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WO2024207393A1 - Aqueously dispersed epoxy resin composition, paint, and article - Google Patents

Aqueously dispersed epoxy resin composition, paint, and article Download PDF

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Publication number
WO2024207393A1
WO2024207393A1 PCT/CN2023/086775 CN2023086775W WO2024207393A1 WO 2024207393 A1 WO2024207393 A1 WO 2024207393A1 CN 2023086775 W CN2023086775 W CN 2023086775W WO 2024207393 A1 WO2024207393 A1 WO 2024207393A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
compound
resin composition
mass
aqueously dispersed
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/CN2023/086775
Other languages
French (fr)
Inventor
Xingsheng WANG
Tetsuya Yamazaki
Shiliang Wang
Shizheng HOU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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 DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to PCT/CN2023/086775 priority Critical patent/WO2024207393A1/en
Priority to CN202380090137.8A priority patent/CN120457177A/en
Priority to TW113112636A priority patent/TW202444787A/en
Publication of WO2024207393A1 publication Critical patent/WO2024207393A1/en
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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

Definitions

  • the present invention relates to an aqueously dispersed epoxy resin composition, a paint, and an article.
  • Epoxy resin compositions generally give cured products that are excellent in mechanical characteristics and electrical characteristics and have good properties, such as bonding properties, solvent resistance, water resistance, and heat resistance. Thus, epoxy resin compositions are used in wide ranges of applications including insulating materials in electric and electronic components, adhesives, paints, and civil engineering and building materials.
  • Epoxy resin compositions for these applications are generally solvent-diluted compositions using various types of organic solvents.
  • VOC volatile organic compounds
  • a known aqueously dispersed epoxy resin composition is one obtained by first reacting polyethylene glycol with trimellitic anhydride, then reacting the product with an excess epoxy resin to synthesize an emulsifier, and adding the emulsifier to an epoxy resin followed by addition of water (see, for example, PTL 1) .
  • Another aqueously dispersed epoxy resin composition that is known is obtained by first reacting polyethylene glycol with an acid anhydride, then reacting the product with an excess epoxy resin to synthesize an emulsifier, which is then recovered, and adding the recovered emulsifier to an epoxy resin followed by addition of water (see, for example, PTL 2) .
  • these aqueously dispersed epoxy resin compositions are insufficient in storage stability and give cured products that do not meet the current increasing levels of performances (for example, anticorrosive properties) .
  • An object of the present invention is to provide an aqueously dispersed epoxy resin composition that has high storage stability and is capable of forming a cured film having excellent anticorrosive properties; a paint containing the aqueously dispersed epoxy resin composition; and an article having a cured film from the paint.
  • the present inventors carried out extensive studies to achieve the above object. As a result, the present inventors have found that the object is achieved with an aqueously dispersed epoxy resin composition that contains an aqueous medium and an epoxy resin essentially obtained from a compound having at least two epoxy groups in the molecule and a compound obtained from specific polyvalent active hydrogen compounds and an acid anhydride and having at least two carboxyl groups in the molecule.
  • the present invention has been completed based on the finding.
  • the present invention pertains to an aqueously dispersed epoxy resin composition that contains an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule; and an aqueous medium (B) , wherein the compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1) , and an acid anhydride (a2-3) , and the content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
  • an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule
  • the aqueously dispersed epoxy resin composition of the present invention can be prepared by a simple method and has high storage stability.
  • a paint containing the aqueously dispersed epoxy resin composition has excellent anticorrosive properties and thus may be suitably used in particular as an anticorrosive paint.
  • An aqueously dispersed epoxy resin composition of the present invention contains an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule; and an aqueous medium (B) , wherein the compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1) , and an acid anhydride (a2-3) , and the content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
  • the epoxy resin (A) used here is one obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule.
  • Examples of the compounds (a1) having at least two epoxy groups in the molecule include bisphenol-type epoxy resins synthesized from a bisphenol and an epihalohydrin; novolac-type epoxy resins synthesized from a phenol/alkylphenol novolac and an epihalohydrin; biphenol-type epoxy resins; epoxy resins synthesized from a compound diol having aromatic rings adj acent to one another, such as naphthalenediol, and an epihalohydrin; glycidylamines synthesized from an aromatic amine and an epihalohydrin; epoxy resins synthesized from an aliphatic amine and an epihalohydrin; epoxy resins synthesized from an aliphatic alcohol and an epihalohydrin; epoxy resins obtained by reacting a diene compound-phenol condensate, such as dicyclopentadiene-phenol condensate, with an epihalohydrin;
  • Examples of the compounds (a1) further include compounds obtained by modifying the epoxy resins described above through reaction with modifiers, such as polyphenol compounds, polycarboxylic compounds, and polyamine compounds.
  • bisphenol-type epoxy resins and novolac-type epoxy resins are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
  • Bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and phenol novolac-type epoxy resins are more preferable.
  • a monofunctional epoxy resin may be used in combination with the compound (a1) .
  • the monofunctional epoxy resins include butyl glycidyl ether, 2-ethylhexanol glycidyl ether, C12-13 alcohol glycidyl ether, phenyl glycidyl ether, o-cresol glycidyl ether, p-sec-butyl glycidyl ether, t-butylphenol glycidyl ether, cardanol glycidyl ether, and glycidyl neodecanoate.
  • the monofunctional epoxy resins may be used singly, or two or more may be used in combination.
  • the amount in which the compound (a1) is used is preferably in the range of 55 to 70 mass%of the total mass of the essential ingredients for the epoxy resin (A) , that is, the total mass of the compound (a1) and the compound (a2) having at least two carboxyl groups in the molecule. If the amount of the compound (a1) used is less than 55 mass%, cured films have insufficient anticorrosive properties. If the amount is in excess of 70 mass%, it is difficult to concurrently satis fy the water dispersibility and the anticorrosive properties of cured films.
  • the compound (a2) having at least two carboxyl groups in the molecule (hereinafter, also written simply as the “compound (a2) " ) is one obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton, and an acid anhydride (a2-3) .
  • the polyvalent active hydrogen compound (a2-1) may be a compound that contains ethylene glycol, propylene glycol, and/or tetramethylene ether glycol as repeating units, and has a molecular weight distribution. Such compounds may be used singly, or two or more may be used in combination.
  • the terminal active hydrogen moiety may be, for example, a hydroxyl group or an amino group.
  • the polyvalent active hydrogen compounds (a2-1) include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, a compound in which polyethylene glycol and polypropylene glycol are condensed, a compound in which polypropylene glycol is introduced in glycerin, a compound in which polyethylene glycol and polypropylene glycol are condensed and introduced in glycerin, and polycarbonate diol polymerized through carbonate groups.
  • polyvalent active hydrogen compounds (a2-1) examples include “Jeffamine D-series” and “Jeffamine T-series” manufactured by Huntsman.
  • the polyvalent active hydrogen compounds may be used singly, or two or more may be used in combination.
  • polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
  • the polyvalent active hydrogen compound (a2-1) is used so that the content thereof will be in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
  • the polyvalent active hydrogen compound (a2-2) may be any compound that has an alicyclic skeleton in the molecule and has active hydrogen at a terminal. Examples include 2, 2'-isopropylidenecyclohexanol, 2, 4'-isopropylidenecyclohexanol, 4, 4'-isopropylidenecyclohexanol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, tricyclo [5, 2, 1, 0 2, 6 ] decane-4, 8-dimethanol, 2, 2'-methylenebiscyclohexylamine, 2, 4
  • 4, 4'-isopropylidenecyclohexanol, 1, 4-cyclohexanedimethanol, 1, 3-diaminocyclohexane, and 4, 4'-methylenebiscyclohexylamine are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
  • 4, 4'-Isopropylidenecyclohexanol and 1, 4-cyclohexanedimethanol are more preferable.
  • the mass ratio [ (a2-2) / (a2-1) ] of the polyvalent active hydrogen compound (a2-2) to the polyvalent active hydrogen compound (a2-1) is preferably in the range of 0.3 to 6.
  • the acid anhydride (a2-3) is not particularly limited and may be any acid anhydride distributed as an industrial product. Examples include succinic anhydride, octylsuccinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, phthalic anhydride, methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methylnadic anhydride, trimellitic anhydride, pyromellitic anhydride, and dodecanedioic anhydride.
  • the acid anhydrides may be used singly, or two or more may be used in combination.
  • methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl-hexahydrophthalic anhydride are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
  • the compound (a2) may be produced by any method without limitation.
  • the compound (a2) may be obtained by a method in which the essential ingredients including the polyvalent active hydrogen compound (a2-1) , the polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton, and the acid anhydride (a2-3) are stirred in a container under a nitrogen atmosphere while performing heating at 90 to 200°C.
  • the polyvalent active hydrogen compound (a2-1) is water absorptive.
  • the above method preferably involves vacuum heating treatment at an initial stage of the reaction to remove water contained in the compound (a2-1) . In this manner, the compound (a2) may be obtained stably.
  • the amount in which the compound (a2) is used is preferably in the range of 30 to 45 mass%of the total mass of the essential ingredients for the epoxy resin (A) , that is, the total mass of the compound (a1) and the compound (a2) . If the amount of the compound (a2) used is less than 30 mass%, it is difficult to concurrently satisfy the water dispersibility and the anticorrosive properties of cured films. If the amount is in excess of 45 mass%, cured films have insufficient anticorrosive properties.
  • the epoxy resin (A) may be produced by any method without limitation.
  • the epoxy resin (A) may be obtained by a method in which the essential ingredients including the compound (a1) and the compound (a2) are stirred under a nitrogen atmosphere while performing heating at 100 to 200°C. This method may involve a catalyst to shorten the reaction time.
  • the catalysts include tertiary amines, such as triethylamine, tributylamine, benzyldimethylamine, 2, 4, 6-tris (dimethylaminomethyl) phenol, and N-methylpiperazine, and salts thereof; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2, 4-dicyano-6- [2-methylimidazolyl-1] -ethyl-S-triadine, and 2-ethyl-4-methylimidazole tetraphenylborate, and salts thereof; diazabicyclo compounds, such as 1, 5-diazabicyclo [5, 4, 0] -7-undecane, 1, 5-diazabicyclo [4, 3, 0] -5-nonene, 1, 4-diazabicyclo [2, 2,
  • the solid epoxy equivalent in the epoxy resin (A) is preferably in the range of 300 to 1, 300 g/eq. because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties. If the solid epoxy equivalent is less than 300 g/eq., films are hard but brittle. If the solid epoxy equivalent is in excess of 1, 300 g/eq., the reactivity with a curing agent is lowered and the water resistance is deteriorated.
  • the aqueous medium (B) may be ion-exchanged water or distilled water.
  • the aqueous media may be used singly, or two or more may be used in combination.
  • the aqueously dispersed epoxy resin composition of the present invention may be produced by any method without limitation.
  • the aqueously dispersed epoxy resin composition may be obtained by mixing the epoxy resin (A) and the aqueous medium (B) together.
  • the epoxy resin (A) and the aqueous medium (B) may be mixed together using a reaction vessel equipped with a stirring blade; a kneading device, such as a kneader, a continuous kneader, a taper roll machine, a single-screw extruder, a twin-screw extruder, a triple-screw extruder, a universal mixer, Plastomill, or a Votator-type kneading device; a rotary dispersing mixer, such as a homomixer, a static mixer, FILMIX, Ebara Milder, CLEARMIX, ULTRA-TURRAX, CAVITRON, or BIO-MIXER; an ultrasonic disperser; or a device having no mobile sections and performs mixing by the flow of a fluid itself, such as an in-line mixer.
  • a kneading device such as a kneader, a continuous
  • an organic solvent may be used before the addition of the aqueous medium (B) , or together with the aqueous medium (B) .
  • the organic solvent is not necessarily a water-soluble solvent, and is not particularly limited as long as the organic solvent can dissolve the resin resulting from the reaction and is inert to the resin at the time of use.
  • ester compounds such as ethyl acetate, 3-methoxybutyl acetate, methoxypropyl acetate, and cellosolve acetate
  • alcohol compounds such as methanol, ethanol, and isopropanol
  • cellosolve compounds such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve
  • glyme compounds such as monoglyme, diglyme, and triglyme
  • propylene glycol monoalkyl ether compounds such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, and propylene glycol mono-tert-butyl ether
  • ketone compounds such as acetone and methyl ethyl
  • the organic solvent may remain in the aqueously dispersed epoxy resin composition or may be evaporated by distillation under reduced pressure.
  • the mass ratio [ (A) / (B) ] of the epoxy resin (A) to the aqueous medium (B) is preferably in the range of 20/80 to 75/25, and more preferably in the range of 40/60 to 70/30.
  • the aqueously dispersed epoxy resin composition of the present invention may further contain a curing agent.
  • curing agents examples include basic curing agents.
  • Examples of the basic curing agents include aliphatic polyamines, alicyclic polyamines, Mannich bases, amine-epoxy adducts, polyamidepolyamines, and liquid aromatic polyamines.
  • the curing agents may be used singly, or two or more may be used in combination.
  • aliphatic polyamines examples include polyalkylenepolyamines, such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine, and 1, 4-bis- (3-aminopropyl) piperazine, m-xylenediamine, and p-xylenediamine.
  • Examples of the alicyclic polyamines include 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, and isophoronediamine.
  • Mannich bases examples include condensation products of (1) a polyamine, such as triethylenetriamine, isophoronediamine, m-xylenediamine, or p-xylenediamine, (2) an aldehyde, such as formaldehyde, and (3) a monovalent or polyvalent cresol or xylenol, or a phenol, such as p-tert-butylphenol or resorcin, having at least one aldehyde reactive site in the nucleus.
  • a polyamine such as triethylenetriamine, isophoronediamine, m-xylenediamine, or p-xylenediamine
  • an aldehyde such as formaldehyde
  • a monovalent or polyvalent cresol or xylenol or a phenol, such as p-tert-butylphenol or resorcin, having at least one aldehyde reactive site in the nucleus.
  • Examples of the amine-epoxy adducts include (1) reaction products of (a) a polyamine, such as triethylenetriamine, tetraethylenepentamine, isophoronediamine, m-xylenediamine, or p-xylenediamine, with (b) an epoxy resin, for example, a glycidyl ether, such as phenyl glycidyl ether, butyl glycidyl ether, diglycidyl ether of bisphenol A, or diglycidyl ether of bisphenol F; and (2) reaction products of the above polyamine with a glycidyl ester, such as "Cardura E" (registered trademark, Yuka Shell Epoxy K.K. ) .
  • a polyamine such as triethylenetriamine, tetraethylenepentamine, isophoronediamine, m-xylenediamine, or p-xylenediamine
  • an epoxy resin for example, a g
  • polyamidepolyamines examples include those obtained by reaction of a polyamine with a polycarboxylic acid or a dimerized fatty acid, such as reaction products between ethylene diamine and a dimer acid.
  • liquid aromatic polyamines examples include reaction products of an aromatic polyamine with a glycidyl ether or a glycidyl ester.
  • aromatic polyamines include diaminodiphenylmethane and diaminodiphenylsulfone.
  • glycidyl ethers include phenyl glycidyl ether, butyl glycidyl ether, diglycidyl ether of bisphenol A, and diglycidyl ether of bisphenol F.
  • the glycidyl esters include "Cardura E" .
  • the curing agent is preferably used in such an amount that the ratio [epoxy equivalent/amine equivalent] of the epoxy equivalent in the aqueously dispersed epoxy resin composition of the present invention to the amine equivalent in the basic curing agent is in the range of 0.75 to 1.25.
  • the aqueously dispersed epoxy resin composition of the present invention may contain other resin components, such as polyester-based aqueous resins and acrylic-based aqueous resins.
  • the aqueously dispersed epoxy resin composition of the present invention may contain additives.
  • the additives include anti-cissing agents, anti-sagging agents, flowing agents, anti-foaming agents, curing accelerators, UV absorbers, and light stabilizers.
  • the aqueously dispersed epoxy resin composition of the present invention may be used in any application without limitation.
  • Examples of the use applications include paints, adhesives, fiber-sizing agents, and concrete primers.
  • aqueously dispersed epoxy resin composition of the present invention When used in a paint application, it is preferable to add, for example, various pigments, such as antirust pigments, coloring pigments, and extender pigments, and various additives as required.
  • various pigments such as antirust pigments, coloring pigments, and extender pigments, and various additives as required.
  • antirust pigments examples include flake pigments, such as zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, and graphite.
  • coloring pigments examples include carbon black, titanium oxide, zinc sulfide, and red oxide.
  • extender pigments examples include barium sulfate, calcium carbonate, talc, and kaolin.
  • the additives are preferably added in an amount of 10 to 70 parts by mass with respect to 100 parts by mass of the solids in the aqueously dispersed epoxy resin composition.
  • the aqueously dispersed epoxy resin composition of the present invention may be applied by any method without limitation.
  • Some exemplary application methods include roll coating, spraying, brushes, spatulas, bar coaters, dip coating, and electrodeposition.
  • the application may be followed by drying at room temperature and thermal curing.
  • the heating temperature in the thermal curing is preferably in the range of 50 to 250°C, and particularly preferably in the range of 60 to 230°C.
  • the amount of heating time is preferably in the range of 2 to 30 minutes, and particularly preferably in the range of 5 to 20 minutes.
  • the aqueously dispersed epoxy resin composition of the present invention may be used in general applications, such as aqueous paints for building interiors, aqueous paints for building exteriors and inorganic construction materials, aqueous paints for iron rust prevention, and aqueous paints for automobile repairing, and industrial applications, such as automotive paints and for beverage cans.
  • the aqueously dispersed epoxy resin composition of the present invention has excellent anticorrosive properties and set-to-touch properties, and is suitably used as a heavy-duty aqueous paint for iron rust prevention in such structures as steel structures and bridges, in particular, as an aqueous primer paint for iron rust prevention.
  • the aqueously dispersed epoxy resin composition of the present invention may be used as an adhesive in any manner without limitation.
  • the aqueously dispersed epoxy resin composition may be applied to substrates with a spray, a brush, or a spatula, and the bonding surfaces of the substrates may be joined to each other.
  • a strong bonding layer may be formed at the joint by fixing the periphery of the joint or by pressing the substrates to each other.
  • Suitable substrates are steel sheets or plates, concretes, mortars, wood, resin sheets, and resin films.
  • the aqueously dispersed epoxy resin composition is more preferably applied after the substrates are subjected to various surface treatments, for example, physical treatments, such as polishing, electrical treatments, such as corona treatment, and chemical treatments, such as chemical conversion treatment.
  • the aqueously dispersed epoxy resin composition of the present invention may be used as a fiber-sizing agent in any manner without limitation.
  • the aqueously dispersed epoxy resin composition may be applied to just-spun fibers with a roller coater, and the fiber strand may be wound and dried.
  • Any fibers may be used without limitation.
  • the fibers include inorganic fibers, such as glass fibers, ceramic fibers, asbestos fibers, carbon fibers, and stainless steel fibers, natural fibers, such as cotton and hemp, and synthetic fibers, such as polyesters, polyamides, and urethanes.
  • the shapes of the fibers as substrates include short fibers, long fibers, yarns, mats, and sheets.
  • the amount in which the fiber-sizing agent is used is preferably 0.1 to 2 mass% in terms of solid resin relative to the fibers.
  • a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 50.0 parts by mass of polyethylene glycol ( "PEG-3500” manufactured by Jiangsu Haian Petroleum Chemical Factory) and 156.3 parts by mass of hydrogenated bisphenol A.
  • polyethylene glycol "PEG-3500” manufactured by Jiangsu Haian Petroleum Chemical Factory
  • heating and stirring at 200 rpm were initiated.
  • the nitrogen supply was suspended at 110°C, and dehydration was performed under reduced pressure for 1 hr.
  • the pressure was increased again by supplying nitrogen, and 221.0 parts by mass of methyl-tetrahydrophthalic anhydride ( "HN-2000” manufactured by Showa Denko Materials Co., Ltd. ) was added.
  • the temperature was increased to 130°C, and the reaction was performed for 5 hr. There were added 667.0 parts by mass of a bisphenol A-type liquid epoxy resin ( "EPICLON 850-S" manufactured by DIC CORPORATION) and 0.5 parts by mass of triphenylphosphine. The reaction was performed for another 5 hr. The resin in the flask was liquid, and the acid value was less than 0.1. Next, while cooling the content, 274 parts by mass of methyl ethyl ketone was added. A uniform solution was thus obtained. While keeping the temperature at 50°C or below, the stirring rotational speed was increased to 3,000 rpm and 960 parts by mass of ion-exchanged water was added over a period of 3 hr.
  • an aqueously dispersed epoxy resin composition (1) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 7,000 mPa ⁇ s, and a particle diameter d50 of 0.18 ⁇ m.
  • an aqueously dispersed epoxy resin composition (2) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 6,000 mPa ⁇ s, and a particle diameter d50 of 0.31 ⁇ m.
  • EXAMPLE 1 The procedures in EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in EXAMPLE 1 was changed to 25.0 parts by mass, and further 25.0 parts by mass of polypropylene glycol ( "PPG-2000" manufactured by Jiangsu Haian Petroleum Chemical Factory) was used in combination therewith, and that the amount of methyl-tetrahydrophthalic anhydride used in EXAMPLE 1 was changed to 221.3 parts by mass.
  • an aqueously dispersed epoxy resin composition (4) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 3,000 mPa ⁇ s, and a particle diameter d50 of 0.52 ⁇ m.
  • EXAMPLE 1 The procedures in EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in EXAMPLE 1 was changed to 30.0 parts by mass, and further 20.0 parts by mass of polytetramethylene ether glycol ( "PTMG3000” manufactured by Mitsubishi Chemical Corporation) was used in combination therewith, and that the amount of methyl-tetrahydrophthalic anhydride used in EXAMPLE 1 was changed to 221.3 parts by mass.
  • an aqueously dispersed epoxy resin composition (5) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 2,200 mPa ⁇ s, and a particle diameter d50 of 0.57 ⁇ m.
  • an aqueously dispersed epoxy resin composition (6) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 2,000 mPa ⁇ s, and a particle diameter d50 of 0.80 ⁇ m.
  • an aqueously dispersed epoxy resin composition (7) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 7, 400 mPa ⁇ s, and a particle diameter d50 of 0.25 ⁇ m.
  • a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 30.0 parts by mass of polyethylene glycol ( "PEG-3500” manufactured by Jiangsu Haian Petroleum Chemical Factory) and 206.3 parts by mass of hydrogenated bisphenol A.
  • polyethylene glycol "PEG-3500” manufactured by Jiangsu Haian Petroleum Chemical Factory
  • heating and stirring at 200 rpm were initiated.
  • the nitrogen supply was suspended at 110°C, and dehydration was performed under reduced pressure for 1 hr.
  • the pressure was increased again by supplying nitrogen, and 288.2 parts by mass of methyl-tetrahydrophthalic anhydride was added.
  • the temperature was increased to 130°C, and the reaction was performed for 5 hr.
  • an aqueously dispersed epoxy resin composition (R1) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 400 mPa ⁇ s, and a particle diameter d50 of 2.30 ⁇ m.
  • COMPARATIVE EXAMPLE 1 The procedures in COMPARATIVE EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in COMPARATIVE EXAMPLE 1 was changed to 150.0 parts by mass, the amount of hydrogenated bisphenol A was changed to 75.0 parts by mass, the amount of methyl-tetrahydrophthalic anhydride was changed to 118.0 parts by mass, the amount of "EPICLON 850-S" was changed to 750.0 parts by mass, the amount of methyl ethyl ketone was changed to 273 parts by mass, and the amount of ion-exchanged water was changed to 959 parts by mass.
  • an aqueously dispersed epoxy resin composition (R2) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 9,200 mPa ⁇ s, and a particle diameter d50 of 0.17 ⁇ m.
  • a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 200 parts by mass of polyethylene glycol ( "PEG-4000” manufactured by Jiangsu Haian Petroleum Chemical Factory) .
  • the nitrogen supply was suspended at 110°C, and the system was maintained at a reduced pressure for 1 hr.
  • the pressure was increased again by supplying nitrogen, and 37.6 parts by mass of "EPICLON 850-S" and 0.3 parts by mass of boron trifluoride-ethyl ether complex (a reagent) were added.
  • the reaction was performed at 130°C for 5 hr.
  • the product was recovered as an epoxy resin (r3) that was solid at room temperature.
  • the epoxy equivalent of the epoxy resin (r3) was 2,500 g/eq.
  • an aqueously dispersed epoxy resin composition (R3) was obtained that had a non-volatile content of 60 mass%, a Brookfield viscosity of 300 mPa ⁇ s, and a particle diameter d50 of 0.91 ⁇ m.
  • a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 400 parts by mass of polyethylene glycol ( "PEG-4000” manufactured by Jiangsu Haian Petroleum Chemical Factory) .
  • polyethylene glycol "PEG-4000” manufactured by Jiangsu Haian Petroleum Chemical Factory
  • heating and stirring at 200 rpm were initiated.
  • the nitrogen supply was suspended at 110°C, and the system was maintained at a reduced pressure for 1 hr.
  • the pressure was increased again by supplying nitrogen, and 38.4 parts by mass of trimellitic anhydride (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC. ) was added.
  • the reaction was performed at 110°C until the acid value became constant.
  • an aqueously dispersed epoxy resin composition (R4) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 250 mPa ⁇ s, and a particle diameter d50 of 1.30 ⁇ m.
  • a sample weighing exactly 1.0000 g was placed on an aluminum Petri dish and was spread thin. The sample was stored at 150°Cfor 1 hr. The non-volatile content was calculated based on the weights before and after the treatment.
  • the diameter d50 was determined by measuring the 50%cumulative particle diameter with "UPA-150"manufactured by MicrotracBEL.
  • Approximately 90 g of the aqueously dispersed epoxy resin composition obtained in EXAMPLE or COMPARATIVE EXAMPLE was added to a 100 ml-volume glass bottle and was stored at room temperature (25°C) . The appearance was visually observed after the predetermined time and the storage stability was evaluated based on the following criteria.
  • Table 1 describes the properties and the evaluation results of the aqueously dispersed epoxy resin compositions (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
  • Paints (1) to (7) and (R1) to (R4) were prepared according to the formulations described in Tables 2 and 3.
  • the paints were sprayed to cold-rolled steel plates ( "SPCC-SB" manufactured by TP Giken K.K., the surface had been degreased with xylene and water-polished with sandpaper No. 240) to form a film having a dry thickness of about 60 ⁇ m.
  • the films were cured at 25°Cfor 1 week and were tested under the following conditions. [Method for measuring impact strength]
  • Impact strength was measured by a method in accordance with GB/T 1732-1993.
  • Adhesion was measured by a method in accordance with GB/T 9286-1998.
  • Pencil hardness was measured by a method in accordance with GB/T 6739-2006.
  • Water resistance was evaluated by a method in accordance with GB/T 1733-1993, specifically, by checking for a change in the color of the film and determining the presence or absence of blisters or rust. The absence of a chromatic change, blisters, and rust indicates high water resistance.
  • the film was tested by a method in accordance with ASTM B117. After 1000 hours from the test, the film surface was inspected to determine the presence or absence of blisters and to measure the width of separation that had expanded from a slit. The salt spray resistance was thus measured. The absence of blisters and a smaller width of separation indicate higher anticorrosive properties.
  • Tables 2 and 3 describe the compositions of the paints (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
  • D 755W Dispersant TEGO DISPERSE 755W manufactured by EVONIK
  • BYK-346 Wetting agent manufactured by BYK
  • BYK-024" Anti-foaming agent manufactured by BYK
  • BYK-425" Thickener manufactured by BYK
  • HALOX FLASH-X 150 Flash rust inhibitor manufactured by ICL Phosphate Specialty
  • Iron oxide "R-516L” manufactured by Titan Kogyo, Ltd.
  • HLOX SZP-391 Anticorrosive pigment manufactured by ICL Phosphate Specialty
  • Precipitated barium sulfate Filler manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.
  • Table 4 describes the evaluation results of the paints (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
  • EXAMPLES 1 to 7 described in Table 1 represent examples of the aqueously dispersed epoxy resin compositions of the present invention. These aqueously dispersed epoxy resin compositions are shown to have high storage stability. Furthermore, the paints using these aqueously dispersed epoxy resin compositions gave cured films having excellent anticorrosive properties (EXAMPLES 8 to 14) .
  • COMPARATIVE EXAMPLE 1 described in Table 1 represents an example of aqueously dispersed epoxy resin compositions in which the ratio [ (a2-1) / (a1 + a2) ] specified in the present invention is outside the range of 3 to 10 (2.6) .
  • This aqueously dispersed epoxy resin composition was markedly low in storage stability. Furthermore, the paint using this aqueously dispersed epoxy resin composition gave a cured film having very poor anticorrosive properties (COMPARATIVE EXAMPLE 5) .
  • COMPARATIVE EXAMPLE 2 described in Table 1 represents an example of aqueously dispersed epoxy resin compositions in which the ratio [ (a2-1) / (a1 + a2) ] specified in the present invention is outside the range of 3 to 10 (13.7) .
  • This aqueously dispersed epoxy resin composition exhibited excellent storage stability.
  • the paint using this aqueously dispersed epoxy resin composition gave a cured film having very poor anticorrosive properties (COMPARATIVE EXAMPLE 6) .
  • COMPARATIVE EXAMPLES 3 and 4 described in Table 1 represent examples of aqueously dispersed epoxy resin compositions containing no polyvalent active hydrogen compound (a2-2) . These aqueously dispersed epoxy resin compositions were markedly low in storage stability. Furthermore, the paints using these aqueously dispersed epoxy resin compositions gave cured films having very poor anticorrosive properties (COMPARATIVE EXAMPLES 7 and 8) .

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Abstract

An aqueously dispersed epoxy resin composition is provided that has high storage stability and is capable of forming a cured film having excellent anticorrosive properties. The aqueously dispersed epoxy resin composition includes an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule; and an aqueous medium (B). The compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1), and an acid anhydride (a2-3). The content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass% of the total mass of the compound (a1) and the compound (a2).

Description

AQUEOUSLY DISPERSED EPOXY RESIN COMPOSITION, PAINT, AND ARTICLE [Technical Field]
The present invention relates to an aqueously dispersed epoxy resin composition, a paint, and an article.
[Background Art]
Epoxy resin compositions generally give cured products that are excellent in mechanical characteristics and electrical characteristics and have good properties, such as bonding properties, solvent resistance, water resistance, and heat resistance. Thus, epoxy resin compositions are used in wide ranges of applications including insulating materials in electric and electronic components, adhesives, paints, and civil engineering and building materials.
Epoxy resin compositions for these applications, in particular, for example, paint applications, are generally solvent-diluted compositions using various types of organic solvents. In recent years, however, the total volume of volatile organic compounds (VOC) is limited from the point of view of global environmental protection including air pollution control and working environment improvement. Attracts are then drawn to aqueously dispersed epoxy resin compositions free from organic solvents.
For example, a known aqueously dispersed epoxy resin composition is one obtained by first reacting polyethylene glycol with trimellitic anhydride, then reacting the product with an excess epoxy resin to synthesize an emulsifier, and adding the emulsifier to an epoxy resin followed by addition of water (see, for example, PTL 1) . Another aqueously dispersed epoxy resin composition that is known is obtained by first reacting polyethylene glycol with an acid anhydride, then  reacting the product with an excess epoxy resin to synthesize an emulsifier, which is then recovered, and adding the recovered emulsifier to an epoxy resin followed by addition of water (see, for example, PTL 2) . Unfortunately, these aqueously dispersed epoxy resin compositions are insufficient in storage stability and give cured products that do not meet the current increasing levels of performances (for example, anticorrosive properties) .
Thus, there has been a demand for materials that have high storage stability and excellent anticorrosive properties.
[Citation List] [Patent Literature]
[PTL 1]
Chinese Patent Application Publication No. 105801868
[PTL 2]
Chinese Patent Application Publication No. 108503846
[Summary of Invention]
[Technical Problem]
An object of the present invention is to provide an aqueously dispersed epoxy resin composition that has high storage stability and is capable of forming a cured film having excellent anticorrosive properties; a paint containing the aqueously dispersed epoxy resin composition; and an article having a cured film from the paint.
[Solution to Problem] 
The present inventors carried out extensive studies to achieve the above object. As a result, the present inventors have found that the object is achieved with an aqueously dispersed epoxy resin composition that contains an aqueous medium and an epoxy resin essentially obtained from a compound having at least two epoxy groups in the molecule and a compound obtained from specific polyvalent active hydrogen compounds and an acid  anhydride and having at least two carboxyl groups in the molecule. The present invention has been completed based on the finding.
Specifically, the present invention pertains to an aqueously dispersed epoxy resin composition that contains an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule; and an aqueous medium (B) , wherein the compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1) , and an acid anhydride (a2-3) , and the content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
[Advantageous Effects of Invention]
The aqueously dispersed epoxy resin composition of the present invention can be prepared by a simple method and has high storage stability. A paint containing the aqueously dispersed epoxy resin composition has excellent anticorrosive properties and thus may be suitably used in particular as an anticorrosive paint.
[Description of Embodiments]
An aqueously dispersed epoxy resin composition of the present invention contains an epoxy resin (A) obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule; and an aqueous medium (B) , wherein the compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active  hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1) , and an acid anhydride (a2-3) , and the content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
The epoxy resin (A) used here is one obtained from essential ingredients including a compound (a1) having at least two epoxy groups in the molecule, and a compound (a2) having at least two carboxyl groups in the molecule.
Examples of the compounds (a1) having at least two epoxy groups in the molecule (hereinafter, sometimes written simply as the "compounds (a1) ") include bisphenol-type epoxy resins synthesized from a bisphenol and an epihalohydrin; novolac-type epoxy resins synthesized from a phenol/alkylphenol novolac and an epihalohydrin; biphenol-type epoxy resins; epoxy resins synthesized from a compound diol having aromatic rings adj acent to one another, such as naphthalenediol, and an epihalohydrin; glycidylamines synthesized from an aromatic amine and an epihalohydrin; epoxy resins synthesized from an aliphatic amine and an epihalohydrin; epoxy resins synthesized from an aliphatic alcohol and an epihalohydrin; epoxy resins obtained by reacting a diene compound-phenol condensate, such as dicyclopentadiene-phenol condensate, with an epihalohydrin; glycidylamines obtained by reacting a polycarboxylic acid with an epihalohydrin; and compounds having an epoxy ring formed by oxidation of a double bond in the molecule with a peroxide. These compounds may be used singly, or two or more may be used in combination.
Examples of the compounds (a1) further include compounds obtained by modifying the epoxy resins described above through reaction with modifiers, such as polyphenol compounds, polycarboxylic compounds, and polyamine compounds.
Among those described above, bisphenol-type epoxy resins and novolac-type epoxy resins are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties. Bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and phenol novolac-type epoxy resins are more preferable.
To control the viscosity or to control the reactivity, a monofunctional epoxy resin may be used in combination with the compound (a1) . Examples of the monofunctional epoxy resins include butyl glycidyl ether, 2-ethylhexanol glycidyl ether, C12-13 alcohol glycidyl ether, phenyl glycidyl ether, o-cresol glycidyl ether, p-sec-butyl glycidyl ether, t-butylphenol glycidyl ether, cardanol glycidyl ether, and glycidyl neodecanoate. The monofunctional epoxy resins may be used singly, or two or more may be used in combination.
To ensure that the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties, the amount in which the compound (a1) is used is preferably in the range of 55 to 70 mass%of the total mass of the essential ingredients for the epoxy resin (A) , that is, the total mass of the compound (a1) and the compound (a2) having at least two carboxyl groups in the molecule. If the amount of the compound (a1) used is less than 55 mass%, cured films have insufficient anticorrosive properties. If the amount is in excess of 70 mass%, it is difficult to concurrently satis fy the water dispersibility and the anticorrosive properties of cured films.
The compound (a2) having at least two carboxyl groups in the molecule (hereinafter, also written simply as the "compound (a2) " ) is one obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2)  having an alicyclic skeleton, and an acid anhydride (a2-3) .
For example, the polyvalent active hydrogen compound (a2-1) may be a compound that contains ethylene glycol, propylene glycol, and/or tetramethylene ether glycol as repeating units, and has a molecular weight distribution. Such compounds may be used singly, or two or more may be used in combination.
In the polyvalent active hydrogen compound (a2-1) , the terminal active hydrogen moiety may be, for example, a hydroxyl group or an amino group. Examples of the polyvalent active hydrogen compounds (a2-1) include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, a compound in which polyethylene glycol and polypropylene glycol are condensed, a compound in which polypropylene glycol is introduced in glycerin, a compound in which polyethylene glycol and polypropylene glycol are condensed and introduced in glycerin, and polycarbonate diol polymerized through carbonate groups. Examples of the commercially available polyvalent active hydrogen compounds (a2-1) include "Jeffamine D-series" and "Jeffamine T-series" manufactured by Huntsman. The polyvalent active hydrogen compounds may be used singly, or two or more may be used in combination.
Among those described above, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
To ensure that the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties, the polyvalent active hydrogen compound (a2-1) is used so that the content thereof will be in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
The polyvalent active hydrogen compound (a2-2) may be any compound that has an alicyclic skeleton in the molecule and has active hydrogen at a terminal. Examples include 2, 2'-isopropylidenecyclohexanol, 2, 4'-isopropylidenecyclohexanol, 4, 4'-isopropylidenecyclohexanol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, tricyclo [5, 2, 1, 02, 6] decane-4, 8-dimethanol, 2, 2'-methylenebiscyclohexylamine, 2, 4'-methylenebiscyclohexylamine, and 4, 4'-methylenebiscyclohexylamine. The polyvalent active hydrogen compounds may be used singly, or two or more may be used in combination.
Among those described above, 4, 4'-isopropylidenecyclohexanol, 1, 4-cyclohexanedimethanol, 1, 3-diaminocyclohexane, and 4, 4'-methylenebiscyclohexylamine are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties. 4, 4'-Isopropylidenecyclohexanol and 1, 4-cyclohexanedimethanol are more preferable.
To ensure that the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties, the mass ratio [ (a2-2) / (a2-1) ] of the polyvalent active hydrogen compound (a2-2) to the polyvalent active hydrogen compound (a2-1) is preferably in the range of 0.3 to 6.
The acid anhydride (a2-3) is not particularly limited and may be any acid anhydride distributed as an industrial product.  Examples include succinic anhydride, octylsuccinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, phthalic anhydride, methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methylnadic anhydride, trimellitic anhydride, pyromellitic anhydride, and dodecanedioic anhydride. The acid anhydrides may be used singly, or two or more may be used in combination.
Among those described above, methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl-hexahydrophthalic anhydride are preferable because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties.
The compound (a2) may be produced by any method without limitation. For example, the compound (a2) may be obtained by a method in which the essential ingredients including the polyvalent active hydrogen compound (a2-1) , the polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton, and the acid anhydride (a2-3) are stirred in a container under a nitrogen atmosphere while performing heating at 90 to 200℃. The polyvalent active hydrogen compound (a2-1) is water absorptive. Thus, the above method preferably involves vacuum heating treatment at an initial stage of the reaction to remove water contained in the compound (a2-1) . In this manner, the compound (a2) may be obtained stably.
To ensure that the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties, the amount in which the compound (a2) is used is preferably in the range of 30 to 45 mass%of the total mass of the essential ingredients for the epoxy resin (A) , that is, the total mass of the compound (a1) and the compound (a2) . If the amount of the compound (a2)  used is less than 30 mass%, it is difficult to concurrently satisfy the water dispersibility and the anticorrosive properties of cured films. If the amount is in excess of 45 mass%, cured films have insufficient anticorrosive properties.
The epoxy resin (A) may be produced by any method without limitation. For example, the epoxy resin (A) may be obtained by a method in which the essential ingredients including the compound (a1) and the compound (a2) are stirred under a nitrogen atmosphere while performing heating at 100 to 200℃. This method may involve a catalyst to shorten the reaction time.
Examples of the catalysts include tertiary amines, such as triethylamine, tributylamine, benzyldimethylamine, 2, 4, 6-tris (dimethylaminomethyl) phenol, and N-methylpiperazine, and salts thereof; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2, 4-dicyano-6- [2-methylimidazolyl-1] -ethyl-S-triadine, and 2-ethyl-4-methylimidazole tetraphenylborate, and salts thereof; diazabicyclo compounds, such as 1, 5-diazabicyclo [5, 4, 0] -7-undecane, 1, 5-diazabicyclo [4, 3, 0] -5-nonene, 1, 4-diazabicyclo [2, 2, 2] octane, and 1, 8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate; phosphines, such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl) phosphine; and phosphonium salts, such as tetraphenylphosphonium salt, methyltributylphosphonium salt, methyltricyanoethylphosphonium salt, and tetrabutylphosphonium salt. The catalysts may be used singly, or two or more may be used in combination. Among those described above, triphenylphosphine is preferable.
The solid epoxy equivalent in the epoxy resin (A) is preferably  in the range of 300 to 1, 300 g/eq. because the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties. If the solid epoxy equivalent is less than 300 g/eq., films are hard but brittle. If the solid epoxy equivalent is in excess of 1, 300 g/eq., the reactivity with a curing agent is lowered and the water resistance is deteriorated.
For example, the aqueous medium (B) may be ion-exchanged water or distilled water. The aqueous media may be used singly, or two or more may be used in combination.
The aqueously dispersed epoxy resin composition of the present invention may be produced by any method without limitation. For example, the aqueously dispersed epoxy resin composition may be obtained by mixing the epoxy resin (A) and the aqueous medium (B) together.
For example, the epoxy resin (A) and the aqueous medium (B) may be mixed together using a reaction vessel equipped with a stirring blade; a kneading device, such as a kneader, a continuous kneader, a taper roll machine, a single-screw extruder, a twin-screw extruder, a triple-screw extruder, a universal mixer, Plastomill, or a Votator-type kneading device; a rotary dispersing mixer, such as a homomixer, a static mixer, FILMIX, Ebara Milder, CLEARMIX, ULTRA-TURRAX, CAVITRON, or BIO-MIXER; an ultrasonic disperser; or a device having no mobile sections and performs mixing by the flow of a fluid itself, such as an in-line mixer.
In the method for producing the aqueously dispersed epoxy resin composition, an organic solvent may be used before the addition of the aqueous medium (B) , or together with the aqueous medium (B) . The organic solvent is not necessarily a water-soluble solvent, and is not particularly limited as long as the organic  solvent can dissolve the resin resulting from the reaction and is inert to the resin at the time of use. Examples include ester compounds, such as ethyl acetate, 3-methoxybutyl acetate, methoxypropyl acetate, and cellosolve acetate; alcohol compounds, such as methanol, ethanol, and isopropanol; cellosolve compounds, such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve; glyme compounds, such as monoglyme, diglyme, and triglyme; propylene glycol monoalkyl ether compounds, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, and propylene glycol mono-tert-butyl ether; and ketone compounds, such as acetone and methyl ethyl ketone. Among those described above, cellosolve compounds, propylene glycol monoalkyl ether compounds, and ketone compounds are preferable.
The organic solvent may remain in the aqueously dispersed epoxy resin composition or may be evaporated by distillation under reduced pressure.
To ensure that the aqueously dispersed epoxy resin composition that is obtained has high storage stability and can form a cured film having excellent anticorrosive properties, the mass ratio [ (A) / (B) ] of the epoxy resin (A) to the aqueous medium (B) is preferably in the range of 20/80 to 75/25, and more preferably in the range of 40/60 to 70/30.
Where necessary, the aqueously dispersed epoxy resin composition of the present invention may further contain a curing agent.
Examples of the curing agents include basic curing agents.
Examples of the basic curing agents include aliphatic polyamines, alicyclic polyamines, Mannich bases, amine-epoxy  adducts, polyamidepolyamines, and liquid aromatic polyamines. The curing agents may be used singly, or two or more may be used in combination.
Examples of the aliphatic polyamines include polyalkylenepolyamines, such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine, and 1, 4-bis- (3-aminopropyl) piperazine, m-xylenediamine, and p-xylenediamine.
Examples of the alicyclic polyamines include 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, and isophoronediamine.
Examples of the Mannich bases include condensation products of (1) a polyamine, such as triethylenetriamine, isophoronediamine, m-xylenediamine, or p-xylenediamine, (2) an aldehyde, such as formaldehyde, and (3) a monovalent or polyvalent cresol or xylenol, or a phenol, such as p-tert-butylphenol or resorcin, having at least one aldehyde reactive site in the nucleus.
Examples of the amine-epoxy adducts include (1) reaction products of (a) a polyamine, such as triethylenetriamine, tetraethylenepentamine, isophoronediamine, m-xylenediamine, or p-xylenediamine, with (b) an epoxy resin, for example, a glycidyl ether, such as phenyl glycidyl ether, butyl glycidyl ether, diglycidyl ether of bisphenol A, or diglycidyl ether of bisphenol F; and (2) reaction products of the above polyamine with a glycidyl ester, such as "Cardura E" (registered trademark, Yuka Shell Epoxy K.K. ) .
Examples of the polyamidepolyamines include those obtained by reaction of a polyamine with a polycarboxylic acid or a dimerized fatty acid, such as reaction products between ethylene diamine and a dimer acid.
Examples of the liquid aromatic polyamines include reaction products of an aromatic polyamine with a glycidyl ether or a glycidyl ester. Examples of the aromatic polyamines include diaminodiphenylmethane and diaminodiphenylsulfone. Examples of the glycidyl ethers include phenyl glycidyl ether, butyl glycidyl ether, diglycidyl ether of bisphenol A, and diglycidyl ether of bisphenol F. Examples of the glycidyl esters include "Cardura E" .
The curing agent is preferably used in such an amount that the ratio [epoxy equivalent/amine equivalent] of the epoxy equivalent in the aqueously dispersed epoxy resin composition of the present invention to the amine equivalent in the basic curing agent is in the range of 0.75 to 1.25.
Where necessary, the aqueously dispersed epoxy resin composition of the present invention may contain other resin components, such as polyester-based aqueous resins and acrylic-based aqueous resins.
Where necessary, the aqueously dispersed epoxy resin composition of the present invention may contain additives. Examples of the additives include anti-cissing agents, anti-sagging agents, flowing agents, anti-foaming agents, curing accelerators, UV absorbers, and light stabilizers.
The aqueously dispersed epoxy resin composition of the present invention may be used in any application without limitation. Examples of the use applications include paints, adhesives, fiber-sizing agents, and concrete primers.
When the aqueously dispersed epoxy resin composition of the present invention is used in a paint application, it is preferable to add, for example, various pigments, such as antirust pigments, coloring pigments, and extender pigments,  and various additives as required.
Examples of the antirust pigments include flake pigments, such as zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, and graphite.
Examples of the coloring pigments include carbon black, titanium oxide, zinc sulfide, and red oxide.
Examples of the extender pigments include barium sulfate, calcium carbonate, talc, and kaolin.
The additives are preferably added in an amount of 10 to 70 parts by mass with respect to 100 parts by mass of the solids in the aqueously dispersed epoxy resin composition.
When used as a paint, the aqueously dispersed epoxy resin composition of the present invention may be applied by any method without limitation. Some exemplary application methods include roll coating, spraying, brushes, spatulas, bar coaters, dip coating, and electrodeposition. The application may be followed by drying at room temperature and thermal curing. The heating temperature in the thermal curing is preferably in the range of 50 to 250℃, and particularly preferably in the range of 60 to 230℃. The amount of heating time is preferably in the range of 2 to 30 minutes, and particularly preferably in the range of 5 to 20 minutes.
For example, the aqueously dispersed epoxy resin composition of the present invention may be used in general applications, such as aqueous paints for building interiors, aqueous paints for building exteriors and inorganic construction materials, aqueous paints for iron rust prevention, and aqueous paints for automobile repairing, and industrial applications, such as automotive paints and for beverage cans. The aqueously  dispersed epoxy resin composition of the present invention has excellent anticorrosive properties and set-to-touch properties, and is suitably used as a heavy-duty aqueous paint for iron rust prevention in such structures as steel structures and bridges, in particular, as an aqueous primer paint for iron rust prevention.
The aqueously dispersed epoxy resin composition of the present invention may be used as an adhesive in any manner without limitation. For example, the aqueously dispersed epoxy resin composition may be applied to substrates with a spray, a brush, or a spatula, and the bonding surfaces of the substrates may be joined to each other. A strong bonding layer may be formed at the joint by fixing the periphery of the joint or by pressing the substrates to each other. Suitable substrates are steel sheets or plates, concretes, mortars, wood, resin sheets, and resin films. Where necessary, the aqueously dispersed epoxy resin composition is more preferably applied after the substrates are subjected to various surface treatments, for example, physical treatments, such as polishing, electrical treatments, such as corona treatment, and chemical treatments, such as chemical conversion treatment.
The aqueously dispersed epoxy resin composition of the present invention may be used as a fiber-sizing agent in any manner without limitation. For example, the aqueously dispersed epoxy resin composition may be applied to just-spun fibers with a roller coater, and the fiber strand may be wound and dried. Any fibers may be used without limitation. Examples of the fibers include inorganic fibers, such as glass fibers, ceramic fibers, asbestos fibers, carbon fibers, and stainless steel fibers, natural fibers, such as cotton and hemp, and synthetic fibers, such as polyesters, polyamides, and urethanes. Examples of the shapes of the fibers as substrates include short fibers, long fibers, yarns, mats, and sheets. The amount in which the fiber-sizing agent is used is preferably 0.1 to 2 mass% in terms of solid resin relative to the fibers.
[EXAMPLES] 
Hereinbelow, the present invention will be described in detail based on EXAMPLES and COMPARATIVE EXAMPLES. However, it should be construed that the scope of the present invention is not limited to those EXAMPLES below.
(EXAMPLE 1: Preparation of aqueously dispersed epoxy resin composition (1) )
A four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 50.0 parts by mass of polyethylene glycol ( "PEG-3500" manufactured by Jiangsu Haian Petroleum Chemical Factory) and 156.3 parts by mass of hydrogenated bisphenol A. In a nitrogen atmosphere, heating and stirring at 200 rpm were initiated. The nitrogen supply was suspended at 110℃, and dehydration was performed under reduced pressure for 1 hr. The pressure was increased again by supplying nitrogen, and 221.0 parts by mass of methyl-tetrahydrophthalic anhydride ( "HN-2000" manufactured by Showa Denko Materials Co., Ltd. ) was added. The temperature was increased to 130℃, and the reaction was performed for 5 hr. There were added 667.0 parts by mass of a bisphenol A-type liquid epoxy resin ( "EPICLON 850-S" manufactured by DIC CORPORATION) and 0.5 parts by mass of triphenylphosphine. The reaction was performed for another 5 hr. The resin in the flask was liquid, and the acid value was less than 0.1. Next, while cooling the content, 274 parts by mass of methyl ethyl ketone was added. A uniform solution was thus obtained. While keeping the temperature at 50℃ or below, the stirring rotational speed was increased to 3,000 rpm and 960 parts by mass of ion-exchanged water was added over a period of 3 hr. Subsequently, methyl ethyl ketone was evaporated by reducing the pressure. The concentration was controlled by adding ion-exchanged water. Thus, an aqueously dispersed epoxy resin composition (1) was obtained that had a non-volatile  content of 55 mass%, a Brookfield viscosity of 7,000 mPa·s, and a particle diameter d50 of 0.18 μm.
(EXAMPLE 2: Preparation of aqueously dispersed epoxy resin composition (2) )
The procedures in EXAMPLE 1 were repeated, except that the hydrogenated bisphenol A used in EXAMPLE 1 was replaced by 94.6 parts by mass of cyclohexanedimethanol ( "CHDM-D" manufactured by EASTMAN) , and that the amounts were changed to 222.8 parts by mass of methyl-tetrahydrophthalic anhydride, 716.2 parts by mass of "EPICLON 850-S" , 270 parts by mass of methyl ethyl ketone, and 951 parts by mass of ion-exchanged water. Thus, an aqueously dispersed epoxy resin composition (2) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 6,000 mPa·s, and a particle diameter d50 of 0.31 μm.
(EXAMPLE 3: Preparation of aqueously dispersed epoxy resin composition (3) )
The procedures in EXAMPLE 1 were repeated, except that the amount of "EPICLON 850-S" used in EXAMPLE 1 was changed to 533.6 parts by mass, and further 133.4 parts by mass of a phenol novolac-type epoxy resin ( "EPICLON N-740" manufactured by DIC CORPORATION) was used in combination therewith. Thus, an aqueously dispersed epoxy resin composition (3) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 5,800 mPa·s, and a particle diameter d50 of 0.22 μm.
(EXAMPLE 4: Preparation of aqueously dispersed epoxy resin composition (4) )
The procedures in EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in EXAMPLE 1 was changed to 25.0 parts by mass, and further 25.0 parts by mass of polypropylene glycol ( "PPG-2000" manufactured by Jiangsu Haian Petroleum Chemical Factory) was used in combination therewith,  and that the amount of methyl-tetrahydrophthalic anhydride used in EXAMPLE 1 was changed to 221.3 parts by mass. Thus, an aqueously dispersed epoxy resin composition (4) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 3,000 mPa·s, and a particle diameter d50 of 0.52 μm.
(EXAMPLE 5: Preparation of aqueously dispersed epoxy resin composition (5) )
The procedures in EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in EXAMPLE 1 was changed to 30.0 parts by mass, and further 20.0 parts by mass of polytetramethylene ether glycol ( "PTMG3000" manufactured by Mitsubishi Chemical Corporation) was used in combination therewith, and that the amount of methyl-tetrahydrophthalic anhydride used in EXAMPLE 1 was changed to 221.3 parts by mass. Thus, an aqueously dispersed epoxy resin composition (5) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 2,200 mPa·s, and a particle diameter d50 of 0.57 μm.
(EXAMPLE 6: Preparation of aqueously dispersed epoxy resin composition (6) )
The procedures in EXAMPLE 1 were repeated, except that the polyethylene glycol ( "PEG-3500" manufactured by Jiangsu Haian Petroleum Chemical Factory) used in EXAMPLE 1 was replaced by 75.0 parts by mass of "PEG-2000" manufactured by Jiangsu Haian Petroleum Chemical Factory, the amount of hydrogenated bisphenol A was changed to 150.0 parts by mass, the methyl-tetrahydrophthalic anhydride was replaced by 204.1 parts by mass of hexahydrophthalic anhydride ( "RIKACID HH" manufactured by New Japan Chemical Co., Ltd. ) , the amount of "EPICLON 850-S" was changed to 652.2 parts by mass, the amount of methyl ethyl ketone was changed to 270 parts by mass, and the amount of ion-exchanged water was changed to 949 parts by mass. Thus, an aqueously dispersed epoxy resin composition (6)  was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 2,000 mPa·s, and a particle diameter d50 of 0.80 μm.
(EXAMPLE 7: Preparation of aqueously dispersed epoxy resin composition (7) )
The procedures in EXAMPLE 1 were repeated, except that the amount of hydrogenated bisphenol A used in EXAMPLE 1 was changed to 176.5 parts by mass, the methyl-tetrahydrophthalic anhydride used in EXAMPLE 1 was replaced by 230.9 parts by mass of hexahydrophthalic anhydride, "EPICLON 850-S" used in EXAMPLE 1 was replaced by 647.0 parts by mass of a bisphenol F-type liquid epoxy resin ( "EPICLON 830-S" manufactured by DIC CORPORATION) , the amount of methyl ethyl ketone was changed to 276 parts by mass, and the amount of ion-exchanged water was changed to 969 parts by mass. Thus, an aqueously dispersed epoxy resin composition (7) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 7, 400 mPa·s, and a particle diameter d50 of 0.25 μm.
(COMPARATIVE EXAMPLE 1: Preparation of aqueously dispersed epoxy resin composition (R1) )
A four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 30.0 parts by mass of polyethylene glycol ( "PEG-3500" manufactured by Jiangsu Haian Petroleum Chemical Factory) and 206.3 parts by mass of hydrogenated bisphenol A. In a nitrogen atmosphere, heating and stirring at 200 rpm were initiated. The nitrogen supply was suspended at 110℃, and dehydration was performed under reduced pressure for 1 hr. The pressure was increased again by supplying nitrogen, and 288.2 parts by mass of methyl-tetrahydrophthalic anhydride was added. The temperature was increased to 130℃, and the reaction was performed for 5 hr. There were added 637.5 parts by mass of "EPICLON 850-S" and 0.5 parts by mass of triphenylphosphine. The reaction was performed for another 5 hr. Next, while  cooling the content, 290 parts by mass of methyl ethyl ketone was added. A uniform solution was thus obtained. While keeping the temperature at 50℃ or below, the stirring rotational speed was increased to 3,000 rpm and 1,020 parts by mass of ion-exchanged water was added over a period of 3 hr. Subsequently, methyl ethyl ketone was evaporated by reducing the pressure. The concentration was controlled by adding ion-exchanged water. Thus, an aqueously dispersed epoxy resin composition (R1) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 400 mPa·s, and a particle diameter d50 of 2.30 μm.
(COMPARATIVE EXAMPLE 2: Preparation of aqueously dispersed epoxy resin composition (R2) )
The procedures in COMPARATIVE EXAMPLE 1 were repeated, except that the amount of polyethylene glycol used in COMPARATIVE EXAMPLE 1 was changed to 150.0 parts by mass, the amount of hydrogenated bisphenol A was changed to 75.0 parts by mass, the amount of methyl-tetrahydrophthalic anhydride was changed to 118.0 parts by mass, the amount of "EPICLON 850-S" was changed to 750.0 parts by mass, the amount of methyl ethyl ketone was changed to 273 parts by mass, and the amount of ion-exchanged water was changed to 959 parts by mass. Thus, an aqueously dispersed epoxy resin composition (R2) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 9,200 mPa·s, and a particle diameter d50 of 0.17 μm.
(COMPARATIVE EXAMPLE 3: Preparation of aqueously dispersed epoxy resin composition (R3) )
A four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 200 parts by mass of polyethylene glycol ( "PEG-4000" manufactured by Jiangsu Haian Petroleum Chemical Factory) . In a nitrogen atmosphere, heating and stirring at 200 rpm were initiated. The nitrogen supply was suspended at 110℃, and the system was maintained at a reduced pressure for 1 hr. The  pressure was increased again by supplying nitrogen, and 37.6 parts by mass of "EPICLON 850-S" and 0.3 parts by mass of boron trifluoride-ethyl ether complex (a reagent) were added. The reaction was performed at 130℃ for 5 hr. The product was recovered as an epoxy resin (r3) that was solid at room temperature. The epoxy equivalent of the epoxy resin (r3) was 2,500 g/eq.
Next, 500.0 parts by mass of "EPICLON 1050" was added to a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, and was melted in a nitrogen atmosphere at 100℃. While performing cooling, 125 parts by mass of methyl ethyl ketone was added to dissolve the resin. Next, 50.0 parts by mass of the epoxy resin (r3) was added. The mixture was homogenized by stirring at 60℃ for 1 hr, and was cooled to 50℃ or below. The stirring speed was increased to 3,000 rpm. Subsequently, 450 parts by mass of ion-exchanged water was added over a period of 3 hr. The solvent was then evaporated under reduced pressure, and ion-exchanged water was added. Thus, an aqueously dispersed epoxy resin composition (R3) was obtained that had a non-volatile content of 60 mass%, a Brookfield viscosity of 300 mPa·s, and a particle diameter d50 of 0.91 μm.
(COMPARATIVE EXAMPLE 4: Preparation of aqueously dispersed epoxy resin composition (R4) )
A four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 400 parts by mass of polyethylene glycol ( "PEG-4000" manufactured by Jiangsu Haian Petroleum Chemical Factory) . In a nitrogen atmosphere, heating and stirring at 200 rpm were initiated. The nitrogen supply was suspended at 110℃, and the system was maintained at a reduced pressure for 1 hr. The pressure was increased again by supplying nitrogen, and 38.4 parts by mass of trimellitic anhydride (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC. ) was added. The reaction  was performed at 110℃ until the acid value became constant. Subsequently, 9.1 parts by mass of a bisphenol A-type epoxy resin ( "EPICLON 860" manufactured by DIC CORPORATION, epoxy equivalent: 240 g/eq. ) and 0.2 parts by mass of triphenylphosphine were added, and the reaction was performed at 120℃ for 5 hr to give an epoxy resin (r4) that was solid at room temperature. The epoxy equivalent of the epoxy resin (r4) was 3,200 g/eq.
Next, 500.0 parts by mass of "EPICLON 860" was added to a four-necked glass flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube. The temperature was increased to 60℃. Next, 75 parts by mass of the epoxy resin (r4) was added. The mixture was homogenized by stirring at the temperature for 1 hr, and was cooled to 50℃ or below. The stirring speed was increased to 3,000 rpm. Subsequently, 471 parts by mass of ion-exchanged water was added over a period of 3 hr. Thus, an aqueously dispersed epoxy resin composition (R4) was obtained that had a non-volatile content of 55 mass%, a Brookfield viscosity of 250 mPa·s, and a particle diameter d50 of 1.30 μm.
The properties in EXAMPLES and COMPARATIVE EXAMPLES were measured as follows.
[Non-volatile content]
A sample weighing exactly 1.0000 g was placed on an aluminum Petri dish and was spread thin. The sample was stored at 150℃for 1 hr. The non-volatile content was calculated based on the weights before and after the treatment.
[Epoxy equivalent]
Measurement was performed by perchloric acid-acetic acid titration.
[Viscosity]
Measurement was performed in accordance with GB/T 11175-2002.
[Particle diameter]
The diameter d50 was determined by measuring the 50%cumulative particle diameter with "UPA-150"manufactured by MicrotracBEL.
The evaluations described below were performed using the aqueously dispersed epoxy resin compositions (1) to (7) and (R1) to (R4) obtained in EXAMPLES and COMPARATIVE EXAMPLES.
[Method for evaluating the storage stability of the aqueously dispersed epoxy resin compositions]
Approximately 90 g of the aqueously dispersed epoxy resin composition obtained in EXAMPLE or COMPARATIVE EXAMPLE was added to a 100 ml-volume glass bottle and was stored at room temperature (25℃) . The appearance was visually observed after the predetermined time and the storage stability was evaluated based on the following criteria.
A: No separation or sedimentation
B: Separate upper layer
C: Clear separation and sedimentation
Table 1 describes the properties and the evaluation results of the aqueously dispersed epoxy resin compositions (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
[Table 1]
[Evaluation of films]
Paints (1) to (7) and (R1) to (R4) were prepared according to the formulations described in Tables 2 and 3. The paints were sprayed to cold-rolled steel plates ( "SPCC-SB" manufactured by TP Giken K.K., the surface had been degreased with xylene and water-polished with sandpaper No. 240) to form a film having a dry thickness of about 60 μm. The films were cured at 25℃for 1 week and were tested under the following conditions. [Method for measuring impact strength]
Impact strength was measured by a method in accordance with GB/T 1732-1993.
[Method for measuring adhesion]
Adhesion was measured by a method in accordance with GB/T  9286-1998.
[Method for measuring pencil hardness]
Pencil hardness was measured by a method in accordance with GB/T 6739-2006.
[Method for evaluating water resistance]
Water resistance was evaluated by a method in accordance with GB/T 1733-1993, specifically, by checking for a change in the color of the film and determining the presence or absence of blisters or rust. The absence of a chromatic change, blisters, and rust indicates high water resistance.
[Method for evaluating salt spray resistance]
The film was tested by a method in accordance with ASTM B117. After 1000 hours from the test, the film surface was inspected to determine the presence or absence of blisters and to measure the width of separation that had expanded from a slit. The salt spray resistance was thus measured. The absence of blisters and a smaller width of separation indicate higher anticorrosive properties.
Tables 2 and 3 describe the compositions of the paints (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
[Table 2]
[Table 3]
The manufacturers described in Tables 2 and 3 are as follows.
"D 755W" : Dispersant TEGO DISPERSE 755W manufactured by EVONIK
"BYK-346" : Wetting agent manufactured by BYK
"BYK-024" : Anti-foaming agent manufactured by BYK
"DPnB" : Dipropylene glycol butyl ether manufactured by The Dow Chemical Company
"BYK-425" : Thickener manufactured by BYK
"HALOX FLASH-X 150" : Flash rust inhibitor manufactured by ICL Phosphate Specialty
Iron oxide: "R-516L" manufactured by Titan Kogyo, Ltd.
"HALOX SZP-391" : Anticorrosive pigment manufactured by ICL Phosphate Specialty
Precipitated barium sulfate: Filler manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.
Table 4 describes the evaluation results of the paints (1) to (7) and (R1) to (R4) prepared in EXAMPLES and COMPARATIVE EXAMPLES.
[Table 4]
EXAMPLES 1 to 7 described in Table 1 represent examples of the aqueously dispersed epoxy resin compositions of the present invention. These aqueously dispersed epoxy resin compositions are shown to have high storage stability. Furthermore, the paints using these aqueously dispersed epoxy resin compositions gave cured films having excellent anticorrosive properties (EXAMPLES 8 to 14) .
On the other hand, COMPARATIVE EXAMPLE 1 described in Table 1 represents an example of aqueously dispersed epoxy resin compositions in which the ratio [ (a2-1) / (a1 + a2) ] specified in the present invention is outside the range of 3 to 10 (2.6) . This aqueously dispersed epoxy resin composition was markedly low in storage stability. Furthermore, the paint using this aqueously dispersed epoxy resin composition gave a cured film having very poor anticorrosive properties (COMPARATIVE EXAMPLE 5) .
COMPARATIVE EXAMPLE 2 described in Table 1 represents an example of aqueously dispersed epoxy resin compositions in which the ratio [ (a2-1) / (a1 + a2) ] specified in the present invention is outside the range of 3 to 10 (13.7) . This aqueously dispersed epoxy resin composition exhibited excellent storage stability. However, the paint using this aqueously dispersed epoxy resin composition gave a cured film having very poor anticorrosive properties (COMPARATIVE EXAMPLE 6) .
COMPARATIVE EXAMPLES 3 and 4 described in Table 1 represent examples of aqueously dispersed epoxy resin compositions containing no polyvalent active hydrogen compound (a2-2) . These aqueously dispersed epoxy resin compositions were markedly low in storage stability. Furthermore, the paints using these aqueously dispersed epoxy resin compositions gave cured films having very poor anticorrosive properties (COMPARATIVE EXAMPLES 7 and 8) .

Claims (8)

  1. An aqueously dispersed epoxy resin composition comprising:
    an epoxy resin (A) obtained from essential ingredients including:
    a compound (a1) having at least two epoxy groups in the molecule, and
    a compound (a2) having at least two carboxyl groups in the molecule; and
    an aqueous medium (B) , wherein
    the compound (a2) is obtained from essential ingredients including a polyvalent active hydrogen compound (a2-1) having repeating alkylene units, a polyvalent active hydrogen compound (a2-2) having an alicyclic skeleton and distinct from the polyvalent active hydrogen compound (a2-1) , and an acid anhydride (a2-3) , and
    the content of the polyvalent active hydrogen compound (a2-1) is in the range of 3 to 10 mass%of the total mass of the compound (a1) and the compound (a2) .
  2. The aqueously dispersed epoxy resin composition according to Claim 1, wherein the compound (a1) comprises a bisphenol-type epoxy resin and/or a novolac-type epoxy resin.
  3. The aqueously dispersed epoxy resin composition according to Claim 1, wherein the mass ratio [ (a2-2) / (a2-1) ] of the polyvalent active hydrogen compound (a2-2) to the polyvalent active hydrogen compound (a2-1) is in the range of 0.3 to 6.
  4. The aqueously dispersed epoxy resin composition according to Claim 1, wherein the polyvalent active hydrogen compound (a2-1) comprises one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
  5. The aqueously dispersed epoxy resin composition according to  Claim 1, wherein the polyvalent active hydrogen compound (a2-2) comprises cyclohexanedimethanol and/or hydrogenated bisphenol A.
  6. The aqueously dispersed epoxy resin composition according to Claim 1, wherein the acid anhydride (a2-3) comprises one or more selected from the group consisting of succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, methyl-tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  7. A paint comprising the aqueously dispersed epoxy resin composition described in any one of Claims 1 to 6.
  8. An article comprising a cured film from the paint described in Claim 7.
PCT/CN2023/086775 2023-04-07 2023-04-07 Aqueously dispersed epoxy resin composition, paint, and article Pending WO2024207393A1 (en)

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