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
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
  • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
  • C08G10/04—Chemically-modified polycondensates
• • 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
  • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
  • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
  • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
  • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
• • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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 emulsified epoxy resin composition, a method for producing the same, and a paint.
• Epoxy resin compositions using these epoxy resin curing agents are used in the field of paints such as anticorrosion paints for ships, bridges, land and sea iron structures, linings, reinforcements, crack repair materials, sealing materials, injection materials, and primers for concrete structures. Screeds, top coats, FRP reinforcement, building flooring, water supply and sewage linings, pavement materials, adhesives, etc. in the civil engineering and construction fields; widely used in the field.
• Making the epoxy resin-based paint water-based means, for example, using a water-based epoxy resin, which is emulsified by adding an emulsifier and water to an epoxy resin, as a main agent.
• a cured coating film of a water-based epoxy resin composition containing a water-based epoxy resin as a main component and using a hydrophilic epoxy resin curing agent has a problem that the coating performance such as water resistance, hardness, and appearance is not sufficient. was there.
• Patent Document 1 discloses the use of a water-based epoxy resin curing agent containing a reaction composition containing a reaction product of styrene and a predetermined amine compound. It is described that the water-based epoxy resin composition used has good curability and excellent coating film properties such as water resistance, hardness and appearance.
• the water-based epoxy resin composition disclosed in Patent Document 1 has room for improvement in improving the salt water resistance of the cured product. Furthermore, the epoxy resin and epoxy resin curing agent used in the water-based epoxy resin composition need to be emulsified and dispersed stably in water. and the combination of emulsifiers.
• An object of the present invention is to provide an emulsified epoxy resin composition, a method for producing the same, and a paint that have good emulsifiability, excellent appearance and water resistance of the coating film, and excellent salt water resistance.
• Epoxy resin (A), epoxy resin curing agent (B) containing aromatic ring-containing polyamine compound or modified product thereof, alkylene oxide adduct of aromatic hydrocarbon formaldehyde resin and alkylene oxide of modified aromatic hydrocarbon formaldehyde resin An emulsified epoxy resin composition containing at least one resin (C) selected from the group consisting of adducts and water.
• an emulsified epoxy resin composition that has good emulsifiability, excellent coating film appearance, water resistance, and salt water resistance, and a method for producing the same.
• the epoxy resin composition is suitably used for various paints such as anticorrosion paints.
• the emulsified epoxy resin composition of the present invention (hereinafter also simply referred to as “epoxy resin composition” or “composition of the present invention”) comprises an epoxy resin (A) (hereinafter simply referred to as “component (A)”) , an epoxy resin curing agent (B) containing an aromatic ring-containing polyamine compound or a modified product thereof (hereinafter simply referred to as “epoxy resin curing agent (B)” or “component (B)”), aromatic hydrocarbon formaldehyde resin At least one resin (C) selected from the group consisting of alkylene oxide adducts and alkylene oxide adducts of modified aromatic hydrocarbon-formaldehyde resins (hereinafter also simply referred to as “resin (C)” or “component (C)”) ), as well as water.
• component (A) an epoxy resin curing agent
• B aromatic hydrocarbon formaldehyde resin
• the composition of the present invention having the above constitution has good emulsifiability, and the coating film is excellent in appearance, water resistance, and salt water resistance. Although the reason for this is not certain, it is considered as follows.
• the composition of the present invention contains an epoxy resin curing agent (B) containing an aromatic ring-containing polyamine compound or a modified product thereof. Since the aromatic ring-containing polyamine compound has high hydrophobicity and crystallinity, it is believed that this is the reason why a coating film having excellent water resistance and salt water resistance can be formed.
• Resin (C) has a hydrophobic portion derived from an aromatic hydrocarbon formaldehyde resin or modified aromatic hydrocarbon formaldehyde resin and a hydrophilic portion derived from a (poly)alkylene oxide structure, and acts as an emulsifier. Since the resin (C) has a structure derived from an aromatic hydrocarbon and has a wide molecular weight distribution, it has high emulsifiability with respect to the epoxy resin (A) and the epoxy resin curing agent (B) used in the present invention. , it is thought that a coating film having good appearance and water resistance can be formed. Each component used in the composition of the present invention is described below.
• the epoxy resin (A) is not particularly limited as long as it has two or more glycidyl groups capable of reacting with active hydrogen in the epoxy resin curing agent (B) described below and can be emulsified and dispersed in water. Any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds may be used.
• the epoxy resin (A) is an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule, from the viewpoint of emulsifiability by the resin (C), and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. is preferred.
• the epoxy resin examples include an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from paraxylylenediamine, and 1,3-bis(aminomethyl).
• the above epoxy resins can be used in combination of two or more.
• the epoxy resin (A) is a glycidylamino group derived from metaxylylenediamine.
• the main component is at least one selected from the group consisting of resin (C) from the viewpoint of emulsification, appearance, water resistance, and from the viewpoint of forming a coating film excellent in salt water resistance, availability and economy.
• resin (C) from the viewpoint of emulsification, appearance, water resistance, and from the viewpoint of forming a coating film excellent in salt water resistance, availability and economy.
• resin (C) from the viewpoint of emulsification, appearance, water resistance, and from the viewpoint of forming a coating film excellent in salt water resistance, availability and economy.
• resin (C) from the viewpoint of emulsification, appearance, water resistance, and from the viewpoint of forming a coating film excellent in salt water resistance, availability and economy.
• the term "main component" as used herein means that other components may be included within the scope of the present invention, preferably 50 to 100% by mass, more preferably 70 to
• the epoxy equivalent of the epoxy resin (A) is preferably 80 g/equivalent or more, more preferably 100 g/equivalent or more, still more preferably 120 g/equivalent or more, from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. , More preferably 150 g/equivalent or more, and from the viewpoint of low viscosity and curability of the obtained epoxy resin composition, preferably 1000 g/equivalent or less, more preferably 800 g/equivalent or less, still more preferably 500 g/equivalent Below, more preferably 300 g/equivalent or less.
• the epoxy resin curing agent (B) contains an aromatic ring-containing polyamine compound or a modified product thereof.
• the aromatic ring-containing polyamine compound includes at least one selected from the group consisting of aromatic ring-containing aliphatic polyamines and aromatic polyamines.
• the aromatic ring-containing polyamine compound should have two or more amino groups, preferably 2 to 5, more preferably 2 to 4, still more preferably 2 to 3. Even more preferably, the aromatic ring-containing polyamine compound is an aromatic ring-containing diamine having two amino groups.
• Aliphatic polyamines containing aromatic rings include o-xylylenediamine, m-xylylenediamine (meta-xylylenediamine; MXDA), p-xylylenediamine (para-xylylenediamine; PXDA), and the like.
• Aromatic polyamines include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl Ketone, 3,3'-diaminodiphenyl ketone, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-
• the aromatic ring-containing polyamine compound is preferably an aromatic ring-containing aliphatic polyamine from the viewpoint of forming a coating film excellent in emulsifiability, appearance, water resistance, and salt water resistance by the resin (C). More preferably, it is a polyamine compound (b1) represented by the following formula (1). H2N -CH2 - A- CH2 - NH2 (1) (In formula (1), A is a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.)
• Modified product of aromatic ring-containing polyamine compound Modified aromatic ring-containing polyamine compounds include Mannich reaction products of phenol compounds, aldehyde compounds, and aromatic ring-containing polyamine compounds; reaction products of unsaturated hydrocarbon compounds and aromatic ring-containing polyamine compounds; at least one epoxy a reaction product of an epoxy compound having a group and an aromatic ring-containing polyamine compound; a reaction product of a carboxylic acid or its derivative and an aromatic ring-containing polyamine compound; and the like.
• modified aromatic ring-containing polyamine compounds include phenol compounds, aldehyde compounds, and At least one selected from the group consisting of Mannich reaction products of aromatic ring-containing polyamine compounds and reaction products of unsaturated hydrocarbon compounds and aromatic ring-containing polyamine compounds is preferred.
• reaction product of X and Y means a reaction product (adduct) of X and Y, a by-product other than the reaction product, an unreacted raw material X, Y etc. are also included. The same is true for the "Mannich reaction product of X, Y, and Z.”
• Phenolic compounds used in Mannich reaction products of phenolic compounds, aldehyde compounds, and aromatic ring-containing polyamine compounds include naturally occurring phenolic compounds such as phenol, alkylphenols, alkenylphenols, terpenephenols, and cardanol. .
• the number of carbon atoms in the alkyl group in the alkylphenol is preferably 1 to 24, more preferably 1 to 18, from the viewpoint of emulsifiability of the resin (C) and formation of a coating film excellent in appearance, water resistance, and salt water resistance.
• the number of carbon atoms in the alkenyl group in the alkenylphenol is preferably 2-24, more preferably 2-18.
• phenol compounds include phenol, cresol, ethylphenol (p-ethylphenol, etc.), isopropylphenol (o-isopropylphenol, p-isopropylphenol, etc.), butylphenol (p-tert-butylphenol, p-sec-butylphenol , o-tert-butylphenol, o-sec-butylphenol, etc.), amylphenol (p-tert-amylphenol, o-tert-amylphenol, etc.), p-octylphenol, nonylphenol, p-cumylphenol, decylphenol, un Decylphenol, p-dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, pentadecenylphenol, pentadecadienylphenol, pentadecatrienylphenol, hexadecylphenol, hepta
• the phenol compound used in the Mannich reaction product is preferably at least one selected from the group consisting of phenol, cresol, p-tert-butylphenol, nonylphenol, and cardanol, and more preferably phenol.
• Aldehyde compounds used in the Mannich reaction product include formaldehyde; formaldehyde-releasing compounds such as trioxane and paraformaldehyde; and other aldehydes such as benzaldehyde.
• formaldehyde formaldehyde-releasing compounds such as trioxane and paraformaldehyde
• other aldehydes such as benzaldehyde.
• at least one selected from the group consisting of formaldehyde and formaldehyde-releasing compounds is preferred.
• it is more preferable to use an aqueous formaldehyde solution from the viewpoint of workability in the Mannich reaction.
• unsaturated hydrocarbon compound used for the reaction product of the unsaturated hydrocarbon compound and the aromatic ring-containing polyamine compound from the viewpoint of reactivity with the aromatic ring-containing polyamine compound, emulsification of the resulting reaction product with the resin (C)
• Unsaturated hydrocarbon compounds having 2 to 10 carbon atoms are preferred from the viewpoint of forming a coating film having excellent properties, appearance, water resistance and salt water resistance.
• unsaturated hydrocarbon compound include unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms and aromatic hydrocarbon compounds having 2 to 10 carbon atoms and having an ethylenically unsaturated bond.
• ethylene propylene
• butene pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene , cyclohexene, cyclohexadiene, styrene, and divinylbenzene.
• ethylenically unsaturated bonds such as styrene and divinylbenzene is preferred, and styrene is more preferred.
• the aromatic ring-containing polyamine compound or modified product thereof used in the present invention is more preferably a polyamine compound (b1) represented by the following formula (1), a phenol compound, an aldehyde compound, and a polyamine compound represented by the following formula (1).
• a polyamine compound (b1) represented by the following formula (1) a phenol compound, an aldehyde compound, and a polyamine compound represented by the following formula (1).
• a phenol compound, an aldehyde compound, and a Mannich reaction product (b2) of a polyamine compound represented by the following formula (1), and styrene and the following formula (1) From the viewpoint of forming an excellent coating film, more preferably a phenol compound, an aldehyde compound, and a Mannich reaction product
• reaction product (b3) with a polyamine compound.
• H2N -CH2 - A- CH2 - NH2 (1) (In formula (1), A is a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.)
• Component (b1) is a polyamine compound represented by the formula (1).
• A is preferably a 1,3-phenylene group or a 1,4-phenylene group, more preferably a 1,3-phenylene group. That is, the polyamine compound (b1) is selected from the group consisting of o-xylylenediamine, m-xylylenediamine (meta-xylylenediamine; MXDA), and p-xylylenediamine (para-xylylenediamine; PXDA). More than one xylylenediamine, preferably one or more selected from the group consisting of meta-xylylenediamine and para-xylylenediamine, more preferably meta-xylylenediamine.
• the Mannich reaction product (b2) is a Mannich reaction product of a phenol compound, an aldehyde compound, and a polyamine compound represented by the formula (1).
• the phenol compound used in the Mannich reaction product (b2) and preferred aspects thereof are the same as described above, and at least one selected from the group consisting of phenol, cresol, p-tert-butylphenol, nonylphenol, and cardanol is preferred, and phenol is more preferred.
• the aldehyde compound used in the Mannich reaction product (b2) and preferred aspects thereof are the same as described above, preferably at least one selected from the group consisting of formaldehyde and formaldehyde-releasing compounds, and more preferably an aqueous formaldehyde solution.
• the polyamine compound represented by the formula (1) and preferred embodiments thereof used in the Mannich reaction product (b2) are the same as described above, and at least one selected from the group consisting of meta-xylylenediamine and para-xylylenediamine is Meta-xylylenediamine is preferred, and meta-xylylenediamine is more preferred. That is, the Mannich reaction product (b2) is more preferably the Mannich reaction product of phenol, formaldehyde and meta-xylylenediamine.
• the method for producing the Mannich reaction product (b2) is not particularly limited, and known methods can be used.
• an aldehyde compound or a solution thereof is added dropwise to a mixture of a polyamine compound represented by the formula (1) (hereinafter also referred to as "raw material polyamine") and a phenol compound at a temperature of preferably 80°C or lower, more preferably 60°C or lower. etc., and after the addition is completed, the temperature is raised to preferably 80 to 180° C., more preferably 90 to 150° C., and the reaction is carried out for 1 to 10 hours while removing the distillate from the reaction system.
• the amounts of the phenol compound, the aldehyde compound, and the starting polyamine used in the Mannich reaction are not particularly limited as long as the resulting reaction product contains an amino group having an active hydrogen, but are preferably within the following ranges. .
• the phenol compound is preferably used in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per 1 mol of the raw material polyamine.
• the amount of the phenol compound used relative to 1 mol of the raw material polyamine is 0.3 mol or more, the appearance of the resulting coating film is good, and when it is 2 mol or less, it can be used as an epoxy resin curing agent for the Mannich reaction product (b2). The curability of is improved.
• the aldehyde compound is preferably used in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per 1 mol of the raw material polyamine. If the amount of the aldehyde compound to be used is 0.3 mol or more per 1 mol of the raw material polyamine, the addition reaction will proceed sufficiently. becomes better.
• the active hydrogen equivalent (hereinafter also referred to as "AHEW") of the Mannich reaction product (b2) is preferably 130 or less from the viewpoint of exhibiting good curing performance even when the amount is small in the epoxy resin composition, It is more preferably 120 or less, still more preferably 110 or less. Moreover, it is preferably 70 or more from the viewpoint of manufacturing easiness.
• the AHEW of the Mannich reaction product (b2) can be determined, for example, by a titration method.
• reaction product (b3) of styrene and polyamine compound represented by formula (1) is a reaction product of styrene and the polyamine compound represented by the formula (1).
• the polyamine compound represented by the formula (1) and preferred aspects thereof are the same as described above, preferably one or more selected from the group consisting of meta-xylylenediamine and para-xylylenediamine, more preferably meta-xylylenediamine.
• the reaction product (b3) contains a compound represented by the following formula (2) in an amount of 10% by mass or more. preferably included.
• A is the same as above.
• the compound represented by the above formula (2) is a reaction product ( hereinafter also referred to as "1:1 adduct").
• the reaction product (b3) includes a 1:1 adduct of styrene and a starting polyamine, which is the compound represented by the above formula (2), a 2:1 adduct of styrene and a starting polyamine, and a 3:1 adduct of styrene and a starting polyamine.
• polyadducts such as polyamines and 4:1 adducts may be contained, among the above adducts, the 1:1 adduct of styrene and starting polyamine has the lowest active hydrogen equivalent.
• the active hydrogen equivalent weight (AHEW) is the molecular weight per active hydrogen equivalent that can react with the epoxy resin that is the main ingredient of the epoxy resin composition. Therefore, the epoxy resin curing agent using the reaction composition (b3) containing the compound represented by the above formula (2) as a main component can exhibit good curing performance even when the amount of the epoxy resin composition is small. .
• the content of the compound represented by the formula (2) in the reaction product (b3) is more preferably 20% by mass or more, still more preferably 30% by mass or more, and even more preferably 45% by mass. % by mass or more and 100% by mass or less.
• the content of the compound represented by the formula (2) in the reaction product (b3) can be determined by gas chromatography (GC) analysis.
• the active hydrogen equivalent weight (AHEW) of the reaction product (b3) is preferably 130 or less, more preferably 120 or less, from the viewpoint of exhibiting good curing performance even when the amount of the reaction product (b3) is small. More preferably, it is 110 or less. Also, from the viewpoint of ease of manufacture, etc., it is preferably 80 or more, more preferably 90 or more. AHEW of the reaction product (b3) can be obtained by the same method as described above.
• the reaction product (b3) is obtained by an addition reaction between styrene and the polyamine compound represented by the formula (1).
• the addition reaction can be carried out by a known method.
• commercially available products such as "Gaskamine 240" manufactured by Mitsubishi Gas Chemical Co., Ltd. can also be used.
• the aromatic ring-containing polyamine compounds or modified products thereof may be used singly or in combination of two or more.
• the content of the aromatic ring-containing polyamine compound or modified product thereof in the epoxy resin curing agent (B) is preferably 30% by mass or more, more preferably 50% by mass or more, from the viewpoint of obtaining the effect of the present invention more effectively. More preferably 70% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
• the epoxy resin curing agent (B) may further contain curing agent components other than the aromatic ring-containing polyamine compound or its modified form.
• curing agent components other than the aromatic ring-containing polyamine compound or its modified form examples include aliphatic polyamine compounds other than the aromatic ring-containing polyamine compound or modified products thereof.
• the content thereof in the epoxy resin curing agent (B) is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less. More preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, and may be 0% by mass.
• the active hydrogen equivalent (AHEW) of the epoxy resin curing agent (B) is preferably 130 or less, more preferably 120 or less, still more preferably 110 or less.
• AHEW of the epoxy resin curing agent (B) is 130 or less, high curability is exhibited even when the amount of the epoxy resin composition is small.
• the AHEW of the curing agent is preferably 34 or more, more preferably 50 or more, still more preferably 70 or more, from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance.
• Resin (C) is at least one resin selected from the group consisting of alkylene oxide adducts of aromatic hydrocarbon formaldehyde resins and alkylene oxide adducts of modified aromatic hydrocarbon formaldehyde resins, and acts as an emulsifier.
• An aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting an aromatic hydrocarbon and formaldehyde.
• the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, pseudocumene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, At least one selected from the group consisting of dimethylanthracene, ethylanthracene, and binaphthyl.
• the aromatic hydrocarbon formaldehyde resin includes a toluene formaldehyde resin obtained by reacting toluene and formaldehyde, a xylene formaldehyde resin obtained by reacting xylene and formaldehyde, and a resin obtained by reacting mesitylene and formaldehyde.
• the content of the xylene formaldehyde resin in the aromatic hydrocarbon formaldehyde resin is preferably 50% by mass or more, more Preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more and 100% by mass or less .
• the weight-average molecular weight (Mw) of the aromatic hydrocarbon formaldehyde resin is preferably 200 to 200 in terms of standard polystyrene from the viewpoint of improving emulsifiability and forming a coating film having excellent appearance, water resistance, and salt water resistance. 10,000, more preferably 300 to 8,000, more preferably 350 to 5,000, even more preferably 400 to 3,000, still more preferably 400 to 1,500, still more preferably 500 to 1,000 000.
• the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) by the method described in Examples.
• the viscosity of the aromatic hydrocarbon formaldehyde resin at 25 ° C. is preferably 30 to 30,000 mPa s, from the viewpoint of improving emulsification and forming a coating film excellent in appearance, water resistance, and salt water resistance
• the viscosity can be measured using a rotational viscometer at 25°C.
• the hydroxyl equivalent weight (g/equivalent) of the aromatic hydrocarbon formaldehyde resin is from the viewpoint of addition of the alkylene oxide described later, from the viewpoint of improving the emulsifiability, and from the viewpoint of forming a coating film that is excellent in appearance, water resistance, and salt water resistance. , preferably 200 to 2,500 g/equivalent, more preferably 500 to 2,000 g/equivalent, still more preferably 800 to 1,800 g/equivalent, and even more preferably 1,000 to 1,500 g/equivalent.
• the hydroxyl equivalent is obtained by measuring the hydroxyl value by the method described in JIS K0070-1992 and converting the value of the hydroxyl value into a hydroxyl equivalent.
• Aromatic hydrocarbon formaldehyde resin may be a commercial product or may be produced by a known method.
• a method for producing an aromatic hydrocarbon formaldehyde resin includes, for example, a method described in Japanese Patent Publication No. 37-5747, etc., in which an aromatic hydrocarbon and formaldehyde are subjected to a condensation reaction in the presence of a catalyst.
• aromatic hydrocarbon formaldehyde resins include, for example, “Nikanol Y-50”, “Nikanol Y-100”, “Nikanol Y-300”, “Nikanol Y- 1000", “Nikanol L”, “Nikanol LL”, “Nikanol LLL”, “Nikanol G”, “Nikanol H”, “Nikanol H-80” and the like.
• the modified aromatic-hydrocarbon-formaldehyde resin is a resin obtained by modifying the above-mentioned aromatic-hydrocarbon-formaldehyde resin with phenols, polyols, or the like. From the viewpoint of improving emulsifiability and forming a coating film excellent in appearance, water resistance, and salt water resistance, the modified aromatic hydrocarbon formaldehyde resin used in the present invention is an aromatic hydrocarbon formaldehyde resin modified with a phenol. It is preferably a resin that has
• phenol examples include the compounds exemplified as the "phenol compound" in the reaction product (b2), and naturally occurring phenol compounds such as phenol, alkylphenol, alkenylphenol, terpenephenol, and cardanol. mentioned.
• the number of carbon atoms in the alkyl group in the alkylphenol is preferably 1-24, more preferably 1-18, and the number of carbon atoms in the alkenyl group in the alkenylphenol is preferably 2-24, more preferably 2-18.
• phenols include phenol, cresol, ethylphenol (p-ethylphenol etc.), isopropylphenol (o-isopropylphenol, p-isopropylphenol etc.), butylphenol (p-tert-butylphenol, p-sec-butylphenol , o-tert-butylphenol, o-sec-butylphenol, etc.), amylphenol (p-tert-amylphenol, o-tert-amylphenol, etc.), p-octylphenol, nonylphenol, p-cumylphenol, decylphenol, un Decylphenol, p-dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, pentadecenylphenol, pentadecadienylphenol, pentadecatrienylphenol, hexadecylphenol, heptadec
• phenols are preferably selected from the group consisting of phenol, cresol, butylphenol, and nonylphenol, from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. It is at least one, more preferably at least one selected from the group consisting of phenol and butylphenol, and still more preferably phenol.
• polyols examples include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, neopentyl glycol, and the like, and these may be used alone or in combination of two or more. can.
• the modified aromatic hydrocarbon formaldehyde resin can be obtained, for example, by reacting the above aromatic hydrocarbon formaldehyde resin with phenols or polyols in the presence of an acid or basic catalyst.
• phenol-modified aromatic hydrocarbon formaldehyde resins include, for example, alkylphenol-modified xylene formaldehyde resins "GHP-150" and “HP-210" manufactured by Fudo Co., Ltd. "HP-70”, phenol-modified (novolak type) xylene formaldehyde resin "NP-100""GP-212""P-100""GP-200””HP-30", phenol-modified (resol type) xylene formaldehyde resin "PR-1440M”, “PR-1440", “GRL” and the like.
• polyol-modified aromatic hydrocarbon formaldehyde resins include polyol-modified xylene formaldehyde resin “K-100” manufactured by Fudo Co., Ltd., and the like.
• alkylene oxide Resin (C) is an alkylene oxide adduct of the aromatic-hydrocarbon-formaldehyde resin or modified aromatic-hydrocarbon-formaldehyde resin.
• the alkylene oxide used for the resin (C) includes at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and from the viewpoint of improving emulsifiability, it preferably consists of ethylene oxide and propylene oxide. It is at least one selected from the group, more preferably ethylene oxide.
• the amount of alkylene oxide added to the aromatic hydrocarbon formaldehyde resin or modified aromatic hydrocarbon formaldehyde resin is alkylene oxide from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. is preferably from 5 to 500, more preferably from 10 to 300, still more preferably from 15 to 200, still more preferably from 15 to 150, and even more preferably from 20 to 100.
• HLB hydrophile-lipophile balance of resin (C) is preferably 8. from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. 0 to 20.0, more preferably 10.0 to 18.0, still more preferably 12.0 to 15.0.
• HLB is a value that indicates the affinity of the emulsifier (the resin (C) in the present invention) for water and oil, and can be obtained from the following equation according to the Griffin method.
• HLB 20 x [(molecular weight of hydrophilic group contained in resin (C))/(molecular weight of resin (C))]
• the hydrophilic group include a hydroxy group and ethylene oxide.
• the weight average molecular weight (Mw) of the resin (C) is preferably 300 to 15 in terms of standard polystyrene, from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. 000, more preferably 350 to 12,000, more preferably 400 to 10,000, even more preferably 400 to 8,000, even more preferably 400 to 6,000, even more preferably 500 to 5,000, Even more preferably 700 to 3,000, and even more preferably 1,000 to 2,500.
• the number average molecular weight (Mn) of the resin (C) is preferably 150 to 10, in terms of standard polystyrene, from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. 000, more preferably 200 to 5,000, more preferably 250 to 3,000, even more preferably 300 to 2,000, even more preferably 300 to 1,500, still more preferably 300 to 1,000 be.
• the dispersity (Mw/Mn) of the resin (C) is preferably 0.05 from the viewpoint of ease of production, improvement of emulsifiability, and formation of a coating film excellent in appearance, water resistance, and salt water resistance.
• the weight-average molecular weight, number-average molecular weight, and degree of dispersion of resin (C) can be measured by gel permeation chromatography (GPC) according to the methods described in Examples.
• the hydroxyl equivalent weight of the resin (C) is preferably from 300 to 6,000 g/equivalent, more preferably from 500 to 500 g/equivalent, from the viewpoint of improving emulsifiability and from the viewpoint of forming a coating film having excellent appearance, water resistance, and salt water resistance.
• the hydroxyl equivalent is determined by measuring the hydroxyl value by the method described in JIS K0070-1992 and converting the hydroxyl value into a hydroxyl equivalent.
• the resin (C) is obtained by reacting the above aromatic hydrocarbon formaldehyde resin or modified aromatic hydrocarbon formaldehyde resin with alkylene oxide under heat and pressure conditions in the presence of a basic catalyst. More specifically, an aromatic hydrocarbon formaldehyde resin or a modified aromatic hydrocarbon formaldehyde resin and a basic catalyst are charged in a reactor such as an autoclave equipped with a heating and pressurizing mechanism, and an alkylene oxide is fed thereto. and a method of reacting under heating and pressurizing conditions.
• the amount of alkylene oxide used with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin or modified aromatic hydrocarbon formaldehyde resin is from the viewpoint of improving emulsification, and a coating film having excellent appearance, water resistance, and salt water resistance. From the viewpoint of forming, preferably 10 to 800 parts by mass, more preferably 15 to 500 parts by mass, still more preferably 20 to 300 parts by mass, even more preferably 30 to 200 parts by mass, still more preferably 50 to 150 parts by mass is.
• the resin (C) is preferably 10 to 800 parts by mass, more preferably 15 to 500 parts by mass, and even more preferably 20 to 300 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 50 to 150 parts by mass are reacted.
• Both an inorganic base and an organic base can be used as the basic catalyst used in the above reaction.
• inorganic bases include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
• organic bases include alkali metal alkoxides such as potassium methoxide and sodium methoxide, and amines such as triethylamine. be done. These can be used individually by 1 type or in combination of 2 or more types.
• inorganic bases are preferred, and alkali metal hydroxides are more preferred, from the viewpoint of improving reaction efficiency and economic efficiency.
• the reaction temperature in the above reaction is preferably 100 to 190°C, more preferably 140 to 190°C, from the viewpoint of improving reaction efficiency.
• the reaction time varies depending on the amount of alkylene oxide used, it is preferably 1 to 30 hours, more preferably 2 to 15 hours, still more preferably 3 to 12 hours.
• the reaction time referred to here includes the feeding time of the alkylene oxide.
• the pressure during the reaction is preferably a pressure higher than normal pressure (1 atm; 0.1013 MPa), preferably 0.12 to 5 MPa, more preferably 0.15 to 2 MPa, still more preferably 0.15 to It is in the range of 1 MPa.
• distilled water distilled water, purified water such as ion-exchanged water (deionized water), tap water, industrial water, and the like can be used.
• the content or content ratio of each component in the emulsified epoxy resin composition is preferably within the following range.
• the ratio of the epoxy resin (A) and the epoxy resin curing agent (B) in the emulsified epoxy resin composition is determined from the viewpoint of curability and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance.
• the ratio of the number of active hydrogens in the epoxy resin curing agent (B) to the number of epoxy groups in the epoxy resin (A) [number of active hydrogens/number of epoxy groups] is preferably 1/0.8 to 1/1 .2, more preferably 1/0.9 to 1/1.1, more preferably 1/1.
• the content of the epoxy resin (A) in the emulsified epoxy resin composition is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. % by mass, more preferably 30 to 50% by mass.
• the content of the epoxy resin (A) in the solid content of the emulsified epoxy resin composition is preferably 30 to 80% by mass, from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance. It is preferably 40 to 70% by mass, more preferably 50 to 70% by mass.
• the "solid content of the emulsified epoxy resin composition” is the total amount of the emulsified epoxy resin composition excluding water and the organic solvent.
• the content of the epoxy resin curing agent (B) in the emulsified epoxy resin composition is preferably 3 to 50% by mass from the viewpoint of curability, appearance, water resistance, and formation of a coating film excellent in salt water resistance. , more preferably 5 to 30% by mass, more preferably 10 to 25% by mass.
• the content of the epoxy resin curing agent (B) in the solid content of the emulsified epoxy resin composition is preferably 10 to 10 from the viewpoint of forming a coating film having excellent curability, appearance, water resistance, and salt water resistance. 60 mass %, more preferably 15 to 50 mass %, still more preferably 15 to 40 mass %, still more preferably 20 to 35 mass %.
• the content of the resin (C) in the emulsified epoxy resin composition is determined from the viewpoint of improving the emulsifiability, and from the viewpoint of forming a coating film excellent in appearance, water resistance, and salt water resistance.
• the content of water in the emulsified epoxy resin composition is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, and more preferably 10 to 80% by mass, from the viewpoint of improving emulsifiability and adjusting the viscosity to a desired range. It is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
• composition of the present invention may further contain known curing accelerators, non-reactive diluents, fillers, modifying components such as plasticizers, and flow control components such as thixotropic agents, as long as the effects of the present invention are not impaired. , pigments, leveling agents, and tackifiers.
• curing accelerators include, for example, tris(dimethylaminomethyl)phenol, benzyl alcohol, salicylic acid, triphenylphosphite, styrenated phenol, bisphenol A, N,N'-bis(3-(dimethylamino) mercaptan-terminated polysulfide compounds such as propyl) urea and “Thiocol LP-3” (manufactured by Toray Fine Chemicals Co., Ltd.).
• the total content of epoxy resin (A), epoxy resin curing agent (B), resin (C) and water in the emulsified epoxy resin composition is preferably 50% by mass or more, more preferably 60% by mass. More preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more and 100% by mass or less.
• composition of the present invention preferably does not contain an organic solvent, and the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, and the lower limit is 0. % by mass.
• the viscosity of the emulsified epoxy resin composition at 25° C. is preferably 500 mPa ⁇ s or less, more preferably 400 mPa ⁇ s or less, and still more preferably 400 mPa ⁇ s or less, from the viewpoint of improving the emulsifiability and forming a coating film with good appearance. It is 350 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less. From the viewpoint of facilitating the formation of a coating film with a desired thickness, it is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
• the viscosity at 25° C. of the emulsified epoxy resin composition can be measured using a rotational viscometer, specifically by the method described in Examples.
• the method for producing the emulsified epoxy resin composition is not particularly limited, but from the viewpoint of obtaining a composition with good emulsifiability and ease of emulsification, the epoxy resin (A), the epoxy resin curing agent (B), and It is preferable to prepare a mixture containing the resin (C) and then to mix the mixture with water. According to this method, an emulsified epoxy resin composition can be easily prepared without mechanical high-speed stirring or the like.
• an epoxy resin (A), an epoxy resin curing agent (B), and a resin (C) are prepared.
• a mixture containing As a method for preparing the mixture, the epoxy resin (A), the epoxy resin curing agent (B), the resin (C), and preferably a part of the water to be blended in the composition are blended, and a known method is used. and a method of mixing using an apparatus.
• the amount of water used in preparing the mixture may be any amount other than the total amount of water blended in the composition, preferably 10 to 50% by mass, more preferably 20 to 40% by weight, of the water blended in the final composition.
• the order in which the epoxy resin (A), the epoxy resin curing agent (B), the resin (C), and water are added when preparing the mixture is not particularly limited, and all components may be blended and mixed at the same time. good.
• the temperature during preparation of the mixture may be room temperature, usually in the range of 0 to 40°C, preferably 10 to 35°C.
• the mixing time during preparation of the mixture is also not particularly limited, and is usually selected in the range of 0.5 minutes to 6 hours.
• the mixture After preparing the mixture, the mixture is mixed with the remaining amount of water to obtain the emulsified epoxy composition of the present invention.
• the preferred range of mixing temperature and mixing time in this case is also the same as above.
• the paint of the present invention contains the emulsified epoxy resin composition. Since the emulsified epoxy resin composition of the present invention has good emulsifiability and excellent appearance and water resistance of the coating film as well as salt water resistance, it is suitably used for various paints such as anticorrosive paints.
• the content of the emulsified epoxy resin composition in the paint is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably, from the viewpoint of forming a coating film having excellent appearance, water resistance, and salt water resistance. 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less.
• a cured product of the emulsified epoxy resin composition is obtained by curing the composition or paint of the present invention by a known method. Curing conditions for the emulsified epoxy resin composition are appropriately selected according to the application and form, and are not particularly limited. The form of the cured product is also not particularly limited, and can be selected depending on the application. For example, when the emulsified epoxy resin composition is used for various coatings, the cured product is usually a film-like cured product.
• the emulsified epoxy resin composition of the present invention has good emulsifiability and is excellent in appearance and water resistance of the coating film as well as in salt water resistance. agents, polymer cement mortars, gas barrier coatings, primers, screeds, top coats, sealants, crack repair materials, road pavement materials and the like.
• Viscosity measurement The viscosity of the emulsified epoxy resin composition at 25° C. was measured using an E-type viscometer “TVE-22H viscometer cone plate type” (manufactured by Toki Sangyo Co., Ltd.).
• the weight average molecular weight (Mw) of the aromatic hydrocarbon formaldehyde resin, and the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw/Mn) of the ethylene oxide adduct thereof (resin (C)) are Using polystyrene as a standard substance, measurement was performed by gel permeation chromatography (GPC) under the following conditions.
• the emulsified epoxy resin composition of each example was applied to a base material (zinc phosphate-treated iron plate) in the same manner as described above to form a coating film (thickness of coating film immediately after coating: 100 ⁇ m or 200 ⁇ m), followed by uncoating.
• a test piece was prepared by sealing the part with a rust preventive paint (Million Primer, Million Clear manufactured by Kansai Paint Co., Ltd.). This test piece was heated at 23° C. and 50% R.I. H. A test in which two diagonally intersecting cuts of 50 mm in length were made using a cutter knife in accordance with JIS K5600-7-9: 2006 on the surface of the coating film after 14 days of storage under conditions. A piece was made.
• Example 1 The above test piece was placed in a salt spray tester ("STP-90" manufactured by Suga Test Instruments Co., Ltd., temperature in the tank: 35 ° C.), and salt water (concentration: 5% by mass) was continuously sprayed. After one week ( In Example 1 and Comparative Example 1, after 1, 2 and 4 weeks, the appearance was visually observed and evaluated according to the following criteria. The presence or absence of spots of rust was confirmed by visually observing the substrate surface in contact with the coating film. If it is A grade or B grade, it is considered as a pass. ⁇ Evaluation Criteria> A: No rust spots on the substrate and no change in coating appearance B: A small amount of rust spots on the substrate, but no problem in use C: Rust spots on the substrate or the coating is peeling off
• the resulting resin had a hydroxyl value of 30 mgKOH/g (hydroxyl equivalent of 1870 g/equivalent), Mn of 600, Mw of 1700 and Mw/Mn of 2.83.
• Example 1 (Production of emulsified epoxy resin composition)
• the epoxy resin (A) a liquid epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/equivalent) having a glycidyloxy group derived from bisphenol A is used as a main agent, and an epoxy resin curing agent ( As B) the Mannich reaction product (b2) of phenol-formaldehyde-meta-xylylenediamine (MXDA) obtained in Preparation Example 1 was used.
• the curing agent was added to the epoxy resin, which is the main component, in the ratio shown in Table 1 so that the number of active hydrogens in the curing agent and the number of epoxy groups in the epoxy resin were equimolar.
• the EO adduct of the xylene formaldehyde resin obtained in Production Example 3 was blended in the amount shown in Table 1, and 30% by mass of water shown in Table 1 (12% by mass of the total amount of the final composition) was blended. and stirred at room temperature (25° C.) to prepare a mixture. Then, the remaining amount of water (28% by mass of the total amount of the final composition) was added and stirred at room temperature to obtain an emulsified epoxy resin composition. The above evaluation was performed using the obtained emulsified epoxy resin composition. Table 1 shows the results.
• Examples 2-4, Comparative Examples 1-3 An emulsified epoxy resin composition was prepared in the same manner as in Example 1, except that the types and amounts of the components used in Example 1 were changed as shown in Table 1, and the evaluation was performed. . Table 1 shows the results. All of the compounding amounts shown in Table 1 are amounts of active ingredients.
• ⁇ Epoxy resin (A)> - jER828 a liquid epoxy resin having a glycidyloxy group derived from bisphenol A, "jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186 g/equivalent ⁇ epoxy resin curing agent (B)> (b2)
• Phenol-formaldehyde-MXDA Mannich reaction product Mannich reaction product of phenol-formaldehyde-meta-xylylenediamine (MXDA) obtained in Production Example 1, AHEW77 (b3)
• Styrene-MXDA reaction product a reaction composition containing a reaction product of styrene and m-xylylenediamine (MXDA), Mitsubishi Gas Chemical Co., Ltd.
• the emulsifying epoxy resin composition of the present invention had good emulsifiability, good coating film appearance, water resistance, and salt water resistance (Examples 1 to 4).
• Comparative Examples 1 and 2 using emulsifiers outside the specified range of the present invention and in Comparative Example 3 using an epoxy resin curing agent that does not contain an aromatic ring-containing polyamine compound or its modified form, emulsifiability, The result was that either the appearance of the coating film or the resistance to salt water was inferior.
• an emulsified epoxy resin composition that has good emulsifiability, excellent coating film appearance, water resistance, and salt water resistance, and a method for producing the same.
• the epoxy resin composition is suitably used for various paints such as anticorrosion paints.

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