WO2020177486A1 - 双组分水性环氧树脂漆 - Google Patents

双组分水性环氧树脂漆 Download PDF

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WO2020177486A1
WO2020177486A1 PCT/CN2020/070706 CN2020070706W WO2020177486A1 WO 2020177486 A1 WO2020177486 A1 WO 2020177486A1 CN 2020070706 W CN2020070706 W CN 2020070706W WO 2020177486 A1 WO2020177486 A1 WO 2020177486A1
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epoxy resin
emulsion
paint
epoxy
equivalent
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PCT/CN2020/070706
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English (en)
French (fr)
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王露一
开卫华
熊荣
徐万钧
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广东华润涂料有限公司
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Priority to EP20766194.3A priority Critical patent/EP3933003A4/en
Priority to US17/310,846 priority patent/US20220106494A1/en
Publication of WO2020177486A1 publication Critical patent/WO2020177486A1/zh

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    • 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
    • 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • 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
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • 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
    • C08G59/54—Amino amides>
    • 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
    • C09D5/002—Priming paints
    • 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
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a two-component waterborne epoxy resin paint, more specifically to a two-component waterborne epoxy resin paint with a balanced pot life and drying speed.
  • Epoxy resin has a wide range of application value in the coating industry. It is well known that epoxy resin-curing system (also known as two-component epoxy resin paint) after curing can obtain good adhesion to substrates, especially metals, and has high mechanical strength, good chemical resistance and corrosion resistance sexual coating. Therefore, epoxy resin paint is considered to be one of the most cost-effective coating compositions in practice.
  • epoxy resin-curing system also known as two-component epoxy resin paint
  • water-based epoxy paint has a shorter pot life, especially at higher application temperatures. For example, at a construction temperature of 40°C, the pot life of conventional two-component waterborne epoxy paints is usually only 1 hour, which severely limits the use of two-component waterborne epoxy paints in areas with higher temperatures (such as tropical areas). )Applications. It has been proposed to replace the fast-drying curing agent with a slow-drying curing agent to increase the pot life of the product by sacrificing the fast-drying performance, but this solution cannot be applied to the actual formulation.
  • the coating industry needs a two-component waterborne epoxy resin paint with a balanced pot life and drying speed.
  • the present invention provides a two-component waterborne epoxy resin paint, which comprises: a) a waterborne epoxy resin emulsion, comprising a low epoxy equivalent epoxy resin with an epoxy equivalent between 400-700g/eq and epoxy A high epoxy equivalent epoxy resin with an equivalent weight greater than 800 g/eq, and b) a curing agent, wherein the weight ratio of the low epoxy equivalent epoxy resin to the high epoxy equivalent epoxy resin is 5:5 to 9 :1; and wherein the aqueous epoxy resin emulsion is stable.
  • the aqueous epoxy resin emulsion is formed by mixing a first emulsion containing the low epoxy equivalent epoxy resin and a second emulsion containing the high epoxy equivalent epoxy resin.
  • the first emulsion is a stable emulsion. More preferably, the first emulsion is a stable emulsion, and the second emulsion is also a stable emulsion.
  • the inventor of the present invention surprisingly found that in the formulation of two-component waterborne epoxy resin paint, the waterborne epoxy resin emulsion is stable and contains a specific weight ratio of low epoxy equivalent epoxy resin and high epoxy equivalent The combination of the two epoxy resins, the resulting two-component waterborne epoxy resin paint not only has a balanced pot life and drying performance, but also shows excellent corrosion resistance.
  • the two-component waterborne epoxy resin paint of the present invention can achieve the above effects for the following reasons.
  • the inventor of the present invention pioneered the discovery that: unlike solvent-based epoxy resin paint, the pot life of water-based epoxy resin paint is not only affected by the reaction between the epoxy group of the epoxy resin and the curing agent, but also Demulsification of resin emulsion is also an important factor affecting the length of the pot life.
  • the water-based epoxy resin emulsion does not demulsify during the activation period, which can cause the activation period of the two-component water-based epoxy resin paint formed from it to be acceptable.
  • the activation period at 40°C can be 2 hours or more long.
  • the water-based epoxy resin emulsion contains a combination of a low epoxy equivalent epoxy resin and a high epoxy equivalent epoxy resin.
  • the high epoxy equivalent epoxy resin provides an initial stage for the epoxy paint film. Polishability, low epoxy equivalent epoxy resin provides crosslinking degree for epoxy resin paint film, so that the two-component epoxy resin paint formed by it has suitable drying performance.
  • the aqueous epoxy resin emulsion contains a combination of a low epoxy equivalent epoxy resin and a high epoxy equivalent epoxy resin in a specific ratio, and the proportion of the low epoxy equivalent epoxy resin is higher. Therefore, the paint film of the two-component epoxy resin paint formed by it has ideal crosslinking density and shows excellent corrosion resistance.
  • the present invention provides a two-component waterborne epoxy resin paint with a balanced long pot life and fast drying speed, and the coating formed by the paint has excellent corrosion resistance.
  • Figure 1 shows the curve of the emulsion particle size at 40°C with time after mixing different types of epoxy resin emulsions and curing agents.
  • composition is described as including or containing specific components, it is expected that the composition does not exclude optional components not involved in the present invention, and it is expected that the composition may consist of or consist of the involved components, or Where a method is described as including or containing specific process steps, it is expected that the method does not exclude optional process steps not involved in the present invention, and it is expected that the method may be constituted or composed of the involved process steps.
  • any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and any upper limit may be combined with any other upper limit to form an unspecified range.
  • every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit in combination with any other point or single numerical value or in combination with other lower or upper limits to form an unspecified range.
  • epoxy equivalent refers to the mass of epoxy resin containing 1 mol of epoxy groups. Generally, the lower the epoxy equivalent, the more epoxy groups contained in the epoxy resin, and the higher the reactivity. In the embodiments of the present invention, the epoxy equivalent of the epoxy resin is usually provided by the supplier.
  • the term “stable” means that the emulsion and curing agent are in accordance with 1: After mixing with an equivalent ratio of 0.8 and storing at 40°C for 2 hours, the particle size of the emulsion does not exceed twice its initial particle size.
  • the "pot life" means that after the two components of the epoxy paint are mixed, the viscosity of the system reaches the initial viscosity at a temperature of 40°C 2 times the time taken.
  • initial sandability is a parameter used to measure the drying performance of two-component waterborne epoxy paint. Generally, the higher the initial sandability, the better the drying performance of the paint film.
  • the term "primer” refers to a coating composition that can be applied to a metal substrate and dried, crosslinked, or otherwise hardened to form a coating having sufficient surface Adhesive non-tacky continuous film.
  • topcoat refers to a coating composition that can be applied to a primer and dried, crosslinked, or otherwise hardened to form a decorative or protective outermost finish ⁇ The material layer. Further, such topcoats can withstand long-term outdoor exposure without showing visible unsatisfactory degradation.
  • intermediate paint refers to a coating composition that can be coated between a primer and a topcoat and dried, crosslinked or otherwise hardened to form an intermediate coating between the primer and the topcoat.
  • under-surface coating refers to a coating composition that can be coated on a metal substrate and dried, crosslinked or otherwise hardened to form a A non-tacky continuous film with sufficient adhesion on the surface of the substrate, and the continuous film formed therefrom can withstand long-term outdoor exposure without showing visible and unsatisfactory deterioration.
  • the present invention provides a two-component waterborne epoxy resin paint, which comprises: a) a waterborne epoxy resin emulsion, comprising a low epoxy equivalent epoxy resin with an epoxy equivalent between 400-700g/eq and epoxy A high epoxy equivalent epoxy resin with an equivalent weight greater than 800 g/eq, and b) a curing agent, wherein the weight ratio of the low epoxy equivalent epoxy resin to the high epoxy equivalent epoxy resin is 5:5 to 9 :1; and wherein, the aqueous epoxy resin emulsion is stable.
  • the water-based epoxy resin emulsion refers to the resin composition that constitutes the main body of the coating formed by the two-component water-based epoxy resin paint of the present invention, and the water-based epoxy resin emulsion is stable.
  • stable type means that after the aqueous epoxy resin emulsion and the curing agent are mixed in an equivalent ratio of 1:0.8 and stored at 40°C for 2 hours, the particle size of the epoxy emulsion does not exceed its Twice the initial particle size.
  • the pot life of water-based epoxy paint is one of the important factors that determine its application value. So far, the coating industry has not realized that: water-based epoxy paint is different from solvent-based epoxy paint. Its pot life is not only affected by the reaction between the epoxy group of the epoxy resin and the curing agent. The demulsification of the emulsion is also an important factor affecting the length of the pot life.
  • the inventor of the present invention pioneered the discovery that using a stable water-based epoxy resin emulsion can be formulated to form a two-component water-based epoxy resin paint with an acceptable pot life, for example, the pot life at 40°C can be 2 hours Or longer, for example 3 hours or longer.
  • the aqueous epoxy resin emulsion comprises a low epoxy equivalent epoxy resin with an epoxy equivalent between 400-700 g/eq and a high epoxy equivalent epoxy with an epoxy equivalent greater than 800 g/eq A resin, wherein the weight ratio of the low epoxy equivalent epoxy resin to the high epoxy equivalent epoxy resin is in the range of 5:5 to 9:1.
  • epoxy resin refers to a polymer or oligomer containing two or more epoxy groups per molecule.
  • each molecule in the epoxy resin may contain up to four epoxy groups.
  • each molecule in the epoxy resin may contain two or three epoxy groups.
  • the epoxy resin may have an epoxy equivalent that varies within a wide range, where the epoxy equivalent refers to the mass of the epoxy resin containing 1 mol of epoxy groups.
  • the epoxy resin may include a low epoxy equivalent epoxy resin and a high epoxy equivalent epoxy resin.
  • epoxy equivalents can be between 400-700 g/eq, preferably between 450-550 g/eq are referred to as low epoxy equivalent epoxy resins.
  • an epoxy resin with a higher epoxy equivalent for example, an epoxy equivalent greater than 800 g/eq is called a high epoxy equivalent epoxy.
  • the epoxy equivalent of the high epoxy equivalent epoxy resin may be in the range of 900 g/eq to 2500 g/eq.
  • the epoxy equivalent of the high epoxy equivalent epoxy resin may be in the range of 850 g/eq to 1200 g/eq.
  • the epoxy equivalent of the high epoxy equivalent epoxy resin may be in the range of 1400g/eq to 2500g/eq, for example in the range of 1600-1800g/eq, or in the range of 1700-2200g/eq Inside.
  • the high epoxy equivalent epoxy resin contained in the aqueous epoxy resin emulsion can obtain a significantly increased glass transition temperature after being mixed with the curing agent, so that the paint film has a better initial stage. Sandability (ie initial hardness), so that the two-component epoxy paint formed from it has suitable drying properties.
  • the high epoxy equivalent epoxy resin will form a cross-linked epoxy resin with a glass transition temperature of 50° C.
  • glass A cross-linked epoxy resin having a transition temperature of 55°C or higher, more preferably a cross-linked epoxy resin having a glass transition temperature of 60°C or higher, and even more preferably a glass transition temperature of 70°C or higher The cross-linked epoxy resin.
  • the low epoxy equivalent epoxy resin contained in the water-based epoxy resin emulsion can provide a sufficient degree of crosslinking, so that the two-component epoxy resin paint film formed therefrom has Ideal crosslink density. Therefore, in the formulation of two-component epoxy resin paint, low epoxy equivalent epoxy resin is also an important component.
  • Suitable epoxy resins include, for example, diglycidyl ethers of polyphenols, such as resorcinol diglycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A
  • the diglycidyl ether of bisphenol F the diglycidyl ether of bisphenol S, the diglycidyl ether of tetramethyl bisphenol
  • the diglycidyl ether of polyhydric alcohols such as the diglycidyl ether of aliphatic glycol Diglycidyl ethers of glycidyl ethers and polyether glycols, such as diglycidyl ethers of C 2-24 alkylene glycols, diglycidyl ethers of poly(ethylene oxide) glycols or poly(propylene oxide) ) Diglycidyl ether of glycol
  • polyglycidyl ether of phenolic resin such as polyglycidyl ether of phenol-formal
  • any one of the low epoxy equivalent epoxy resin and the high epoxy equivalent epoxy resin is a diglycidyl ether of a polyphenol, particularly preferably having the following structural formula (I):
  • D represents -S-, -SS-, -SO-, -SO 2 -, -CO 2 -, -CO-, -O- or has 1 to 10, preferably 1 to 5, more preferably 1 to A divalent alkyl group of 3 carbon atoms, such as -CH 2 -or -C(CH 3 ) 2 -;
  • Each Y is independently halogen, such as F, Cl, Br, or I, or an optionally substituted monovalent C 1 -C 10 hydrocarbon group, such as optionally substituted methyl, ethyl, vinyl, propyl, Allyl or butyl;
  • Each m is independently 0, 1, 2, 3, or 4;
  • n is an integer from 0 to 4, such as 0, 1, 2, 3, or 4.
  • any one of the low epoxy equivalent epoxy resin and the high epoxy equivalent epoxy resin is a bisphenol A type epoxy resin, a bisphenol S type epoxy resin or a bisphenol F having the structural formula (I) Type epoxy resin, where D represents -C(CH 3 ) 2 -, -SO 2 -or -CH 2 -, m represents 0, and n is an integer from 0 to 4.
  • any one of the low epoxy equivalent epoxy resin and the high epoxy equivalent epoxy resin is a bisphenol A type epoxy resin having structural formula (I), wherein D each represents -C(CH 3 ) 2 -, m represents 0, and n is an integer from 0 to 4.
  • the epoxy resin disclosed above can be made, for example, by using epichlorohydrin technology well known to those skilled in the art.
  • any suitable commercially available product can be used, such as E55, E51, E44, E20 available from Shanghai Kaiping Resin Co., Ltd.
  • Epoxy resins are used to provide resin components for aqueous epoxy resin emulsions.
  • this resin component is used as an adhesive to provide adhesion between the coating and the substrate, and to keep the various components (such as fillers) in the epoxy resin component together and impart a certain degree to the paint film.
  • the cohesive strength On the other hand, this resin component has good reactivity with the curing agent, thereby realizing a coating with high mechanical strength.
  • the weight ratio of the low epoxy equivalent epoxy resin to the high epoxy equivalent epoxy resin can be varied within a wide range.
  • the proportion of the low epoxy equivalent epoxy resin is higher.
  • the low epoxy equivalent epoxy resin and the high epoxy equivalent The weight ratio of epoxy equivalent epoxy resin is in the range of 5:5 to 9:1, preferably in the range of 5:5 to 8:2.
  • the inventor of the present invention surprisingly found that the paint film of the two-component epoxy resin paint formed by the above ratio has ideal crosslinking density and exhibits excellent corrosion resistance.
  • the aqueous epoxy resin emulsion further comprises a reactive emulsifier, an optional film-forming aid, and an aqueous medium, wherein the reactive emulsifier is obtained by epoxy resin such as epoxy equivalent lower than The adduct formed by the addition of 600g/eq epoxy resin and nonionic surfactant.
  • the aqueous epoxy resin emulsion with the above composition is stable during the activation period. After being mixed with the curing agent, the particle size of the emulsion at 40° C. is relatively long, such as 2 hours, 3 There is basically no change in a period of hours, 4 hours or longer.
  • the reactive emulsifier is an adduct formed by the addition of an epoxy resin, such as an epoxy resin having an epoxy equivalent of less than 600 g/eq, and a nonionic surfactant.
  • an epoxy resin such as an epoxy resin having an epoxy equivalent of less than 600 g/eq
  • a nonionic surfactant such as an epoxy resin having an epoxy equivalent of less than 600 g/eq
  • the reactive emulsifier can be prepared by appropriate polyaddition reactions known to those of ordinary skill in the art. For example, under catalyst conditions, the polymerization reaction of polyethylene glycol and epoxy resin such as E-20 occurs in water to form a reactive emulsifier.
  • the catalyst is preferably a Lewis acid, more preferably an anionic Lewis acid, and most preferably includes tin tetrachloride, boron trifluoride, methyl persulfate or triphenylphosphine.
  • the catalyst is preferably added in the form of a solution, and the solvent in the catalyst solution is preferably an ether solvent, more preferably ethylene glycol monoethyl ether.
  • the raw materials, raw material ratio, reaction conditions, etc. of the aforementioned synthesis reaction can be determined by those skilled in the art based on experience.
  • the above-mentioned reactive emulsifier may use any suitable commercially available product as an example, such as the EP series waterborne epoxy resin from Allnex Allnex, USA.
  • the film-forming aid is an agent used to assist the film formation of epoxy resin, including but not limited to alcohol ethers, such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monopropyl ether, Propylene glycol monophenyl ether.
  • alcohol ethers such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monopropyl ether, Propylene glycol monophenyl ether.
  • other film-forming aids can also be used.
  • any appropriate commercially available products can be used, such as Texanol, Lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, Dowanol PM, alcohol ester 12, and the like.
  • the above-mentioned film-forming aids can be present in the water-based epoxy resin emulsion, or can be added to the water-based epoxy resin paint according to the present invention to promote the formation
  • any suitable aqueous medium may be used to prepare the aqueous epoxy resin emulsion of the present invention.
  • Suitable aqueous media include water-soluble organic solvents, water and mixtures thereof.
  • the aqueous epoxy resin emulsion is formed by mixing a first emulsion containing the low epoxy equivalent epoxy resin and a second emulsion containing the high epoxy equivalent epoxy resin.
  • the first emulsion is a stable emulsion. More preferably, the first emulsion is a stable emulsion, and the second emulsion is also a stable emulsion.
  • the first emulsion As an example of the first emulsion, any suitable commercially available product can be used, such as Allnex 387 from Allnex Corporation. Preferably, the first emulsion has a solid content of 40-60 wt%.
  • the second emulsion As an example of the second emulsion, any suitable commercially available product can be used, such as 3907 from Huntsman, 900 and 1600 from Nanya. Preferably, the second emulsion has a solid content of 40-60 wt%.
  • the aqueous epoxy resin emulsion contains about 10% to about 70% by weight, preferably about 10% to 60% by weight, more preferably about 25% by weight relative to the total weight of the aqueous epoxy resin emulsion. % To about 55% by weight, still more preferably about 30% to about 50% by weight of the combination of the first emulsion and the second emulsion. Specifically, the aqueous epoxy resin emulsion, relative to the total weight of the aqueous epoxy resin emulsion, contains about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 48% by weight, About 50% by weight of the combination of the first emulsion and the second emulsion.
  • a suitable aqueous epoxy resin emulsion may further contain fillers.
  • fillers refers to any volume extender suitable for aqueous epoxy resin emulsions, which may be inorganic, such as in particulate form. There is no particular limitation on the shape of the particles, and they can have any appropriate shape. The average particle size of the filler can vary within a wide range, for example within a range of about 10 nanometers to about 50 microns.
  • Some fillers, in addition to functioning as volume extenders, also impart one or more desired properties to the composition and/or the coating formed from the composition. For example, some fillers can improve the chemical and/or physical properties, especially the mechanical properties of the coating obtained from the composition. In this case, this filler is also called "reinforcing filler".
  • the filler package contains, for example, silicate, sulfate, carbonate, and silica.
  • Suitable exemplary fillers include, for example, kaolin, wollastonite, calcium carbonate, diatomaceous earth, talc, barium sulfate, magnesium aluminum silicate, silica, and any combination thereof.
  • the total amount of fillers can vary within a wide range, for example, the total amount of the filler is in the range of about 0% to about 40% by weight relative to the total weight of the aqueous epoxy resin emulsion, It is preferably in the range of about 10% by weight to about 30% by weight, more preferably in the range of about 10% by weight to 25% by weight.
  • the aqueous epoxy resin emulsion may further include commonly used additional additives.
  • additional additives may include wetting and dispersing agents, defoamers, leveling agents, rust inhibitors, film forming aids, rheology modifiers, pigments, aqueous solvents, or any combination thereof.
  • Suitable wetting and dispersing agents may include ionic wetting and dispersing agents, non-ionic wetting and dispersing agents, or multifunctional wetting and dispersing agents.
  • ionic wetting and dispersing agents As examples of commercially available wetting and dispersing agents, Dispers 715W, Dispers 740W, Dispers 760W, and Disperbyk194 purchased from Tego, Germany can be used.
  • Suitable defoamers include organosiloxane defoamers, polyether defoamers, polyether modified silicone defoamers, or any combination thereof.
  • organosiloxane defoamers examples include BYK 024, BYK-1660, BYK037 purchased from BYK, Germany, and TEGO foamex 810, purchased from EVONIK, can be used.
  • Suitable rheology modifiers include polyurethane thickeners, cellulose ether thickeners, or any combination thereof.
  • a polyurethane thickener RM-8W thickener available from Rohm & Hass, USA can be used.
  • a cellulose ether thickener Bermocoll EBS 451 FQ purchased from Akzo Noble in the Netherlands can be used.
  • Suitable leveling agents include polysiloxane leveling agents, polyacrylic leveling agents or any combination thereof.
  • a commercially available leveling agent 1660 and BYK420 purchased from BYK in Germany can be used.
  • rust inhibitor is an agent that can prevent corrosion of metal substrates.
  • any suitable commercially available product may be used, such as the flash rust inhibitor Additive F2M commercially available from Hightac; sodium nitrite or a combination thereof.
  • the aqueous epoxy resin emulsion may include pigments.
  • Suitable pigments may include one or more of iron oxide, carbon black, lead oxide, lead carbonate, zinc oxide, titanium oxide, deep ocean blue, chrome green, or chromium oxide, or a combination thereof.
  • titanium oxide is used as a pigment.
  • the film-forming aids described in the water-based epoxy resin emulsion section can be used to promote the formation of the paint film, and the type of the film-forming aids is not particularly limited.
  • each optional ingredient is sufficient to achieve its intended purpose, but preferably, such content does not adversely affect the coating composition or the cured coating obtained therefrom.
  • the total amount of the additional additives is in the range of about 0% to about 60% by weight, preferably about 0.1% to about 55% by weight, relative to the total weight of the aqueous epoxy resin emulsion. %In the range.
  • the preparation of the aqueous epoxy resin emulsion of the present invention can be achieved by any suitable mixing method known to those of ordinary skill in the art.
  • an aqueous epoxy resin emulsion can be made by adding the combination of the first emulsion and the second emulsion, fillers and additional additives (if any) to a container, and then stirring the resulting mixture uniformly.
  • the curing agent used to cure the water-based epoxy resin emulsion comprises selected from aliphatic polyamines, aliphatic amine adducts, amidoamines, amino polyamide resins, cycloaliphatic amines, and aromatic amines. , Aramid, Mannich base, ketimine, dicyandiamide, one or more curing agents.
  • the curing agent is well-known in the art, for example, it is disclosed in "Paint Technology” edited by Liu Dengliang, Fourth Edition, 2010, No. 275-280, the disclosure of which is incorporated by reference. Into this article.
  • the weight ratio of the curing agent to the water-based epoxy resin emulsion may vary in the range of 8:100 to 20:100. Generally speaking, when the weight ratio of the curing agent to the aqueous epoxy resin emulsion is less than 8:100, the curing performance of the resulting coating is poor. Generally speaking, when the weight ratio of the curing agent to the aqueous epoxy resin emulsion is greater than 20:100, the operating performance of the resulting epoxy resin paint and/or the mechanical properties of the resulting coating may decrease.
  • an additional inert diluent that will not affect the reactivity of the curing agent and the aqueous epoxy resin emulsion can be added during the preparation of the curing agent and/or the aqueous epoxy resin emulsion, so as to reduce the components ⁇ viscosity. Therefore, the weight ratio of the curing agent to the aqueous epoxy resin emulsion is not limited to the above range, and can be adjusted according to actual needs.
  • the two-component waterborne epoxy resin paint may be prepared as follows: before application, the waterborne epoxy resin emulsion and the curing agent are simply mixed in a mixing device in a predetermined weight ratio.
  • the mixed epoxy paint can be applied using various methods familiar to those skilled in the art, including spraying (for example, air-assisted, airless or electrostatic spraying), brushing, roller coating, overflow coating, and dipping.
  • the mixed epoxy paint is applied by spraying.
  • Epoxy paint can be applied to various wet film thicknesses.
  • the wet film thickness preferably provides a dry film thickness of about 13 to about 260 ⁇ m (about 0.5 to about 10 mils), and more preferably about 25 to about 75 ⁇ m (about 1 to about 3 mils). ear).
  • the applied coating can be cured by air-drying or by using various drying devices (for example, an oven) familiar to those skilled in the art to accelerate the curing.
  • the preferred heating temperature for curing epoxy paint is about 60°C to about 100°C, and more preferably about 60°C to about 80°C, and the preferred heating time is at least three minutes to less than 60 minutes, less than 45 minutes , Less than 40 minutes. The heating time will tend to decrease with increasing temperature or increasing airflow.
  • Pot life Mix the two components of the water-based epoxy resin paint of the present invention, and then let it stand at 40 ⁇ 1°C, and use a 4# cup to measure the viscosity of the system in seconds (s).
  • Glass transition temperature Centrifuge the emulsion at a speed of 12000r/s for 10 minutes to demulsify and separate the emulsion, then take out the lower solids, dry with N 2 and perform DSC test (10°/min from -20°C to 150°C) , Determine the Tg value from the sudden change point of the DSC curve
  • Initial polishability the two components of the water-based epoxy resin paint of the present invention are mixed to form a paint film, the paint film is dried and taken out of the oven, and immediately polished with 600 grit sandpaper to determine the initial polishability of the paint film.
  • the sandability is judged by a total of five grades of 1-5, of which grade 5 is the best, no paint film adhesion on sandpaper; grade 4 is the second, and a small amount of paint film adhesion on sandpaper is agglomerated; grade 3 is the next , A small amount of medium-sized paint film agglomerated on sandpaper; Grade 2 is the next best, a large number of medium-sized paint film agglomerated on sandpaper; Grade 1 is the worst, a large number of large paint film agglomerated on sandpaper.
  • Adhesion According to ASTM D3359 test standard.
  • Allnex 387 remains stable, while the particle size of Hexion 6520 rapidly increases to the range in less than 1 hour. Therefore, Allnex 387 is a stable emulsion, which can be used as the first emulsion to formulate two-component waterborne epoxy paint.
  • epoxy resin emulsions containing high epoxy equivalents have significantly increased Tg after being mixed with the curing agent.
  • This high epoxy equivalent epoxy resin can form a crosslinked epoxy resin with a Tg greater than 50°C after being mixed with a curing agent, and a higher Tg can provide a better initial hardness. Therefore, Huntsman 3907, NanYa900 and NanYa1600 can be used as the second emulsion, suitable for the preparation of two-component waterborne epoxy paint.
  • Example 1 As shown in Table 3, in Example 1, Allnex 387 was mixed with NY1600 at a ratio of 8:2, and then the resulting emulsion was mixed with the components shown in Table 3 to form an aqueous epoxy resin emulsion as component A . Then, the obtained A component and the B component curing agent are mixed to form the two-component waterborne epoxy resin paint according to Example 1 of the present invention.
  • the two-component waterborne epoxy resin paint of Example 2 was prepared according to the same method, in which the ratio of Allnex387 to NY1600 was 7:3.
  • the epoxy resin emulsion Hexion 6520 was also mixed with the components shown in Table 3 below to form an aqueous epoxy resin emulsion as the A component. Then, the obtained A component and the B component curing agent were mixed to form a comparative two-component waterborne epoxy resin paint for comparison.
  • the pot life of the two-component coating formed by mixing epoxy emulsions with different epoxy equivalents is up to 2h at 40°C, and the viscosity does not change much with time; while the viscosity of the comparative example is after 1 hour It goes up three times.
  • the adhesion, sandability and impact resistance of the two-component coating formed by mixing epoxy emulsion are comparable to those of the comparative example.
  • the water-based epoxy resin paint according to the embodiment of the present invention has a balanced pot life and drying speed.

Abstract

一种双组分水性环氧树脂漆，其包含：a)水性环氧树脂乳液，包含环氧当量介于400-700g/eq之间的低环氧当量环氧树脂；和环氧当量大于800g/eq的高环氧当量环氧树脂，和b)固化剂，其中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内，并且其中所述水性环氧树脂乳液是稳定型的。

Description

双组分水性环氧树脂漆
相关申请的交叉引用
本申请要求享有于2019年03月01日提交的名称为“双组分水性环氧树脂漆”的中国专利申请201910154749.4的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本发明涉及一种双组分水性环氧树脂漆，更具体地涉及具有平衡的活化期和干燥速度的双组分水性环氧树脂漆。
背景技术
环氧树脂在涂料工业中具有广泛的应用价值。公知地，环氧树脂-固化体系(也被称为双组分环氧树脂漆)在固化后可以得到对基材特别是金属具有良好粘性并且具有高机械强度、良好耐化学品性和耐腐蚀性的涂层。因而，环氧树脂漆在实践中被认为是成本效益最好的涂料组合物之一。
随着人们环境保护意识的增强，水性环氧树脂漆的开发越来越受到关注。目前，在双组分水性环氧漆领域中，如何保证同时实现快速干燥和较长活化期二者是长期以来难以解决的行业难题，之前从未被妥善地解决过。较之溶剂型环氧树脂漆，水性环氧树脂漆的活化期更短，特别是在较高的施工温度下更是如此。例如，在40℃的施工温度下，常规双组分水性环氧树脂漆的活化期通常只有1个小时，这严重限制了双组分水性环氧树脂漆在温度较高的区域(比如热带地区)的应用。业已提出了用慢干型固化剂替换快干型固化剂，通过牺牲快速干燥性能来提高产品的活化期，但是这个方案无法应用于实际配方中。
因此，涂料工业中需要具有平衡的活化期和干燥速度的双组分水性环氧树脂漆。
发明内容
本发明提供了一种双组分水性环氧树脂漆，其包含：a)水性环氧树脂乳液，包含环氧当量介于400-700g/eq之间的低环氧当量环氧树脂和环氧当量大于800g/eq的高环氧当量环氧树脂，和b)固化剂，其中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内；并且其中，所述水性环氧树脂乳液为稳定型的。
在本发明的一个实施方式中，所述水性环氧树脂乳液是由包含所述低环氧当量环氧树脂的第一乳液和包含所述高环氧当量环氧树脂的第二乳液混合形成的。优选地，所述第一乳液是稳定型乳液。更优选地，所述第一乳液是稳定型的，并且所述第二乳液也是稳定型乳液。
本发明的发明人惊讶地发现，在双组分水性环氧树脂漆的配制中，水性环氧树脂乳液是稳定型的，并且包含特定重量比的低环氧当量环氧树脂与高环氧当量环氧树脂二者的组合，由此形成的双组分水性环氧树脂漆不仅具有平衡的活化期和干燥性能，还显示优异的耐腐蚀性。
并非希望受缚于任何理论，推测本发明的双组分水性环氧树脂漆能够实现上述效果的原因如下。本发明的发明人开创性地发现：不同于溶剂型环氧树脂漆，水性环氧树脂漆的活化期不仅受环氧树脂的环氧基团与固化剂之间的反应的影响，水性环氧树脂乳液的破乳也是影响活化期长短的一个重要因素。水性环氧树脂乳液在活化期内不发生破乳，可以导致由其形成的双组分水性环氧树脂漆的活化期是可接受的，例如在40℃下的活化期可以为2小时或更长。而且，根据本发明的实施例，水性环氧树脂乳液包含低环氧当量环氧树脂与高环氧当量环氧树脂二者的组合，高环氧当量环氧树脂为环氧树脂漆膜提供初期打磨性，低环氧当量环氧树脂为环氧树脂漆膜提供交联度，从而使得由其形成的双组分环氧树脂漆具有合适的干燥性能。进一步地，根据本发明的实施例，水性环氧树脂乳液包含特定比例的低环氧当量环氧树脂与高环氧当量环氧树脂二者的组合，低环氧当量环氧树脂的比例较高，因而由其形成的双组分环氧树脂漆的漆膜具有理想的交联密度，显示优异的耐腐蚀性能。
因此，本发明提供了一种具有平衡的长活化期和快速干燥速度的双组分水性环氧树脂漆，而且由该漆料形成的涂层具有优异耐腐蚀性。
本发明的一个或多个实施方案的细节在以下的说明书中阐明。根据说明书和权利要求，本发明其它特征、目的和优点将变得清楚。
附图说明
图1示出了不同种类的环氧树脂乳液与固化剂混合之后在40℃下乳液粒径随时间变化的曲线。
定义
在本文中使用时，“一种(a，an)”、“这种(the)”、“至少一种”和“一种或多种”以及不使用数量词的情形可互换使用。因此，例如包含“一种”添加剂的组分可以被解释为表示该组分包含“一种或多种”添加剂。
在组合物被描述为包括或包含特定组分的情况下，预计该组合物中并不排除本发明未涉及的可选组分，并且预计该组合物可由所涉及的组分构成或组成，或者在方法被描述为包括或包含特定工艺步骤的情况下，预计该方法中并不排除本发明未涉及的可选工艺步骤，并且预计该方法可由所涉及的工艺步骤构成或组成。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本文中，术语“环氧当量”是指含有1mol环氧基的环氧树脂的质量。通常，环氧当量越低，环氧树脂中所包含的环氧基越多，反应活性越高。在本发明的实施例中，环氧树脂的环氧当量通常是由供应商提供的。
针对水性环氧树脂乳液、包含低环氧当量环氧树脂的第一乳液和包含高环氧当量环氧树脂的第二乳液使用时，术语“稳定型”是指该乳液与固化剂按照1:0.8的当量比混合并且于40℃储存2小时之后，所述乳液的粒径不超过其初始粒径的两倍。
针对双组分水性环氧树脂漆使用时，“活化期”是指，在将所述环氧树脂漆的两个组分混合完成后，在40℃的温度下，该体系的粘度达到初始粘度2倍所花费的时间。
针对双组分水性环氧树脂漆使用时，“初期打磨性”是用于衡量双组分水性环氧树脂漆的干燥性能的参数。通常，初期打磨性越高，漆膜的干燥性能越优。
当在本文中使用时，术语“底漆”是指这样的涂料组合物，其可被涂覆到金属基材上并且被干燥、交联或以其他方式硬化以形成具有对基材表面的充分粘附性的不发粘的连续膜。
当在本文中使用时，术语“面漆”是指这样的涂料组合物，其可被涂覆到底漆上并且被干燥、交联或以其它方式硬化以形成装饰性或保护性最外侧涂饰物层。进一步地，此类面漆能够经受长期的户外暴露而未显示出可见的令人不满的劣化。
在本文中使用时，术语“中间漆”是指这样的涂料组合物，其可被涂覆在底漆和面漆之间并且被干燥、交联或以其他方式硬化形成介于底漆和面漆之间的一层或多层不发粘的连续膜。
当在本文中使用时，术语“底面合一涂料(DTM)”是指这样的涂料组合物，其可被涂覆到金属基材上并且被干燥、交联或以其他方式硬化以形成具有对基材表面的充分粘附性的不发粘的连续膜，而且由此形成的连续膜能够经受长期的户外暴露而未显示出可见的令人不满的劣化。
当出现在本说明书和权利要求中时，术语“包含”和“包括”及其变体不具有限制性含义。
术语“优选的”和“优选地”是指在某些情况下可提供某些益处的本发明实施方案。然而，在相同或其他情况下，其他实施方案也可能是优选的。另外，一个或多个优选的实施方案的叙述不意味着其他实施方案是不 可用的，并且不旨在将其他实施方案排除在本发明范围外。
具体实施方式
本发明提供了一种双组分水性环氧树脂漆，其包含：a)水性环氧树脂乳液，包含环氧当量介于400-700g/eq之间的低环氧当量环氧树脂和环氧当量大于800g/eq的高环氧当量环氧树脂，和b)固化剂，其中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内；并且其中，所述水性环氧树脂乳液是稳定型的。
水性环氧树脂乳液
在本发明中，水性环氧树脂乳液是指构成由本发明的双组分水性环氧树脂漆形成的涂层的主体的树脂组合物，该水性环氧树脂乳液是稳定型的。在本发明的上下文中，“稳定型”是指该水性环氧树脂乳液与固化剂按照1:0.8的当量比混合并且于40℃储存2小时之后，所述环氧乳液的粒径不超过其初始粒径的两倍。
水性环氧树脂漆的活化期是决定其应用价值的重要因素之一。迄今为止，涂料工业未意识到：水性环氧树脂漆不同于溶剂型环氧树脂漆，其活化期不仅受环氧树脂的环氧基团与固化剂之间的反应的影响，水性环氧树脂乳液的破乳也是影响活化期长短的一个重要因素。本发明的发明人开创性地发现，使用稳定型的水性环氧树脂乳液，可以配制形成具有可接受活化期的双组分水性环氧树脂漆，例如在40℃下的活化期可以为2小时或更长，例如为3小时或更长。
根据本发明的某些实施例，水性环氧树脂乳液包含环氧当量介于400-700g/eq之间的低环氧当量环氧树脂和环氧当量大于800g/eq的高环氧当量环氧树脂，其中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内。
术语“环氧树脂”指每个分子中含有两个或更多个环氧基团的聚合物或低聚物。优选地，环氧树脂中的每个分子可以包含至多四个环氧基团。优选地，环氧树脂中的每个分子可以包含两个或三个环氧基团。根据本发 明的某些实施例，环氧树脂可以具有在较宽范围内变化的环氧当量，其中环氧当量是指含有1mol环氧基的环氧树脂的质量。例如，环氧树脂可以包含低环氧当量环氧树脂和高环氧当量环氧树脂。在本文中，环氧当量可以介于400-700g/eq之间，优选介于450-550g/eq之间的环氧树脂被称为低环氧当量环氧树脂。具有更高环氧当量，例如环氧当量大于800g/eq的环氧树脂被称为高环氧当量环氧树脂。优选地，高环氧当量环氧树脂的环氧当量可以在900g/eq至2500g/eq的范围内。在一些实施方式中，高环氧当量环氧树脂的环氧当量可以在850g/eq至1200g/eq的范围内。在一些实施方式中，高环氧当量环氧树脂的环氧当量可以在1400g/eq至2500g/eq的范围内，例如在1600-1800g/eq的范围内，或者在1700-2200g/eq的范围内。
根据本发明的某些实施例，水性环氧树脂乳液中所包含的高环氧当量环氧树脂在与固化剂混合之后可以会获得明显增加的玻璃化转变温度，使得漆膜具有较好的初期打磨性(即初期硬度)，从而由其形成的双组分环氧树脂漆具有合适的干燥性能。优选地，根据本发明的某些实施例，所述高环氧当量环氧树脂在与所述固化剂混合之后会形成玻璃化转变温度为50℃或更高的交联环氧树脂，优选玻璃化转变温度为55℃或更高的交联环氧树脂，更优选玻璃化转变温度为60℃或更高的交联环氧树脂，甚至还要更优选玻璃化转变温度为70℃或更高的交联环氧树脂。
根据本发明的某些实施例，水性环氧树脂乳液中所包含的低环氧当量环氧树脂可以提供足够的交联度，从而使得由其形成的双组分环氧树脂漆的漆膜具有理想的交联密度。因而，在双组分环氧树脂漆的配制中，低环氧当量环氧树脂也是重要的组分。
适当的环氧树脂包括，例如多元酚的二缩水甘油醚，诸如间苯二酚的二缩水甘油醚、邻苯二酚的二缩水甘油醚、对苯二酚的二缩水甘油醚、双酚A的二缩水甘油醚、双酚F的二缩水甘油醚、双酚S的二缩水甘油醚、四甲基双苯酚的二缩水甘油醚；多元醇的二缩水甘油醚，诸如脂族二醇的二缩水甘油醚和聚醚二醇的二缩水甘油醚，例如C 2-24亚烷基二醇的二缩水甘油醚、聚(环氧乙烷)二醇的二缩水甘油醚或聚(环氧丙烷)二醇的二缩水甘 油醚；酚醛树脂的多缩水甘油醚，诸如苯酚-甲醛树脂的多缩水甘油醚、烷基取代的苯酚-甲醛树脂的多缩水甘油醚、苯酚-羟基苯甲醛树脂的多缩水甘油醚或甲酚-羟基苯甲醛树脂的多缩水甘油醚；或其组合。
根据本发明的某些实施例，低环氧当量环氧树脂与高环氧当量环氧树脂中的任意一种是多元酚的二缩水甘油醚，特别优选具有如下结构式(I)：
Figure PCTCN2020070706-appb-000001
其中，D表示-S-、-S-S-、-SO-、-SO 2-、-CO 2-、-CO-、-O-或具有1至10个、优选1至5个、更优选1至3个碳原子的二价烷基，诸如-CH 2-或-C(CH 3) 2-；
每个Y独立地是卤素，诸如F、Cl、Br或I，或可选被取代的一价C 1-C 10烃基，诸如可选被取代的甲基、乙基、乙烯基、丙基、烯丙基或丁基；
每个m独立地是0、1、2、3或4；和
n是0至4的整数，诸如0、1、2、3或4。
更优选地，低环氧当量环氧树脂与高环氧当量环氧树脂中的任意一种是具有结构式(I)的双酚A型环氧树脂、双酚S型环氧树脂或双酚F型环氧树脂，其中，D分别表示-C(CH 3) 2-、-SO 2-或-CH 2-，m表示0，n是0至4的整数。
最优选地，低环氧当量环氧树脂与高环氧当量环氧树脂中的任意一种是具有结构式(I)的双酚A型环氧树脂，其中，D各自表示-C(CH 3) 2-，m表示0，n是0至4的整数。
以上公开的环氧树脂例如可以采用本领域普通技术人员所熟知的环氧氯丙烷技术制成。或者，作为环氧树脂的实例，可以使用任何适当的可商购产品，诸如购自上海开平树脂有限公司的E55、E51、E44、E20。
环氧树脂被用于为水性环氧树脂乳液提供树脂组分。一方面，这种树脂组分作为粘合剂，用于提供涂层与基材的粘附性，并且使环氧树脂 组分中的各组分(诸如填料)保持在一起并赋予漆膜一定的内聚强度。另一方面，这种树脂组分与固化剂具有良好的反应性，从而实现具有高机械强度的涂层。
在根据本发明的水性环氧树脂乳液中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比可以在较宽的范围内变化。优选地，相较于水性环氧树脂乳液中所包含的高环氧当量环氧树脂的重量，低环氧当量环氧树脂的比例较高，例如，低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内，优选在5:5至8:2的范围内。本发明的发明人惊讶地发现，采用以上配比形成的双组分环氧树脂漆的漆膜具有理想的交联密度，显示优异的耐腐蚀性能。
根据本发明的某些实施例，水性环氧树脂乳液还包含反应型乳化剂、可选的成膜助剂和水性介质，其中所述反应型乳化剂是经由环氧树脂例如环氧当量低于600g/eq的环氧树脂与非离子型表面活性剂的加合形成的加成物。本发明的发明人惊讶地发现，具有以上组成的水性环氧树脂乳液在活化期内是稳定的，在与固化剂混合后，40℃下乳液粒径在较长时间内，诸如2小时、3小时、4小时或更长的时间段内基本没有变化。
根据本发明的一个实施例，反应型乳化剂是经由环氧树脂例如环氧当量低于600g/eq的环氧树脂与非离子型表面活性剂的加合形成的加成物。作为示例性说明，所述反应型乳化剂可以采用本领域普通技术人员所熟知的适当加聚反应制备。例如，在催化剂条件下，经由聚乙二醇和环氧树脂例如E-20在水中发生聚合反应，而形成反应性乳化剂。所述催化剂优选为路易斯酸，更优选为阴离子型路易斯酸，最优选包括四氯化锡、三氟化硼、过硫酸甲或三苯基膦。所述催化剂优选以溶液的形式加入，所述催化剂溶液中的溶剂优选为醚类溶剂，更优选为乙二醇单乙醚。上述合成反应的原料、原料配比、反应条件等可由本领域技术人员依经验确定。或者，上述反应性乳化剂可以使用任意适当的可商购产品作为实例，例如来自美国湛新Allnex公司的EP系列水性环氧树脂。
根据本发明的一个实施例，成膜助剂是用于协助环氧树脂成膜的试剂，包括但不限于醇醚类，例如丙二醇单甲醚、丙二醇单丁醚，乙二醇单 丙醚、丙二醇单苯醚。根据需要，也可以使用其它成膜助剂。作为其它成膜助剂的实例，可以使用任意适当的可商购产品，例如Texanol、Lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、Dowanol PM、醇酯12等。根据需要，上述成膜助剂可以在存在于水性环氧树脂乳液中，也可以被添加到根据本发明的水性环氧树脂漆中以促进漆膜的形成。
根据本发明的一个实施例，可以使用任意适当的水性介质来制备本发明的水性环氧树脂乳液。适当的水性介质包括可水溶性有机溶剂、水及其混合物。
在目前优选的实施方式中，所述水性环氧树脂乳液是由包含所述低环氧当量环氧树脂的第一乳液和包含所述高环氧当量环氧树脂的第二乳液混合形成的。优选地，所述第一乳液是稳定型的乳液。更优选地，所述第一乳液是稳定型的乳液，并且所述第二乳液也是稳定型的乳液。
作为第一乳液的实例，可以使用任何适当的可商购产品，诸如来自美国湛新公司的Allnex 387。优选地，所述第一乳液具有40-60wt％的固含量。
作为第二乳液的实例，可以使用任何适当的可商购产品，诸如来自Huntsman的3907、来自Nanya的900和1600。优选地，所述第二乳液具有40-60wt％的固含量。
优选地，所述水性环氧树脂乳液，相对于所述水性环氧树脂乳液的总重，包含约10重量％至约70重量％、优选约10重量％至60重量％、更优选约25重量％至约55重量％、还更优选约30重量％至约50重量％的所述第一乳液和所述第二乳液的组合。具体地，所述水性环氧树脂乳液，相对于所述水性环氧树脂乳液的总重，包含约30重量％、约35重量％、约40重量％、约45重量％、约48重量％、约50重量％的所述第一乳液和所述第二乳液的组合。
适当的水性环氧树脂乳液可以进一步包含填料。本文使用的术语“填料”指适用于水性环氧树脂乳液的任何体积增量剂，其可以是无机的例如颗粒形式。对颗粒的形状没有特殊限制，其可以具有任何适当的形状。填料的平均粒径可以在宽范围内变化，例如在约10纳米至约50微米的范围 内变化。一些填料除了起到体积增量剂的作用以外还赋予组合物和/或由该组合物形成的涂层一种或多种所需性质。例如，一些填料可以改善化学和/或物理性质，特别可以改善由该组合物得到的涂层的机械性质。在这种情况下，这种填料也被称为“增强填料”。
在本发明的实施方式中，填料包例如包含硅酸盐、硫酸盐、碳酸盐、二氧化硅。适当的示例性填料包括例如高岭土、硅灰石、碳酸钙、硅藻土、滑石、硫酸钡、硅酸镁铝、氧化硅及其任意组合。
根据本发明的某些实施例，填料的总量可以在宽范围内变化，例如其总量相对于所述水性环氧树脂乳液的总重在约0重量％至约40重量％的范围内，优选在约10重量％至约30重量％的范围内，更优选约10重量％至25重量％的范围内。
在本发明的实施方式中，所述水性环氧树脂乳液可以进一步包含常用的附加添加剂。适当的附加添加剂可以包括润湿分散剂、消泡剂、流平剂、防锈剂、成膜助剂、流变改性剂、颜料、水性溶剂或其任意组合。
适当的润湿分散剂可以包括离子型润湿分散剂、非离子型润湿分散剂或多官能团型润湿分散剂。作为可商购润湿分散剂的实例，可以使用购自德国Tego公司的Dispers 715W、Dispers 740W、Dispers 760W、Disperbyk194。
适当的消泡剂包括有机硅氧烷类消泡剂、聚醚类消泡剂、聚醚改性的有机硅类消泡剂或其任意组合。作为可商购消泡剂的实例，可以使用购自德国BYK公司的BYK 024、BYK-1660、BYK037，和购自EVONIK公司的TEGO foamex 810。
适当的流变改性剂(即增稠剂)包括聚氨酯类增稠剂、纤维素醚类增稠剂或其任意组合。作为聚氨酯类增稠剂的实例，可以使用购自美国Rohm&Hass的RM-8W增稠剂。作为纤维素醚类增稠剂的实例，可以使用购自荷兰Akzo Noble的Bermocoll EBS 451 FQ。
适当的流平剂包括聚硅氧烷流平剂、聚丙烯酸类流平剂或其任意组合物。作为可商购流平剂的实例，可以使用购自德国BYK公司的1660、BYK420。
在本文中，“防锈剂”是可以防止金属基材锈蚀的试剂。作为防锈剂的实例，可以使用任意适当的可商购产品，诸如可商购自Hightac的防闪锈剂Additive F2M；亚硝酸钠或其组合。
根据需要的涂层的颜色，水性环氧树脂乳液可以包括颜料。适当的颜料可以包括氧化铁、碳黑、氧化铅、碳酸铅、氧化锌、氧化钛、深海蓝、铬绿或氧化铬中的一种或多种或其组合。在本发明的优选实施方式中，氧化钛被用作颜料。
根据需要，可以使用上述水性环氧树脂乳液部分所述的成膜助剂，以促进漆膜的形成，对所述成膜助剂的种类没有特殊限定。
各个可选成分的含量足以起到其意欲达到目的，但优选地，这样的含量不会不利地影响涂层组合物或由其得到的固化涂层。根据本发明的某些实施例，附加添加剂的总量相对于所述水性环氧树脂乳液的总重在约0重量％至约60重量％的范围内，优选在约0.1重量％至约55重量％的范围内。
本发明的水性环氧树脂乳液的制备可以采用本领域普通技术人员所熟知的任何适当的混合方法来实现。例如水性环氧树脂乳液可以通过如下制成：将第一乳液和第二乳液的组合、填料和附加添加剂(如果有的话)添加到容器中，然后将所得混合物搅拌均匀。
固化剂
在本发明的某些实施例中，用于固化水性环氧树脂乳液的固化剂包含选自脂肪族多元胺、脂肪胺加成物、酰氨基胺、氨基聚酰胺树脂、环脂胺、芳香胺、芳脂胺、曼尼期碱、酮亚胺、双氰胺中一种或多种的固化剂。
在本发明的某些实施例中，所述固化剂是本领域公知的，例如在刘登良主编的《涂料工艺》，第四版，2010，第275-280中公开了，其公开内容通过引用并入本文中。
根据本发明的某些实施例，固化剂与水性环氧树脂乳液的重量比可以在8:100至20:100的范围内变化。一般而言，当固化剂与水性环氧树脂乳 液的重量比小于8:100时，所得涂层的固化性能不良。一般而言，当固化剂与水性环氧树脂乳液的重量比大于20:100时，那么所得环氧树脂漆的操作性能以及/或者所得涂层的机械性质可能会下降。根据实际需要，可以在固化剂和/或水性环氧树脂乳液的制备期间添加额外的不会对以上固化剂和水性环氧树脂乳液的反应性造成影响的惰性稀释剂，以例如降低各组分的粘度。因而，固化剂与水性环氧树脂乳液的重量比并不局限于上述范围，可以根据实际需要调整。
根据本发明的某些实施例，双组分水性环氧树脂漆可以通过如下制备：应用前，将水性环氧树脂乳液与固化剂以预定重量比在混合装置中进行简单混合。混合的环氧树脂漆可使用本领域技术人员熟悉的各种方法来涂覆，包括喷涂(例如，空气辅助、无空气或静电喷涂)、刷涂、辊涂、溢涂和浸渍。在本发明的一个实施方式中，混合的环氧树脂漆通过喷涂来进行涂覆。环氧树脂漆可被涂成各种湿膜厚度。在本发明的实施方式中，湿膜厚度优选地提供约13至约260μm(约0.5至约10密耳)的干膜厚度，且更优选地是约25至约75μm(约1至约3密耳)。可以通过使涂覆的涂层风干或通过使用本领域技术人员熟悉的各种干燥装置(例如，烘箱)加速固化来使其固化。用于固化环氧树脂漆的优选加热温度是约60℃至约100℃，且更优选地是约60℃至约80℃，且优选的加热时间是至少三分钟至小于60分钟、小于45分钟、小于40分钟。加热时间将倾向于随温度增加或气流增加而减少。
下述实施例更具体地描述了本发明公开的内容，这些实施例仅仅用于阐述性说明，因为在本发明公开内容的范围内进行各种修正和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购并且可直接使用而无需进一步处理。
测试方法
活化期：将本发明的水性环氧树脂漆的两个组分混合，然后在40± 1℃的条件下静置，采用4#杯测定该体系的粘度，以秒(s)计。
玻璃化转变温度：将乳液以12000r/s速度离心10分钟，使乳液破乳分离，然后将下层固体取出，N 2吹干后进行DSC测试(10°/min从-20℃升温至150℃)，由DSC曲线突变点确定Tg值。
初期打磨性：将本发明的水性环氧树脂漆的两个组分混合形成漆膜，将漆膜干燥后从烘箱中取出，立即用600目砂纸进行打磨，来确定漆膜的初期打磨性。打磨性是通过1-5共计五个级别分级判定的，其中5级别为最好，砂纸上无漆膜粘附；4级别次之，砂纸上粘附少量漆膜结块；3级别更次之，砂纸上粘附少量中型漆膜结块；2级别更次之，砂纸上粘附大量中型漆膜结块；1级别最差，砂纸上粘附大量大型漆膜结块。
附着力：根据ASTM D3359测试标准。
抗冲击性：根据国标GB 1732测试标准。
实施例
各实例中使用的原料列在如下表1中。
条目 材料 描述
1 Allnex 387(EEW480-550) 低环氧当量环氧树脂乳液
2 Hexion 6520(EEW500-600) 低环氧当量环氧树脂乳液
3 Huntsman 3907(EEW 1760-2200) 高环氧当量环氧树脂乳液
4 NanYa 900(EEW 850-1000) 高环氧当量环氧树脂乳液
5 NanYa1600(EEW1600-1800) 高环氧当量环氧树脂乳液
6 Disperbyk 194 润湿分散剂
7 BYK 037 消泡剂
8 BYK420 流平剂
9 Additive F2M 防锈剂
10 去离子水 水性介质
12 TiO 2 颜料
13 流变改性剂 流变改性剂
14 Dowanol PM 成膜助剂
15 亚硝酸钠 防锈剂
第一乳液的确定
在室温下，将商购的环氧乳液Allnex 387和Hexion 6520分别于固化剂混合，然后采用动态光散射检测在40℃下所得乳液的粒径随时间的变化。测试结果示于图1中。
由结果可见，Allnex 387的粒径保持稳定，而Hexion 6520的粒径在不足1小时的时间段内迅速增大直至范围。因此，Allnex 387是稳定型乳液，可以作为第一乳液用于配制双组分水性环氧树脂漆。
第二乳液
在室温下，将商购的环氧乳液Allnex 387、Huntsman 3907、NanYa900和Nanya 1600分别与固化剂混合，并根据测试方法部分所述，测定所得混合物的玻璃化转变温度，结果示于下表2中。
表2：
  Allnex 387 Huntsman 3907 NanYa900 NanYa 1600
环氧当量/g/eq 480-550 1760-2200 850-1000 1600-1800
Tg/℃ 6.7 32.2 7.5 14.3
与固化剂混合后的Tg/℃ 14.5 74.5 60.9 59.1
由上述结果可见，含有高环氧当量的环氧树脂乳液(例如Huntsman3907、NanYa900和Nanya 1600)在与固化剂混合之后具有明显提高的Tg。这种高环氧当量的环氧树脂在与固化剂混合后能形成Tg大于50℃的交联环氧树脂，而较高的Tg能够提供较好的初期硬度。因此，Huntsman3907、NanYa900和NanYa1600均可被作为第二乳液，适用于配制双组分水性环氧树脂漆。
双组分涂料组合物
如表3所示，在实施例1中，将Allnex 387与NY1600以8:2的比例 混合，然后将所得乳液与表3所示各组分混合，从而形成水性环氧树脂乳液作为A组分。然后，将所得A组分与B组分固化剂进行混合，从而形成根据本发明实施例1的双组分水性环氧树脂漆。按照同样的方法制备实施例2的双组分水性环氧树脂漆，其中Allnex387与NY1600的比例为7:3。
为了比较，将环氧树脂乳液Hexion 6520同样与下表3所示各组分混合，从而形成水性环氧树脂乳液作为A组分。然后，将所得A组分与B组分固化剂进行混合，从而形成用于对比的对比例双组分水性环氧树脂漆。
然后，测试实施例1、实施例2和对比例的双组分水性环氧树脂漆的活化期、粘附性、耐磨性以及抗冲击性，结果如表3所示。
表3：
Figure PCTCN2020070706-appb-000002
Figure PCTCN2020070706-appb-000003
由以上结果可见，通过混拼环氧当量不同的环氧乳液配制形成的双组分涂料的活化期在40℃长达2h，且黏度随时间没有很大变化；而对比例在1小时之后黏度就上升3倍。此外，通过混拼环氧乳液配制形成的双组分涂料的附着力、打磨性与抗冲击性都与对比例相当。由此可见，根据本发明实施例的水性环氧树脂漆具有平衡的活化期和干燥速度。
尽管本发明参照大量实施方式和实施例进行描述，但是本领域普通技术人员根据本发明公开的内容能够认识到可以设计其它实施方式，这并未脱离本发明的保护范围和精神。

Claims (15)

  1. 一种双组分水性环氧树脂漆，其包含：
    a)水性环氧树脂乳液，包含环氧当量介于400-700g/eq之间的低环氧当量环氧树脂和环氧当量大于800g/eq的高环氧当量环氧树脂，和
    b)固化剂，
    其中，所述低环氧当量环氧树脂与所述高环氧当量环氧树脂的重量比在5:5至9:1的范围内；并且
    其中，所述水性环氧树脂乳液是稳定型的。
  2. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述高环氧当量环氧树脂的环氧当量在900g/eq至2500g/eq的范围内。
  3. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述高环氧当量环氧树脂在与所述固化剂混合之后会形成玻璃化转变温度为50℃或更高的交联环氧树脂。
  4. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述低环氧当量环氧树脂和高环氧当量环氧树脂中的任意一个是具有如下结构式(I)的多元酚的二缩水甘油醚：
    Figure PCTCN2020070706-appb-100001
    其中，
    D表示二价C 1-C 10亚烷基，
    每个Y独立地表示H、卤素或可选被取代的一价C 1-C 10烃基，
    每个m独立地表示0、1、2、3或4，
    n是0至4的整数。
  5. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述水性环氧树脂乳液还包括：反应型乳化剂；可选的成膜助剂；和水性介质，其中所述反应型乳化剂是经由环氧树脂与非离子型表面活性剂的加合形成的加成物。
  6. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述水性环氧树脂乳液是由包含所述低环氧当量环氧树脂的第一乳液和包含所述高环氧当量环氧树脂的第二乳液混合形成的。
  7. 如权利要求6所述的双组分水性环氧树脂漆，其中，所述第一乳液是稳定型乳液。
  8. 如权利要求6所述的双组分水性环氧树脂漆，其中，所述第一乳液具有40-60wt％的固含量。
  9. 如权利要求6所述的双组分水性环氧树脂漆，其中，所述第二乳液是稳定型乳液。
  10. 如权利要求6所述的双组分水性环氧树脂漆，其中，所述第二乳液具有40-60wt％的固含量。
  11. 如权利要求6所述的双组分水性环氧树脂漆，其中，所述水性环氧树脂乳液包含，相对于所述水性环氧树脂乳液的总重量，
    10-70wt％的所述第一乳液与所述第二乳液的组合；
    0-30wt％的填料；以及
    0-60wt％的附加添加剂，所述附加添加剂包括润湿分散剂、消泡剂、流平剂、防锈剂、流变改性剂、成膜助剂、水性溶剂、颜料或其任意组合。
  12. 如权利要求1所述的双组分水性环氧树脂漆，其中，所述固化剂包含脂肪族多元胺、脂肪胺加成物、酰氨基胺、氨基聚酰胺树脂、环脂胺、芳香胺、芳脂胺、曼尼期碱、酮亚胺、双氰胺或其任意组合。
  13. 如权利要求1所述的双组分水性环氧树脂漆，其中所述水性环氧树脂乳液与所述固化剂混合之后的体系显示在40℃下至少2小时的活化期。
  14. 如权利要求1所述的双组分水性环氧树脂漆，其中，将所述水性环氧树脂乳液与所述固化剂混合之后的体系形成漆膜，所述漆膜在60℃温度下进行半小时烘烤后，具有5 -或更高的初期打磨性。
  15. 如权利要求1至14中任意一项所述的双组分水性环氧树脂漆，其适于用作底漆、面漆、中间漆或底面合一涂料。
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