WO2014181731A1 - Composition de type émulsion huile dans l'eau et procédé de traitement de surface l'utilisant - Google Patents

Composition de type émulsion huile dans l'eau et procédé de traitement de surface l'utilisant Download PDF

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Publication number
WO2014181731A1
WO2014181731A1 PCT/JP2014/061904 JP2014061904W WO2014181731A1 WO 2014181731 A1 WO2014181731 A1 WO 2014181731A1 JP 2014061904 W JP2014061904 W JP 2014061904W WO 2014181731 A1 WO2014181731 A1 WO 2014181731A1
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Prior art keywords
emulsion composition
oil
parts
mass
water
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Ceased
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PCT/JP2014/061904
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English (en)
Japanese (ja)
Inventor
惇 ▲桑▼原
中村　公彦
秀和 椋野
恒彦 西村
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Resonac Holdings Corp
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Showa Denko KK
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Priority to SG11201509083YA priority Critical patent/SG11201509083YA/en
Priority to CN201480026234.1A priority patent/CN105377925B/zh
Priority to JP2015515851A priority patent/JP6408462B2/ja
Publication of WO2014181731A1 publication Critical patent/WO2014181731A1/fr
Priority to PH12015502545A priority patent/PH12015502545A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to an oil-in-water emulsion composition that can be used in the fields of coating agents, paints, inks, adhesives, anticorrosives, and fiber treatment agents, and a surface treatment method using the oil-in-water emulsion composition.
  • an emulsion composition containing a synthetic resin is excellent in drying properties, so that the viscosity can be lowered even if the concentration of non-volatile components is increased. Therefore, emulsion compositions containing synthetic resins are widely used in the fields of coating agents, paints, inks, adhesives, anticorrosives, and fiber treatment agents.
  • the cured product obtained from the emulsion composition of styrene acrylic resin or polyvinyl acetate obtained by the emulsion polymerization method is more resistant to water and acid than the cured product of solvent-based resin such as thermosetting resin and ultraviolet curable resin. And base resistance tend to be greatly inferior. Therefore, in order to solve these problems, a crosslinked emulsion composition obtained by utilizing a crosslinking technique or the like has been proposed.
  • an epoxy (meth) acrylate resin, a high-boiling polymerizable monomer, a nonionic emulsifier, an anionic emulsifier (however, each emulsifier has only a disclosure of a non-reactive emulsifier), a curing agent and water are included.
  • a crosslinked emulsion composition for high-temperature curing is known (see Patent Document 1).
  • Patent Document 1 when the crosslinked emulsion composition described in Patent Document 1 is used, a step of curing by heat treatment at a high temperature is essential, and cannot be employed in a situation where there is no high-temperature drying facility.
  • an oil-in-water emulsion composition [A] containing a polyester acrylate resin, a surfactant, a curing agent and water, a polyester acrylate resin, and a curing accelerator And a cross-linked emulsion composition obtained by mixing an oil-in-water emulsion composition [B] containing water see Patent Document 2.
  • JP 05-271366 A Japanese Patent Laid-Open No. 02-036206
  • an object of the present invention is to provide an emulsion composition that can be easily cured at room temperature and can achieve high water resistance, high acid resistance, and high base resistance, and uses the emulsion composition. It is to provide a surface treatment method.
  • the present inventors have found that the following oil-in-water emulsion composition can be easily cured at room temperature, and has water resistance, acid resistance and resistance.
  • the present inventors have found that a cured coating film excellent in basicity can be obtained, and have completed the present invention.
  • the present invention relates to the following [1] to [10].
  • the reactive surfactant (D) is at least one selected from an ionic reactive surfactant and a nonionic reactive surfactant. object.
  • the polymerizable unsaturated monomer (B) is alkyl (meth) acrylate, alkenyl (meth) acrylate, alkylene glycol di (meth) acrylate, alkoxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate,
  • a surface treatment method for a material selected from metal, plastic, concrete, mortar, wood and glass, the oil-in-water emulsion composition according to any one of the above [1] to [6] A surface treatment by preparing a coating solution by adding (F) and applying the coating solution to the surface of the material, followed by curing at 0 to 50 ° C. to form a cured coating film on the surface of the material Method.
  • the curing agent (F) is at least one selected from ketone peroxides, hydroperoxides, and peroxyesters.
  • the surface treatment method according to any one of [7] to [9] above, wherein the metal according to [7] contains at least one selected from iron and aluminum.
  • the oil-in-water emulsion composition of the present invention is industrially advantageous because it can be easily cured at room temperature and can be used even without a high-temperature drying facility. Moreover, the hardened
  • the oil-in-water emulsion composition of the present invention is (Meth) acrylate-based epoxy resin (A) 100 parts by mass, 1 to 200 parts by mass of a polymerizable unsaturated monomer (B), Curing accelerator (C) 0.1 to 10 parts by mass, It is an oil-in-water type emulsion composition containing 1 to 50 parts by weight of a reactive surfactant (D) and 10 to 200 parts by weight of water (E), that is, a 0 il in water type (O / W type) emulsion composition.
  • A 100 parts by mass, 1 to 200 parts by mass of a polymerizable unsaturated monomer
  • Curing accelerator C
  • D reactive surfactant
  • E water
  • the component (A) (meth) acrylate epoxy resin is a resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ⁇ - ⁇ unsaturated monobasic acid.
  • the “(meth) acrylate-based epoxy resin” is obtained by reacting an acid having a carbon-carbon double bond at the so-called ⁇ - ⁇ position such as acrylic acid, methacrylic acid, crotonic acid and the epoxy compound. All epoxy resins are shown.
  • Examples of the epoxy resin having two or more epoxy groups in one molecule include bisphenol type epoxy resin, novolac type epoxy resin, halogenated bisphenol type epoxy resin, halogenated novolac type epoxy resin, cyanurate type epoxy resin, and dimer acid-modified.
  • An epoxy resin etc. are mentioned.
  • bisphenol type epoxy resins, novolac type epoxy resins, and halogenated bisphenol type epoxy resins are preferable. All can be manufactured by a well-known method, and a commercial item can also be used.
  • Preferred examples of the “bisphenol type” include bisphenol A type, bisphenol AP type, bisphenol B type, bisphenol BP type, bisphenol C type, bisphenol E type, bisphenol F type, and bisphenol G type. More preferred.
  • bisphenol A is 2,2-bis (4-hydroxyphenyl) propane
  • bisphenol AP is 1,1-bis (4-hydroxyphenyl) -1-phenylethane
  • bisphenol B is 2,2-bis (4- Hydroxyphenyl) butane
  • bisphenol BP is bis (4-hydroxyphenyl) diphenylmethane
  • bisphenol C is 2,2-bis (3-methyl-4-hydroxyphenyl) propane
  • bisphenol E is 1,1-bis (4-hydroxyphenyl) ) Ethane
  • bisphenol F refers to bis (4-hydroxyphenyl) methane
  • bisphenol G refers to 2,2-bis (4-hydroxy-3-isopropylphenyl) propane.
  • halogenation bromination is preferable.
  • the epoxy resin having two or more epoxy groups in one molecule is preferably an epoxy resin having one epoxy group at both ends of the molecule.
  • the epoxy equivalent of an epoxy resin having two or more epoxy groups in one molecule is preferably 130 to 800 g / eq, more preferably 150 to 600 g / eq, and more preferably 150 to 400 g / eq.
  • Examples of the ⁇ - ⁇ unsaturated monobasic acid include acrylic acid, methacrylic acid, and crotonic acid. Among these, acrylic acid and methacrylic acid are preferable, and methacrylic acid is more preferable.
  • limiting in particular in reaction with the epoxy resin which has 2 or more of epoxy groups in 1 molecule, and an unsaturated monobasic acid A well-known method is employable. Specifically, an epoxy resin having two or more epoxy groups in one molecule and an ⁇ - ⁇ unsaturated monobasic acid are mixed so that the epoxy group and the carboxyl group are approximately equivalent, and preferably a stabilizer.
  • the acid value is preferably 30 mgKOH / g or less, more preferably 4 to 25 mgKOH / g. More preferably, a method of reacting until it becomes 6 to 20 mg KOH / g can be employed.
  • a known polymerization inhibitor can be used as the stabilizer.
  • hydroquinone compounds such as hydroquinone, methylhydroquinone, trimethylhydroquinone and t-butylhydroquinone
  • thioether compounds such as phenothiazine and distearylthiodipropionate
  • copper dialkyldithiocarbamate the alkyl group is a methyl group, ethyl group, propyl group or Butyl group
  • copper acetate copper salicylate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, copper acrylate, etc .
  • manganese dialkyldithiocarbamate alkyl groups are methyl, ethyl, Propyl group or butyl group
  • manganese diphenyldithiocarbamate manganese formate, manganese acetate, manganese octoate, manganese naphthenate, manganese permanganate, ethylenediaminete
  • the (meth) acrylate-based epoxy resin may be modified.
  • the modification include urethane modification, phenol modification, cresol modification, acid modification, acid anhydride modification, acid pendant modification, phosphoric acid pendant modification, silicon modification, allyl ether modification, acetoacetylation modification, and partial esterification modification.
  • Etc. (A) A component may be used individually by 1 type and may use 2 or more types together.
  • the oil-in-water emulsion composition of the present invention contains a polymerizable unsaturated monomer as the component (B).
  • the component (A) and the component (B) may be collectively referred to as “resin component”.
  • the polymerizable unsaturated monomer (B) alkyl (meth) acrylate, alkenyl (meth) acrylate, alkylene glycol di (meth) acrylate, alkoxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate , Acrylonitrile, styrene and its derivatives, and vinyl compounds.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like, and the carbon number of the alkyl group is preferably 1 to 10.
  • alkenyl (meth) acrylates include allyl (meth) acrylate, and the alkenyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.
  • alkylene glycol di (meth) acrylate examples include ethylene glycol di (meth) acrylate, and the number of carbon atoms in the alkylene glycol moiety is preferably 2 or 3, and more preferably 2.
  • alkoxyalkyl (meth) acrylate examples include methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, and the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
  • dialkylaminoalkyl (meth) acrylate examples include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • the alkyl groups of the dialkylamino group may be the same as or different from each other.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the carbon number of the alkyl group that is substituted with the dialkylamino group and bonded to the oxygen atom of the acryloyloxy group is preferably 1 to 5, and more preferably 1 to 3.
  • styrene derivative examples include ⁇ -methylstyrene, o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene.
  • vinyl compound examples include vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinylidene chloride.
  • styrene and derivatives thereof, and alkylene glycol di (meth) acrylate are preferable, styrene and ethylene glycol di (meth) acrylate are more preferable, styrene and ethylene glycol dimethacrylate are further preferable, and styrene is particularly preferable.
  • the component (B) has an effect of facilitating the formation of a cured coating film when the oil-in-water emulsion composition is cured at room temperature.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the oil-in-water emulsion composition of the present invention can be cured at room temperature, as described above, it has a low boiling point (for example, less than 200 ° C., lower one is 180 ° C. or lower, and further 160 ° C. The following can also be used advantageously.
  • the content of the component (B) is 1 to 200 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of the component (B) is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and further preferably 15 to 60 parts by mass with respect to 100 parts by mass of the component (A). Particularly preferred is 20 to 55 parts by mass.
  • (C): Curing accelerator As the curing accelerator as component (C), a curing agent (F) that is added when the oil-in-water emulsion composition of the present invention is cured at room temperature, specifically, one that can reduce organic peroxide is used. Can do.
  • the metal soap is, for example, a long-chain fatty acid such as stearic acid, lauric acid, ricinoleic acid, octylic acid, naphthenic acid, and, for example, lithium, magnesium, calcium, barium, aluminum, zinc, iron, cobalt, manganese , Salts of metals such as zirconium (however, metals other than sodium and potassium).
  • the carbon number of the long-chain fatty acid is preferably 6 to 25, more preferably 6 to 20, still more preferably 6 to 15, and particularly preferably 7 to 12.
  • the metal is preferably iron, cobalt, manganese, more preferably cobalt.
  • the metal soap is preferably an iron-containing metal soap such as iron naphthenate, a cobalt-containing metal soap such as cobalt naphthenate and cobalt octylate, or a manganese-containing metal soap such as manganese octylate, more preferably a cobalt-containing metal. Soap, more preferably cobalt octylate.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the content of component (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of component (A). If it is less than 0.1 parts by mass, curing at room temperature becomes difficult. On the other hand, even if the amount exceeds 10 parts by mass, the effect of the component (C) reaches its peak, which only increases the manufacturing cost. From the same viewpoint, the content of the component (C) is preferably 0.3 to 7 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0 to 100 parts by mass of the component (A). .3 to 3 parts by mass.
  • (D): Reactive surfactant As the component (D), it is necessary to use a reactive surfactant in order to suppress the separation of the surfactant from the resin component and to increase the water resistance, acid resistance and base resistance of the cured coating film. With a non-reactive surfactant, the water resistance, acid resistance and base resistance of the cured coating film are insufficient.
  • “reactive” means having radical reactivity
  • the reactive surfactant preferably has at least one carbon-carbon double bond in the molecule.
  • “non-reactive” means having no radical reactivity
  • the non-reactive surfactant is one having no carbon-carbon double bond in the molecule.
  • the reactive surfactant (D) includes an ionic reactive surfactant and a nonionic (nonionic) reactive surfactant, and it is preferable to use at least one selected from these. Either one of an ionic reactive surfactant and a nonionic reactive surfactant may be used, but it is more preferable to use them in combination.
  • the ionic reactive surfactant may be any of an anionic reactive surfactant, a cationic reactive surfactant, and an amphoteric reactive surfactant. From the viewpoint of ease of emulsification, the anionic reactive surfactant is used. Activators are preferred.
  • anionic reactive surfactant examples include ⁇ -sulfo- ⁇ - (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt [Co., Ltd. Adeka soap (registered trademark) SR-10, SR-1025, etc. manufactured by ADEKA], ⁇ -sulfo- ⁇ - (1- (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-) 1,2-ethanediyl) ammonium salt [Adeka soap (registered trademark) SE-10, SE-1025A, etc.
  • alkylallylsulfosuccinate [Latemul (registered trademark) S-180A, S-180 manufactured by Kao Corporation, etc., Elminol manufactured by Sanyo Chemical Industries, Ltd. ( Registered trademark) JS-20, etc., but is not particularly limited thereto.
  • ⁇ -sulfo- ⁇ - (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1) from the viewpoint of water resistance, acid resistance and base resistance of the cured coating film , 2-ethanediyl) ammonium salt [ADEKA rear soap (registered trademark) SR-10, SR-1025, etc., manufactured by ADEKA Corporation] is preferable.
  • Nonionic reactive surfactants include, for example, ⁇ -hydro- ⁇ - (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) [manufactured by ADEKA Corporation.
  • ADEKA rear soap (registered trademark) ER-10, ER-20, ER-30, ER-40], polyoxyalkylene alkenyl ether [Latemul (registered trademark) PD-420, PD-430, PD manufactured by Kao Corporation] -450], polyoxyethylene alkylpropenyl phenyl ether [AQUALON (registered trademark) RN20, RN30, RN50 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], and the like, but are not particularly limited thereto.
  • ⁇ -hydro- ⁇ - (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1) , 2-ethanediyl) [ADEKA rear soap (registered trademark) ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation] is preferable.
  • the content of the nonionic surfactant in the component (D) is preferably 80. It is 90 mass% or more more preferably.
  • the content of component (D) is 1 to 50 parts by mass with respect to 100 parts by mass of component (A). When the amount is less than 1 part by mass, the stability of the emulsion is lowered.
  • the content of the component (D) is preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 35 parts by mass with respect to 100 parts by mass of the component (A). Particularly preferred is 15 to 30 parts by mass.
  • a non-reactive surfactant together with the reactive surfactant which is (D) component.
  • a non-reactive surfactant is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 10 parts by mass with respect to 100 parts by mass of component (D). Or less.
  • known non-reactive anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used.
  • Non-reactive anionic surfactants include, for example, higher alcohol sulfates such as sodium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl naphthalene sulfonates; potassium alkenyl succinates; dialkyl sulfos Succinate; Semi-cured bovine fatty acid salt such as semi-cured bovine fatty acid potassium; Alkyl diaryl ether disulfonate such as sodium alkyldiphenyl ether disulfonate; Sulfate ester of polyoxyalkylene alkyl ether such as sulfate salt of polyoxyethylene alkyl ether Salt; sulfate ester salt of polyoxyalkylene alkyl aryl ether such as sulfate ester salt of polyoxyethylene alkyl phenyl ether; polyoxyethylene lauryl ether acetic acid Polyoxyalkylene alkyl
  • non-reactive cationic surfactant examples include alkyl ammonium salts such as dodecyl ammonium chloride.
  • Non-reactive nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene Ethylene fatty acid ester, polyoxyethylene acyl ester, polyoxyethylene hydrogenated sterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester Etc.
  • the oil-in-water emulsion composition of the present invention contains 10 to 200 parts by mass of water as the component (E) with respect to 100 parts by mass of the component (A).
  • the content of water is preferably 10 to 150 parts by weight, more preferably 10 to 100 parts by weight, still more preferably 10 to 70 parts by weight, particularly preferably 100 parts by weight of component (A). Is 10 to 50 parts by mass.
  • the water is preferably pure water such as ion exchange water or distilled water.
  • water (E) is dropped into a mixed solution containing the components (A) to (D) and other components described later as required. And obtained by phase inversion emulsification.
  • the oil-in-water emulsion composition of the present invention may contain various additives such as reinforcing materials, fillers, and pigments as necessary. Moreover, you may contain water-soluble polymers, such as polyvinyl alcohol, polyester, polyethyleneglycol, and polyvinylpyrrolidone. When the water-soluble polymer is contained, the effect of improving the stability of the component (A) can be obtained.
  • the oil-in-water emulsion composition of the present invention contains these other components, the content thereof is preferably 30 parts by mass or less, more preferably 20 parts by mass with respect to 100 parts by mass of component (A). Hereinafter, it is more preferably 10 parts by mass or less.
  • the total content of the components (A) to (E) in the oil-in-water emulsion composition is preferably 50% by mass or more. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Especially preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more.
  • the method for preparing the oil-in-water emulsion composition of the present invention is not particularly limited as long as it becomes an oil-in-water emulsion composition.
  • a method of mixing the components (A) to (D) and other components as necessary to obtain a mixed solution and dropping water into the mixed solution to carry out phase inversion emulsification is preferable.
  • the so-called W / O type emulsion in which the continuous phase is an oil phase instead of adding water all at once, by “dropping” water, the so-called W / O type emulsion in which the continuous phase is an oil phase, and so-called O / W type in which the continuous phase is water. It changes neatly into an emulsion.
  • the speed of dropping water is not particularly limited as long as it is not too early, but is preferably about 10 to 300 ml / h, and more preferably 50 to 150 ml / h.
  • a coating solution is prepared by adding a curing agent (F) to the oil-in-water emulsion composition of the present invention, and the coating solution is applied to the surface of the material and then cured at 0 to 50 ° C.
  • a method of forming a cured coating film on the surface of the material can be preferably used.
  • curing agent (F) As a hardening
  • the curing agent an organic peroxide is preferably used.
  • organic peroxide examples include, for example, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; t-butyl hydroperoxide, cumene Hydroperoxides such as hydroperoxide, diisopropylbenzene hydroperoxide and 2,5-dimethylhexanone-2,5-hydroperoxide; peroxy such as t-butylperoxybenzoate and t-butylperoxylaurate
  • ester examples include, but are not limited to, esters.
  • the organic peroxide preferably has a 10-hour half-life temperature of 30 to 170 ° C.
  • curing agent may be used individually by 1 type, and may use 2 or more types together.
  • the addition amount of the curing agent (F) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and further preferably 1 to 1 part by mass with respect to 100 parts by mass of the oil-in-water emulsion composition. It is 7 parts by mass, particularly preferably 1 to 5 parts by mass.
  • the addition amount of the curing agent (F) is 0.5 parts by mass or more with respect to 100 parts by mass of the oil-in-water emulsion composition, sufficient curing speed and sufficient hardness can be obtained, and the water resistance of the cured coating film can be obtained. , Acid resistance and base resistance are excellent. Moreover, if it is 10 mass parts or less, coating-film formation ease will not fall.
  • the temperature for curing is preferably 5 to 50 ° C., more preferably 10 to 50 ° C., still more preferably 15 to 45 ° C., and particularly preferably 15 to 40 ° C. from the viewpoint of the curing rate.
  • the film thickness of the formed cured coating film is preferably from the viewpoint of surface treatment, generally from the viewpoint of satisfying both that it is desired not to be too large and that the surface treatment effect is maintained for a long time. It is 1 to 2 mm, more preferably 0.3 to 2 mm, still more preferably 0.5 to 2 mm, and particularly preferably 0.5 to 1.5 mm.
  • the film thickness of a cured coating film can be adjusted to the said range by adjusting the film thickness of the swelling coating film at the time of application
  • Materials such as metal, plastic, concrete, mortar, wood, and glass are materials that can be used in situations where they come into contact with rainwater or industrial wastewater, and surface treatment using the oil-in-water emulsion composition of the present invention is desired.
  • the metal preferably contains at least one selected from iron and aluminum. These are components contained in metals that are often used particularly in contact with rainwater or industrial wastewater.
  • iron may be substantially 100 mass%, and may also contain metals other than iron (for example, chromium etc.), such as stainless steel.
  • the glass is not particularly limited as long as it becomes an amorphous solid exhibiting a glass transition phenomenon when heated.
  • a glass containing silicate as a main component may be used, or a glass containing components other than silicate as a main component, for example, acrylic glass, chalcogen glass, metal glass, organic glass, or the like may be used.
  • the surface of the glass to be surface-treated may be smooth or uneven.
  • the acid value of the (meth) acrylate epoxy resin (A) obtained by the reaction was 10 mgKOH / g.
  • 0.3 g of hydroquinone and 600 g of styrene as component (B) were added and dissolved by stirring well.
  • the resin component thus obtained is referred to as resin component (VE-1).
  • the blending ratio of the component (B) in the resin component is 30 parts by mass with respect to 100 parts by mass of the component (A).
  • 1.0 g of cobalt octylate is used as the component (C)
  • an anionic reactive surfactant “Adekari Soap (registered trademark) SR-10 is used as the component (D).
  • the oil-in-water emulsion composition 1 was prepared by stirring well while dropping 30 g of water at 100 ml / h. In the emulsion composition, the surfactant was not separated from the resin component, and the emulsion was stable.
  • Example 2 In Example 1, the same operation was performed except that 600 g of ethylene glycol dimethacrylate was used instead of 600 g of styrene (the obtained resin component is referred to as a resin component (VE-2)), and an oil-in-water type was obtained. Emulsion composition 2 was prepared. In the emulsion composition, the surfactant was not separated from the resin component, and the emulsion was stable.
  • Aldite registered trademark
  • resin component (VE-3) The resin component thus obtained is referred to as resin component (VE-3).
  • the blending ratio of the component (B) in the resin component is 45 parts by mass with respect to 100 parts by mass of the component (A).
  • 1.0 g of cobalt octylate is used as the component (C)
  • an anionic reactive surfactant “Adekari Soap (registered trademark) SR-10 is used as the component (D).
  • EPICRON registered trademark
  • resin component (VE-4) The resin component thus obtained is referred to as resin component (VE-4).
  • the blending ratio of the component (B) in the resin component is 25 parts by mass with respect to 100 parts by mass of the component (A).
  • 1.0 g of cobalt octylate is used as the component (C), and an anionic reactive surfactant “Adekari Soap (registered trademark) SR-10 as the component (D)”.
  • Comparative Example 1 An oil-in-water emulsion composition 5 was prepared in the same manner as in Example 1, except that styrene was not used (the obtained resin component is referred to as resin component (VE-5)). In the emulsion composition, the surfactant was not separated from the resin component, and the emulsion was stable.
  • Table 1 summarizes the components (A) and (B) used in Examples 1 to 4 and Comparative Example 1 and the blending ratios thereof.
  • Comparative Example 2 100 g of the resin component (VE-1) obtained in Example 1, 1.0 g of cobalt octylate as the (C) component, and an anionic reactive surfactant “Adekari Soap (registered trademark)” as the (D) component SR-10 "(manufactured by ADEKA Corporation) 3 g and nonionic reactive surfactant” Adekaria Soap (registered trademark) ER-30 "(manufactured by ADEKA Corporation) 65 g were added to the resulting mixture (E) An oil-in-water emulsion composition 6 was prepared by stirring well while dropping 30 g of water as a component at 100 ml / h. In the emulsion composition, the surfactant was not separated from the resin component, and the emulsion was stable.
  • Example 3 an anionic non-reactive surfactant “Latemul (registered trademark) E-118B” (manufactured by Kao Corporation) was used in place of the anionic reactive surfactant.
  • An oil-in-water emulsion composition was prepared in the same manner except that a nonionic non-reactive surfactant “Emulgen (registered trademark) 1135-S70” (manufactured by Kao Corporation) was used instead of the surfactant.
  • Product 7 was prepared. In the emulsion composition, the surfactant was not separated from the resin component, and the emulsion was stable.
  • Examples 5 to 8 and Comparative Examples 4 to 6 Oil-in-water emulsion composition obtained in Examples 1 to 4 or Comparative Examples 1 to 3 and a curing agent “328E” (t-butyl peroxybenzoate and cumene hydroperoxide diluted with a solvent.
  • Kayaku Akzo Stock (Manufactured by the company) was mixed at the blending amounts shown in Table 3 to prepare a coating solution, and the coating solution was applied onto a glass with a polyester film so that the wet film thickness was 1 mm. After coating, the cured coating film was obtained by leaving it for 3 days in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The polyester film stretched on the glass is for preventing the coating film from sticking to the glass. The ease of formation of the cured coating film and the water resistance, acid resistance and base resistance of the cured coating film were evaluated according to the following methods. The results are shown in Table 3.
  • oil-in-water emulsion compositions No. 1 to No. 4 cured coatings at room temperature compared to using oil-in-water emulsion compositions No. 6 and No. 7. It can be seen that the water resistance, acid resistance and base resistance of the cured coating film are significantly superior. Moreover, it turns out that oil-in-water emulsion composition No. 5 is a composition with which formation of a cured coating film is difficult.
  • the oil-in-water emulsion composition of the present invention can be used in the fields of coating agents, paints, inks, adhesives, anticorrosives, and fiber treatment agents.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Cette invention concerne : une composition de type émulsion qui peut facilement durcir à température ambiante et est capable d'atteindre une résistance à l'eau élevée, une résistance aux acides élevée et une résistance aux bases élevée ; et un procédé de traitement de surface l'utilisant. La composition de type émulsion selon l'invention est typiquement une composition de type émulsion huile dans l'eau qui contient 100 parties en poids de (A) une résine (méth)acrylate-époxy, 1 à 200 parties en poids de (B) un monomère insaturé polymérisable, 0,1 à 10 parties en poids de (C) un accélérateur de durcissement, 1 à 50 parties en poids de (D) un tensioactif réactif et 10 à 200 parties en poids (E) d'eau. Le procédé de traitement de surface selon l'invention est spécifiquement un procédé de traitement de surface en métal, plastique, béton, mortier, bois ou verre consistant à préparer un liquide de revêtement par ajout (F) d'un durcissement à la composition de type émulsion huile dans l'eau décrite ci-dessus, et à appliquer le liquide de revêtement à une surface métallique avant de le durcir à 0-50 °C, pour former ainsi un film de revêtement durci sur la surface métallique.
PCT/JP2014/061904 2013-05-10 2014-04-28 Composition de type émulsion huile dans l'eau et procédé de traitement de surface l'utilisant Ceased WO2014181731A1 (fr)

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SG11201509083YA SG11201509083YA (en) 2013-05-10 2014-04-28 Oil-in-water emulsion composition and surface treatment method using same
CN201480026234.1A CN105377925B (zh) 2013-05-10 2014-04-28 水包油型乳液组合物和使用其的表面处理方法
JP2015515851A JP6408462B2 (ja) 2013-05-10 2014-04-28 水中油型エマルジョン組成物及びこれを用いた表面処理方法
PH12015502545A PH12015502545A1 (en) 2013-05-10 2015-11-06 Oil-in-water emulsion composition and surface treatment method using same

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CN105418419A (zh) * 2015-11-02 2016-03-23 安庆市虹泰新材料有限责任公司 一种二聚酸改性的环氧树脂及其制备方法
CN108367985A (zh) * 2015-12-07 2018-08-03 昭和电工株式会社 砂浆组合物及其制造方法、混凝土结构体、以及混凝土构架的基底调整方法
WO2018155032A1 (fr) 2017-02-27 2018-08-30 昭和電工株式会社 Composition d'émulsion de résine aqueuse durcissable
JP2019038972A (ja) * 2017-08-29 2019-03-14 昭和電工建材株式会社 防食ライニング材及びコンクリート構造物の防食方法
WO2024099751A1 (fr) * 2022-11-10 2024-05-16 Allnex Belgium, S.A. Composition aqueuse durcissable par rayonnement

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CN105693914B (zh) * 2016-03-25 2017-10-10 北京同华道路养护有限责任公司 一种抗轮胎痕迹树脂乳液封层及其施工方法
FR3100249B1 (fr) * 2019-08-28 2021-10-29 Arkema France Procédé de traitement de dispersions polymères basé sur l’utilisation de peroxydes organiques spécifiques

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CN105418419A (zh) * 2015-11-02 2016-03-23 安庆市虹泰新材料有限责任公司 一种二聚酸改性的环氧树脂及其制备方法
CN108367985A (zh) * 2015-12-07 2018-08-03 昭和电工株式会社 砂浆组合物及其制造方法、混凝土结构体、以及混凝土构架的基底调整方法
EP3388404A4 (fr) * 2015-12-07 2019-06-12 Showa Denko K.K. Composition de mortier et son procédé de fabrication, structure en béton et procédé de réglage de fondation à ossature en béton
WO2018155032A1 (fr) 2017-02-27 2018-08-30 昭和電工株式会社 Composition d'émulsion de résine aqueuse durcissable
KR20190118162A (ko) 2017-02-27 2019-10-17 쇼와 덴코 가부시키가이샤 경화형 수계 수지 에멀전 조성물
JPWO2018155032A1 (ja) * 2017-02-27 2019-12-19 昭和電工株式会社 硬化型水系樹脂エマルジョン組成物
JP2019038972A (ja) * 2017-08-29 2019-03-14 昭和電工建材株式会社 防食ライニング材及びコンクリート構造物の防食方法
JP7112188B2 (ja) 2017-08-29 2022-08-03 昭和電工建材株式会社 コンクリート構造物の防食工法
WO2024099751A1 (fr) * 2022-11-10 2024-05-16 Allnex Belgium, S.A. Composition aqueuse durcissable par rayonnement

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PH12015502545B1 (en) 2016-02-22
JPWO2014181731A1 (ja) 2017-02-23
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MY174072A (en) 2020-03-08
SG11201509083YA (en) 2015-12-30
JP6408462B2 (ja) 2018-10-17
PH12015502545A1 (en) 2016-02-22

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