammonia, trimethylamine, triethylamine and butylamine: alcohol amines such as dimethylaminoethanol, diethanolamine and aminomethylpropanol; polyvalent amines such as ethylenediamine and diethylenetriamine; Examples include morpholine.
  • ammonia and volatile amines are preferable from the viewpoint of water resistance of the resulting coating film.
  • the water-based coating composition of the present invention can be used by appropriately mixing conventionally known raw materials such as organic solvents, antifoaming agents, surfactants, lubricants, waxes, pigments and the like as necessary. .
  • organic solvent examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, amyl alcohol, n-hexanol, octanol, 2 -Alkyl alcohols such as ethylhexyl alcohol; glycol ethers such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, hexyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol; methyl cellosolve acetate, ethyl cellosolve acetate Glycol ether esters, dioxane, dimethylformamide, tetrahydrofuran, methyl ethyl ketone, diacetone alcohol Or the like can
  • antifoaming agent examples include acrylic, vinyl ether, and dimethylpolysiloxane antifoaming agents, and two or more of these can be used in combination.
  • the water-based coating composition of the present invention can be applied to various base materials, such as untreated or surface-treated metal plates such as aluminum plates, steel plates, tin plates, etc., and epoxy-based, vinyl on these metal plates.
  • base materials such as untreated or surface-treated metal plates such as aluminum plates, steel plates, tin plates, etc., and epoxy-based, vinyl on these metal plates.
  • metal plates coated with a primer such as a system, and those obtained by processing these metal plates into cans.
  • the form of the can to which the water-based coating composition of the present invention is applied is a two-piece can composed of two parts, a lid part and a body part integrated with the bottom part, and three forms of a lid part, a bottom part, and a body part.
  • a three-piece can, a bottle can, and the like composed of parts can be mentioned, and the aqueous coating composition of the present invention can be applied to each part. Since the film obtained from the aqueous coating composition of the present invention is excellent in processability and corrosion resistance, it is suitable for coating a lid portion that repeatedly undergoes uneven deformation during the production process of a beverage can or the like.
  • the aqueous coating composition of the present invention can be used for painting the inner surface of the can, particularly for repairing the seam portion (joint portion) of the inner surface of the can, painting the outer surface of the can lid, the outer surface of the can such as a tab.
  • the substrate with the aqueous coating composition of the present invention various known methods such as roll coater coating, spray coating, dip coating, and electrodeposition coating can be applied. Of these, roll coater coating or spray coating is preferable.
  • the thickness of the coating film may be appropriately selected depending on the application, but is preferably about 3 to 20 ⁇ m in terms of dry film thickness.
  • the drying condition of the coated film is usually 10 seconds to 30 minutes under the condition that the maximum temperature of the material is 120 to 300 ° C., preferably 15 seconds to 10 minutes under the condition that the temperature is 200 to 280 ° C. Is within the range.
  • parts and % mean “parts by mass” and “% by mass”, respectively.
  • emulsion of shell monomer mixture (a2-1) 27 parts deionized water, 5 parts "Newcol 714-SF", 15 parts styrene, 10 parts methyl methacrylate, 5 parts isobutyl methacrylate, 5 parts ethyl acrylate, 10.1 parts 2-ethylhexyl acrylate, 1-hydroxyethyl acrylate 1 Part, 3.9 parts of methacrylic acid, and 0.05 part of ammonium persulfate were mixed and stirred to obtain an emulsion of the shell monomer mixture (a2-1).
  • an amount corresponding to 4% of the total mass of the emulsion of the core monomer mixture (a1-1) and 1 part of a 5% aqueous ammonium persulfate solution were added with stirring, and the mixture was kept at 85 ° C. for 15 minutes. Thereafter, while maintaining the temperature at 85 ° C., the entire remaining amount of the emulsion of the core monomer mixture (a1-1) was added dropwise over 2 hours and aged for 1 hour.
  • the obtained core-shell type acrylic resin particles A-1 are core-shell type acrylic resin particles having a crosslinked core part, and the average particle size is 180 nm (submicron particle size distribution measuring device “COULTER N4 type” (manufactured by Beckman Coulter). Used, diluted with deionized water and measured at 20 ° C.), and the solids concentration of the dispersion was 40% by weight.
  • the acid value of the core-shell type acrylic resin particles A-1 was 50 mgKOH / g.
  • Production Example 1 except that the composition of the emulsion of the core monomer mixture (a1-1) and the emulsion of the shell monomer mixture (a2-1) was changed as shown in Table 1-1 and Table 1-2 below. In the same manner, dispersions of core-shell type acrylic resin particles A-2 to A-16 were obtained.
  • a reaction vessel equipped with a heating and cooling device and equipped with a stirrer, a thermometer, a thermostat, a reflux condenser, a nitrogen introducing tube and a dropping device was attached with 95 parts of deionized water and 0.1 part of “New Coal 714-SF”.
  • the contents were heated to 85 ° C. while charging 1 part and stirring and mixing under a nitrogen stream.
  • an amount corresponding to 2% of the total mass of the emulsion of the monomer mixture (a17) and 1 part of a 5% aqueous solution of ammonium persulfate were added with stirring, and the mixture was kept at 85 ° C. for 15 minutes. Thereafter, while the temperature was maintained at 85 ° C., the entire remaining amount of the emulsion of the monomer mixture (a17) was dropped over 4 hours and aged for 1 hour.
  • the obtained single-layer acrylic resin particles A-17 were cross-linked single-layer acrylic resin particles having an average particle size of 180 nm (submicron particle size distribution measuring device “COULTER N4 type” (manufactured by Beckman Coulter, Inc.). The sample was diluted with deionized water and measured at 20 ° C.), and the solid content concentration of the dispersion was 40% by mass. The acid value of the single-layer acrylic resin particles A-17 was 50 mgKOH / g.
  • a reaction vessel equipped with a heating and cooling device and equipped with a stirrer, a thermometer, a thermostat, a reflux condenser, a nitrogen introducing tube and a dropping device was attached with 95 parts of deionized water and 0.1 part of “New Coal 714-SF”.
  • the contents were heated to 85 ° C. while charging 1 part and stirring and mixing under a nitrogen stream.
  • an amount corresponding to 2% of the total mass of the emulsion of the monomer mixture (a18) and 1 part of a 5% aqueous solution of ammonium persulfate were added with stirring, and the mixture was kept at 85 ° C. for 15 minutes. Thereafter, while the temperature was maintained at 85 ° C., the entire remaining amount of the emulsion of the monomer mixture (a18) was dropped over 4 hours and aged for 1 hour.
  • the obtained single-layer acrylic resin particles A-18 were cross-linked single-layer acrylic resin particles having an average particle size of 180 nm (submicron particle size distribution measuring device “COULTER N4 type” (manufactured by Beckman Coulter, Inc.). The sample was diluted with deionized water and measured at 20 ° C.), and the solid content concentration of the dispersion was 40% by mass. The acid value of the single-layer acrylic resin particles A-18 was 50 mgKOH / g.
  • the glass transition temperature, solid content concentration, acid value and average particle diameter of the obtained core-shell type acrylic resin particles A-1 to A-16 and single-layer type acrylic resin particles A-17 and A-18 are shown in Table 1 1 and Table 1-2.
  • a radical polymerizable unsaturated monomer mixture (30 parts of methyl methacrylate, 13 parts of butyl methacrylate, 10 parts of styrene, 17 parts of ethyl acrylate, 20 parts of methacrylic acid and 10 parts of N-butoxymethylacrylamide) and a polymerization initiator solution (t -A mixture of 2 parts of butyl peroxy-2-ethylhexanoate and 20 parts of propylene glycol npropyl ether) was dropped into the reactor with a metering pump over 4 hours. Aged for 0.5 hours.
  • a polymerization initiator solution (a mixed solution of 0.5 parts of t-butylperoxy-2-ethylhexanoate and 20 parts of propylene glycol n-propyl ether) was added dropwise over 0.5 hours. Aged for 2 hours. Thereafter, 13 parts of N, N-dimethylaminoethanol was added and stirred. Then, it was cooled to room temperature to obtain a solution of an acrylic aqueous resin (B-1) having a solid content of 40% by mass.
  • the acrylic aqueous resin (B-1) had a glass transition temperature of 30 ° C., an acid value of 130 mgKOH / g, and a weight average molecular weight of 30,000.
  • Example 1 250 parts (solid content 100 parts) of the dispersion of core-shell type acrylic resin particles A-1 having a solid content of 40% by mass obtained in Production Example 1 and CKS-3898 (trade name, Showa Denko KK) having a solid content of 50% by mass. 10 parts (5 parts solid content) and 15 parts butyl cellosolve are mixed with stirring with a disper, and the solid content is adjusted by adding deionized water. An aqueous coating composition E-1 having a content of 20% by mass was obtained.
  • Examples 2 to 11, Comparative Examples 1 to 9 In the same manner as in Example 1, each component was mixed with stirring according to each formulation shown in Table 3-1 and Table 3-2 below, and deionized water was added to the mixed mixture to adjust the solid content. Aqueous coating compositions E-2 to 11 and 17 to 25 having a solid content of 20% by mass were prepared. In addition, the compounding quantity of each component in a table
  • Example 12 A dispersion of core-shell type acrylic resin particles A-1 having a solid content of 40% by mass obtained in Production Example 1 and a solution of acrylic aqueous resin (B-1) having a solid content of 40% by mass and a solid content of 40% by mass 12.5 parts (5 parts solids), 10 parts CKS-3898 (5 parts solids) and 15 parts butyl cellosolve with stirring with a disper are mixed with deionized water.
  • aqueous coating composition E-12 having a solid content of 20% by mass.
  • Example 13 to 16 In the same manner as in Example 12, the respective components were mixed with stirring according to the respective formulations shown in Table 3-1 and Table 3-2 below, deionized water was added to adjust the solid content, and the solid content was 20% by mass. Aqueous coating compositions E-13 to 16 were prepared. In addition, the compounding quantity of each component in a table
  • test plate Each water-based paint composition obtained in the examples and comparative examples was coated on a # 0.251 aluminum plate having a thickness of 0.25 mm that had been subjected to a phosphoric acid chromate treatment so as to have a dry coating thickness of 5 ⁇ m. Then, it was cured by baking at 200 ° C. for 1 minute to obtain a test coating plate. The performance test was performed according to the following test method.
  • the test coating plate was made into a lid using a lid-making press to produce a can lid having a coating surface on the inner surface side.
  • the prepared can lid is immersed in boiling water at 100 ° C. for 10 minutes, and then the opening piece (tab) provided on the top surface of the can lid is pulled upward with the coating film surface facing downward.
  • the part was opened.
  • the peeling width of the coating film from the opening edge part of the opening part was measured, and the following reference

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement aqueuse permettant d'enduire des boîtes qui ne comprend pas de résine produite à l'aide de bisphénol A ou une matière première comprenant du bisphénol A, qui présente une excellente stabilité du revêtement en stockage et qui peut former un film de revêtement présentant une résistance à l'eau, une résistance à la corrosion et une aptitude au façonnage excellentes. La composition de revêtement aqueuse pour enduire des boîtes comprend des particules de résine acrylique de type cœur/enveloppe (A) dans lesquelles une partie formant cœur est réticulée. La température de transition vitreuse de la résine acrylique qui compose la partie formant enveloppe varie de 35 à 105 °C, la température de transition vitreuse de la résine acrylique qui compose la partie formant cœur varie de -10 à 25 °C, la masse de la partie formant cœur varie de 10 à 90 % en masse sur la base de la masse totale de la partie formant cœur et de la part formant enveloppe, et les particules de résine acrylique de type cœur/enveloppe (A) possèdent un groupe acide.
PCT/JP2014/057360 2013-08-01 2014-03-18 Composition de revêtement aqueuse WO2015015827A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014543375A JP5649763B1 (ja) 2013-08-01 2014-03-18 水性塗料組成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013-160743 2013-08-01
JP2013160743 2013-08-01
JP2013-167934 2013-08-13
JP2013167934 2013-08-13

Publications (1)

Publication Number Publication Date
WO2015015827A1 true WO2015015827A1 (fr) 2015-02-05

Family

ID=52431379

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/057360 WO2015015827A1 (fr) 2013-08-01 2014-03-18 Composition de revêtement aqueuse

Country Status (1)

Country Link
WO (1) WO2015015827A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016113561A (ja) * 2014-12-16 2016-06-23 関西ペイント株式会社 缶被覆用水性塗料組成物
WO2018169309A3 (fr) * 2017-03-15 2018-11-08 한화케미칼 주식회사 Émulsion, son procédé de production et procédé de formation d'une couche de revêtement l'utilisant
CN109810593A (zh) * 2017-11-22 2019-05-28 东洋油墨Sc控股株式会社 水性涂料、涂装板及被覆罐
CN109913060A (zh) * 2019-01-11 2019-06-21 河北晨阳工贸集团有限公司 水性丙烯酸氨基烤漆及其制备方法
JP2020002244A (ja) * 2018-06-27 2020-01-09 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および水性塗料組成物の製造方法
WO2020022073A1 (fr) * 2018-07-27 2020-01-30 関西ペイント株式会社 Composition de revêtement aqueuse
WO2020022077A1 (fr) * 2018-07-27 2020-01-30 関西ペイント株式会社 Composition de peinture à base d'eau
JP2020532613A (ja) * 2017-09-01 2020-11-12 エスダブリューアイエムシー・エルエルシー 多段階ポリマーラテックス、そのようなラテックスを含有するコーティング組成物、及びそれによりコーティングされた物品
WO2021084804A1 (fr) * 2019-11-01 2021-05-06 関西ペイント株式会社 Composition de revêtement à base d'eau
EP3676342A4 (fr) * 2017-09-01 2021-07-07 Swimc LLC Latex polymères à étages multiples, compositions de revêtement contenant de tels latex, et articles en étant revêtus
CN113620569A (zh) * 2021-08-29 2021-11-09 咸宁南玻光电玻璃有限公司 一种改善浮法工艺玻璃油墨附着力的方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0445102A (ja) * 1990-06-12 1992-02-14 Kansai Paint Co Ltd 乳化重合体の製造方法及びその製造方法で得られる乳化重合体
JPH07286137A (ja) * 1994-04-13 1995-10-31 Natl Starch & Chem Investment Holding Corp 有機溶媒を含まず、多段階ポリマーをベースとするラテックスペイント塗料
JPH0967543A (ja) * 1995-09-04 1997-03-11 Dekusutaa Midorando Kk コアシェル微粒子分散塗料
JPH10316866A (ja) * 1997-05-22 1998-12-02 Mitsui Chem Inc 重合体粒子
JP2001205737A (ja) * 2000-01-28 2001-07-31 Nippon Steel Corp 樹脂被覆金属基材およびそれを含む容器
JP2001514312A (ja) * 1997-08-28 2001-09-11 アトフィナ 凝集助剤無しに低温で皮膜を形成するコア／シェル構造の疎水ポリマーをベースとしたラテックス
JP2002012816A (ja) * 2000-06-30 2002-01-15 Nippon Paint Co Ltd 水性塗料組成物
JP2004059622A (ja) * 2002-07-25 2004-02-26 Kansai Paint Co Ltd 水性塗料組成物
JP2007291343A (ja) * 2006-03-24 2007-11-08 Kansai Paint Co Ltd 缶用塗料組成物
JP2008297380A (ja) * 2007-05-30 2008-12-11 Toyo Ink Mfg Co Ltd 水性塗料及びその製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0445102A (ja) * 1990-06-12 1992-02-14 Kansai Paint Co Ltd 乳化重合体の製造方法及びその製造方法で得られる乳化重合体
JPH07286137A (ja) * 1994-04-13 1995-10-31 Natl Starch & Chem Investment Holding Corp 有機溶媒を含まず、多段階ポリマーをベースとするラテックスペイント塗料
JPH0967543A (ja) * 1995-09-04 1997-03-11 Dekusutaa Midorando Kk コアシェル微粒子分散塗料
JPH10316866A (ja) * 1997-05-22 1998-12-02 Mitsui Chem Inc 重合体粒子
JP2001514312A (ja) * 1997-08-28 2001-09-11 アトフィナ 凝集助剤無しに低温で皮膜を形成するコア／シェル構造の疎水ポリマーをベースとしたラテックス
JP2001205737A (ja) * 2000-01-28 2001-07-31 Nippon Steel Corp 樹脂被覆金属基材およびそれを含む容器
JP2002012816A (ja) * 2000-06-30 2002-01-15 Nippon Paint Co Ltd 水性塗料組成物
JP2004059622A (ja) * 2002-07-25 2004-02-26 Kansai Paint Co Ltd 水性塗料組成物
JP2007291343A (ja) * 2006-03-24 2007-11-08 Kansai Paint Co Ltd 缶用塗料組成物
JP2008297380A (ja) * 2007-05-30 2008-12-11 Toyo Ink Mfg Co Ltd 水性塗料及びその製造方法

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016113561A (ja) * 2014-12-16 2016-06-23 関西ペイント株式会社 缶被覆用水性塗料組成物
JP7488653B2 (ja) 2017-03-15 2024-05-22 ハンファ ケミカル コーポレーション エマルジョン、エマルジョンの製造方法、及びエマルジョンを用いたコーティング膜の形成方法
WO2018169309A3 (fr) * 2017-03-15 2018-11-08 한화케미칼 주식회사 Émulsion, son procédé de production et procédé de formation d'une couche de revêtement l'utilisant
JP2020514476A (ja) * 2017-03-15 2020-05-21 ハンファ ケミカル コーポレーションＨａｎｗｈａ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ エマルジョン、エマルジョンの製造方法、及びエマルジョンを用いたコーティング膜の形成方法
US12006380B2 (en) 2017-09-01 2024-06-11 Swimc Llc Multi-stage polymeric latexes, coating compositions containing such latexes, and articles coated therewith
JP2020532613A (ja) * 2017-09-01 2020-11-12 エスダブリューアイエムシー・エルエルシー 多段階ポリマーラテックス、そのようなラテックスを含有するコーティング組成物、及びそれによりコーティングされた物品
US11466162B2 (en) 2017-09-01 2022-10-11 Swimc Llc Multi-stage polymeric latexes, coating compositions containing such latexes, and articles coated therewith
EP3676342A4 (fr) * 2017-09-01 2021-07-07 Swimc LLC Latex polymères à étages multiples, compositions de revêtement contenant de tels latex, et articles en étant revêtus
US11427654B2 (en) 2017-09-01 2022-08-30 Swimc Llc Multi-stage polymeric latexes, coating compositions containing such latexes, and articles coated therewith
US11208565B2 (en) * 2017-11-22 2021-12-28 Toyo Ink Sc Holdings Co., Ltd. Water-soluble paint and coated can
CN109810593A (zh) * 2017-11-22 2019-05-28 东洋油墨Sc控股株式会社 水性涂料、涂装板及被覆罐
CN109810593B (zh) * 2017-11-22 2022-03-08 东洋油墨Sc控股株式会社 水性涂料、涂装板及被覆罐
JP2020002244A (ja) * 2018-06-27 2020-01-09 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および水性塗料組成物の製造方法
WO2020022077A1 (fr) * 2018-07-27 2020-01-30 関西ペイント株式会社 Composition de peinture à base d'eau
JPWO2020022077A1 (ja) * 2018-07-27 2021-08-05 関西ペイント株式会社 水性塗料組成物
JPWO2020022073A1 (ja) * 2018-07-27 2021-08-02 関西ペイント株式会社 水性塗料組成物
JP7280263B2 (ja) 2018-07-27 2023-05-23 関西ペイント株式会社 水性塗料組成物
JP7381466B2 (ja) 2018-07-27 2023-11-15 関西ペイント株式会社 水性塗料組成物及び塗装物品
WO2020022073A1 (fr) * 2018-07-27 2020-01-30 関西ペイント株式会社 Composition de revêtement aqueuse
CN109913060A (zh) * 2019-01-11 2019-06-21 河北晨阳工贸集团有限公司 水性丙烯酸氨基烤漆及其制备方法
JPWO2021084804A1 (ja) * 2019-11-01 2021-11-18 関西ペイント株式会社 水性塗料組成物
CN114555729A (zh) * 2019-11-01 2022-05-27 关西涂料株式会社 水性涂料组合物
WO2021084804A1 (fr) * 2019-11-01 2021-05-06 関西ペイント株式会社 Composition de revêtement à base d'eau
CN114555729B (zh) * 2019-11-01 2023-03-14 关西涂料株式会社 水性涂料组合物
CN113620569A (zh) * 2021-08-29 2021-11-09 咸宁南玻光电玻璃有限公司 一种改善浮法工艺玻璃油墨附着力的方法
CN113620569B (zh) * 2021-08-29 2023-07-11 咸宁南玻光电玻璃有限公司 一种改善浮法工艺玻璃油墨附着力的方法

Similar Documents

Publication Publication Date Title
WO2015015827A1 (fr) Composition de revêtement aqueuse
JP6940605B2 (ja) アクリルポリマー及びこのようなポリマーを含有する組成物
JP7110111B2 (ja) スチレンを含まないコポリマー、及びこのようなコポリマーを含有するコーティング組成物
JP6355132B2 (ja) 缶被覆用水性塗料組成物
CA2917500C (fr) Compositions de revetement presentant une adherence amelioree a des contenants
JP2010504257A (ja) 食品用および飲料用容器ならびにコーティング方法
JP2009501263A (ja) 電着性水性樹脂性分散液、並びにそれらの調製方法
JP2023081934A (ja) 多段階ポリマーラテックス、そのようなラテックスを含有するコーティング組成物、及びそれによりコーティングされた物品
JP2009191284A (ja) 金属表面処理剤
JP5073315B2 (ja) 缶用塗料組成物
JP5127519B2 (ja) 水性メタリック塗料組成物
JP5649763B1 (ja) 水性塗料組成物
JPH10316717A (ja) エポキシ樹脂エマルジョン及び水性塗料の製造法
JP2008297379A (ja) 水性塗料及びその製造方法
TWI662152B (zh) 水性金屬表面處理劑、金屬表面處理方法及表面處理金屬板
JP6274988B2 (ja) 食品接触用塗料組成物
JP2008297380A (ja) 水性塗料及びその製造方法
JP2020041063A (ja) 水性塗料、および被覆缶
JP4936092B2 (ja) 水性樹脂組成物及び該組成物の硬化塗膜を有する塗装金属材料
JP7381466B2 (ja) 水性塗料組成物及び塗装物品
JP5322375B2 (ja) 水性被覆組成物
JP2022175544A (ja) エマルション型アニオン電着塗料、塗装方法、および塗装物品の製造方法
JP3158863B2 (ja) 水性樹脂分散体およびその製造方法
JP2022096728A (ja) 水性塗料、缶蓋、及び飲料缶
JPWO2020022077A1 (ja) 水性塗料組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2014543375

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14831317

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14831317

Country of ref document: EP

Kind code of ref document: A1