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WO2024207393A1 - Composition de résine époxy dispersée dans l'eau, peinture et article - Google Patents

Composition de résine époxy dispersée dans l'eau, peinture et 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
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English (en)
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/fr
Priority to CN202380090137.8A priority patent/CN120457177A/zh
Priority to TW113112636A priority patent/TW202444787A/zh
Publication of WO2024207393A1 publication Critical patent/WO2024207393A1/fr
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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de résine époxy dispersée dans l'eau qui a une stabilité au stockage élevée et est apte à former un film durci ayant d'excellentes propriétés anticorrosives. La composition de résine époxy dispersée dans l'eau comprend une résine époxy (A) obtenue à partir d'ingrédients essentiels comprenant un composé (a1) ayant au moins deux groupes époxy dans la molécule, et un composé (a2) ayant au moins deux groupes carboxyle dans la molécule; et un milieu aqueux (B). Le composé (a2) est obtenu à partir d'ingrédients essentiels comprenant un composé d'hydrogène actif polyvalent (a2-1) ayant des motifs d'alkylène récurrents, un composé d'hydrogène actif polyvalent (a2-2) ayant un squelette alicyclique et distinct du composé d'hydrogène actif polyvalent (a2-1), et un anhydride d'acide (a2-3). La teneur du composé d'hydrogène actif polyvalent (a2-1) est dans la plage de 3 à 10 % en masse de la masse totale du composé (a1) et du composé (a2).
PCT/CN2023/086775 2023-04-07 2023-04-07 Composition de résine époxy dispersée dans l'eau, peinture et article Pending WO2024207393A1 (fr)

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PCT/CN2023/086775 WO2024207393A1 (fr) 2023-04-07 2023-04-07 Composition de résine époxy dispersée dans l'eau, peinture et article
CN202380090137.8A CN120457177A (zh) 2023-04-07 2023-04-07 水分散性环氧树脂组合物、涂料及物品
TW113112636A TW202444787A (zh) 2023-04-07 2024-04-03 水分散性環氧樹脂組成物、塗料及物品

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1265695A (zh) * 1997-08-14 2000-09-06 国际壳牌研究有限公司 环氧树脂的水分散体
US20030004230A1 (en) * 1999-12-27 2003-01-02 Yuji Hirose Water-based coating composition
JP2007154091A (ja) * 2005-12-07 2007-06-21 Dainippon Ink & Chem Inc 水性樹脂組成物
CN102933634A (zh) * 2010-09-29 2013-02-13 Dic株式会社 水分散性环氧树脂、水性环氧树脂组合物及其固化物
JP2013166850A (ja) * 2012-02-15 2013-08-29 Dic Corp 水性防食塗料および防食塗膜
CN104203762A (zh) * 2012-03-29 2014-12-10 陶氏环球技术有限责任公司 水性分散体
CN113416296A (zh) * 2020-03-06 2021-09-21 Ｋｃｃ公司 水溶性环氧树脂、其制备方法及包含其的水性底漆组合物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1265695A (zh) * 1997-08-14 2000-09-06 国际壳牌研究有限公司 环氧树脂的水分散体
US20030004230A1 (en) * 1999-12-27 2003-01-02 Yuji Hirose Water-based coating composition
JP2007154091A (ja) * 2005-12-07 2007-06-21 Dainippon Ink & Chem Inc 水性樹脂組成物
US20130090413A1 (en) * 2010-09-26 2013-04-11 Dic Corporation Water-dispersible epoxy resin, water-based epoxy resin composition and cured product thereof
CN102933634A (zh) * 2010-09-29 2013-02-13 Dic株式会社 水分散性环氧树脂、水性环氧树脂组合物及其固化物
JP2013166850A (ja) * 2012-02-15 2013-08-29 Dic Corp 水性防食塗料および防食塗膜
CN104203762A (zh) * 2012-03-29 2014-12-10 陶氏环球技术有限责任公司 水性分散体
CN113416296A (zh) * 2020-03-06 2021-09-21 Ｋｃｃ公司 水溶性环氧树脂、其制备方法及包含其的水性底漆组合物

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