阅读说明：本技术 硬化剂组合物及其硬化剂涂料 (Hardening agent composition and hardening agent coating thereof ) 是由 廖德超 徐森煌 苏崇智 周全 林瑞荣 于 2020-02-14 设计创作，主要内容包括：本发明公开一种硬化剂组合物及其硬化剂涂料,硬化剂组合物其包含：以100重量％的硬化剂组合物计,5至25重量％的含酯基的胺端基加成物、2至25重量％的C8-C22疏水性饱和或不饱和脂肪胺、2至25重量％的聚胺化合物、2至20重量％的硅烷化合物以及10至60重量％的醚类溶剂,本发明的硬化剂组合物有效降低制程繁复及成本,更提升产品的耐盐雾、抗腐蚀以及耐冲击性能。(The invention discloses a hardener composition and a hardener coating thereof, wherein the hardener composition comprises: based on 100 weight percent of the hardener composition, 5 to 25 weight percent of amine end group addition product containing ester groups, 2 to 25 weight percent of C8-C22 hydrophobic saturated or unsaturated fatty amine, 2 to 25 weight percent of polyamine compound, 2 to 20 weight percent of silane compound and 10 to 60 weight percent of ether solvent.)

1. A hardener composition comprising, based on 100 weight percent of the hardener composition:

5 to 25% by weight of an ester group-containing amine end-group adduct;

2 to 25 weight percent of a C8-C22 hydrophobic saturated or unsaturated fatty amine;

2 to 25% by weight of a polyamine compound;

2 to 20 weight percent of a silane compound; and

10 to 60% by weight of an ether solvent;

wherein the ester group-containing amine-terminated adduct comprises the formula:

wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen, up to an average of 4 secondary or tertiary nitrogen atoms; r₂And R₃Each independently selected from H, substituted orUnsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring; r₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

2. The hardener composition of claim 1, wherein the C8-C22 hydrophobic saturated or unsaturated fatty amine is 9-octadecenylamine.

3. The hardener composition of claim 1 wherein the polyamine compound is a polyether amine compound or a polyethoxylated tallow amine compound.

4. The hardener composition of claim 1, wherein the silane compound is an amino silane compound or an epoxy silane compound.

5. The hardener composition of claim 1 wherein the ether solvent is selected from the group consisting of propylene glycol methyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol methyl ether.

6. The hardener composition of claim 1, wherein the ester group containing amine-terminated adduct is end-capped with a monofunctional epoxy compound to provide an end-capped hardener comprising:

wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen, up to an average of 4 secondary or tertiary nitrogen atoms; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring; r₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

7. The hardener composition of claim 6, wherein the monofunctional epoxy is selected from the group consisting of 1, 2-hexenylated oxide, 1, 2-heptenylated oxide, isoheptenylated oxide, 1, 2-octenylated oxide, 1, 2-dodecene monooxide, 1, 2-pentadecenylated oxide, butadiene monooxide, isopentadiene monooxide, styrenated oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, benzyl glycidyl ether, glycidoxypropyltrimethoxysilane, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, and mixtures thereof, P-tert-butylphenyl glycidyl ether and o-tolyl glycidyl ether.

8. A hardener coating comprising, based on 100% by weight of the hardener coating:

10 to 30 weight percent of a waterborne epoxy resin;

1 to 10 weight percent of the hardener composition of claim 1;

0.1 to 5 wt% of a dispersant;

1 to 5 weight percent of a rheology agent;

1 to 10 weight percent of a film former;

5 to 30 weight percent of a solvent; and

10 to 70 wt% of a metal powder.

9. The hardener coating of claim 8, wherein the metal powder is selected from the group consisting of zinc powder, aluminum powder, and magnesium powder.

10. The hardener coating of claim 8, wherein the film former is selected from the group consisting of propylene glycol monomethyl ether or dipropylene glycol butyl ether.

Technical Field

The invention relates to a hardener composition and a hardener coating thereof, in particular to an anhydrous hardener composition for an aqueous epoxy resin dispersion.

Background

The prior art systems in which waterborne epoxy resins are combined with hardeners often suffer from short pot lives, particularly in the case of metal-containing primers such as zinc-rich primers.

The zinc-rich primer has excellent corrosion resistance and is widely applied to various industrial anticorrosion fields. The main anticorrosion principle of the zinc-rich primer coating is to sacrifice zinc powder (anode) in the coating in a corrosive environment to protect a metal layer (cathode). However, since metal powders such as: the zinc powder has the characteristic of high activity, and is easy to react with water to release hydrogen, so that the product performance is influenced, and the safety worry is increased, therefore, the better preservation period is difficult to obtain.

In addition, the related art still has the problems of complicated preparation process, high cost and poor salt spray resistance, and it has become one of the important issues to be solved by the industry to improve the salt spray resistance, corrosion resistance and impact resistance of the product on the basis of overcoming the above-mentioned defects and reducing the process complexity and cost, thereby meeting the market demand.

Disclosure of Invention

The technical problem to be solved by the present invention is to provide an anhydrous hardener composition for aqueous epoxy resin dispersions, which can be applied to the field of zinc-rich primers.

In order to solve the above technical problems, one aspect of the present invention is to provide a hardening agent composition, which comprises, based on 100 wt% of the hardening agent composition: 5 to 25% by weight of an ester group-containing amine-terminated adduct, 2 to 25% by weight of a C8-C22 hydrophobic saturated or unsaturated fatty amine, 2 to 25% by weight of a polyamine compound, 2 to 20% by weight of a silane compound, and 10 to 60% by weight of an ether-based solvent; wherein the ester group-containing amine-terminated adduct comprises the formula:

wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen, up to an average of 4 secondary or tertiary nitrogen atoms; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring; r₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

Preferably, the C8-C22 hydrophobic saturated or unsaturated fatty amine is 9-octadecenylamine.

Preferably, the polyamine compound is a polyether amine compound or a polyethoxytallow amine compound.

Preferably, the silane compound is an aminosilane compound or an epoxysilane compound.

Preferably, the ether solvent is selected from the group consisting of propylene glycol methyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol methyl ether.

In order to solve the above technical problems, another technical solution of the present invention is to provide a hardening agent coating, which comprises, based on 100 wt% of the hardening agent coating: 10 to 30 weight percent of an aqueous epoxy resin; 1 to 10 weight percent of the aforementioned hardener composition of the present invention; 0.1 to 5 wt% of a dispersing agent; 1 to 5 weight percent of a rheology agent; 1 to 10 weight percent of a film former; 5 to 30 weight percent of a solvent; and 10 to 70 wt% of a metal powder.

Preferably, the metal powder is selected from the group consisting of zinc powder, aluminum powder, and magnesium powder.

Preferably, the film former is propylene glycol monomethyl ether or dipropylene glycol butyl ether, or a combination thereof.

The hardening agent composition for the zinc-rich primer has the advantages that through the technical scheme of the specific proportion, the complexity and the cost of the manufacturing process are reduced, and the salt spray resistance, the corrosion resistance and the impact resistance of the product are improved.

For a better understanding of the features and technical content of the present invention, reference should be made to the following detailed description of the invention.

Detailed Description

The following is a description of the embodiments of the "hardener composition and hardener coating material thereof" disclosed in the present invention by specific examples, and those skilled in the art can understand the advantages and effects of the present invention from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention. The following embodiments will further explain the related art contents of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention.

It should be understood that although the terms first, second, third, etc. may be used herein to describe various components or sections, these components or sections should not be limited by these terms. These terms are used primarily to distinguish one element from another element or from one portion to another portion. In addition, the term "or" as used herein should be taken to include any one or combination of more of the associated listed items as the case may be.

The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. For example, "mono-epoxy" refers to one epoxy group or more than one epoxy group. If the specification states a component or element "may", "may" be included or having a certain characteristic, that particular component or element does not necessarily have to be included or have that characteristic.

The term "parts by weight" as used herein means the amount of additive (or resin) per hundred parts of rubber (or resin) (PHR). The term "wt%" stands for weight percent.

Unless otherwise specified, the term "polymer" independently includes polymers, oligomers, copolymers, terpolymers, block copolymers, segmented copolymers, prepolymers, graft copolymers, and any mixtures or combinations thereof. The term "resin" independently includes polymers, oligomers, copolymers, terpolymers, block copolymers, segmented copolymers, prepolymers, graft copolymers, and any mixtures or combinations thereof.

It is to be understood that the term "independently selected" means that the same or different values can be selected for multiple instances of a given variable in a single compound. The term "substituted or unsubstituted" means that the hydrogen group of the specified moiety is replaced by a group of the specified substituent, provided that the substitution results in a stable or chemically feasible compound. The combinations of substituents envisaged by the present invention are preferably those which allow the formation of stable or chemically feasible compounds.

The invention provides an anhydrous hardener composition for aqueous epoxy resin dispersions, which can be further applied to the field of zinc-rich primers.

The present invention provides a hardener composition comprising, based on 100% by weight of the hardener composition: 5 to 25% by weight of an ester group-containing amine-terminated adduct, 2 to 25% by weight of a C8-C22 hydrophobic saturated or unsaturated fatty amine, 2 to 25% by weight of a polyamine compound, 2 to 20% by weight of a silane compound, and 10 to 60% by weight of an ether solvent; wherein the ester group-containing amine end group adduct comprises the formula:

wherein m is 1-100, n is 1-15, X and Y are independently selected from H, methyl, ethyl, hydroxylA methyl group; r₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen, up to an average of 4 secondary or tertiary nitrogen atoms; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring; r₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

In one embodiment of the present invention, the C8-C22 hydrophobic saturated or unsaturated fatty amine is 9-octadecylamine (oleylamine) in an amount of 2 to 25 wt%, preferably 8 to 12 wt%.

In one embodiment of the present invention, the polyamine compound is selected from the group consisting of polyether amine compounds or polyethoxylated tallow amine compounds in an amount of 2 to 25% by weight, preferably 8 to 12% by weight. Specifically, the polyether amine is a compound having a primary amino group or a secondary amino group as a reactive group on one end or both ends of a resin having a polyether skeleton. For example, it may be a commercially available HuntsmanTrade names D230, D400, D2000, T403, T3000, and T5000, and the like.

In one embodiment of the present invention, the silane compound is an aminosilane compound or epoxysilane compound, and the content thereof is 2 to 20 wt%, preferably 5 to 10 wt%. The silane compound has a coating property with the metal powder, and the epoxy silane compound may be, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyldimethoxysilane, such as commercially available Momentive A186, A187, A1871, Coatasil 2287, Coatasil 1770, or ShinEtsu KBM303, KBM403, KBE402, and KBE 403. The aminosilane compound may be N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, such as the commercially available Momentive A1100, A1120, A1130, A1170 and A2120, ShinEtsu KBM602, KBM603, KBM903, KBE603 and KBE 903.

In one embodiment of the present invention, the ether solvent is selected from the group consisting of propylene glycol methyl ether, dipropylene glycol dimethyl ether and dipropylene glycol methyl ether, and the content thereof is 10 to 60 wt%, preferably 25 to 35 wt%.

More specifically, the ester group-containing amine-terminated adduct of the present invention is obtained by a specific preparation method comprising: step S100 (esterification step), carrying out esterification reaction on polybasic acid anhydride and polyhydric alcohol to obtain an ester-based emulsifier; step S200 (chain extension step), reacting an ester-based emulsifier with a bifunctional epoxy compound to obtain a polymer intermediate; step S300, reacting the polymer intermediate with a polyamine compound to obtain an ester group-containing amine-terminated adduct, and step S400 (capping step), reacting the ester group-containing amine-terminated adduct with a monofunctional epoxy compound.

Specifically, step S100 is performed under a nitrogen atmosphere at a ratio of 1.1: mixing a polyol and a polybasic acid anhydride in an equivalent ratio of 1, and reacting at a temperature of 110 to 130 ℃ for 3 hours to perform an esterification reaction between the polyol and the polybasic acid anhydride to obtain an ester-based emulsifier (A) having the formula:

wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring.

Further, the polyols used in the present invention have the following formula:

more specifically, m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl, preferably, the polyol polymer is preferably a polyethylene glycol having a molecular weight of 200 to 8000, preferably, 200 to 8000. The high molecular weight polyethylene glycol PEG may be selected from: PEG200, PEG400, PEG 1000, PEG 2000, PEG 3000, PEG6000, and PEG 8000.

Further, the polybasic acid anhydrides have the following formula:

wherein R is₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring.

For example, the polybasic acid anhydride is selected from the group consisting of Succinic Anhydride (SA), Maleic Anhydride (MA), Phthalic Anhydride (PA), trans-1, 2-cyclohexanecarboxylic anhydride (CDA), tetrahydrophthalic anhydride (TPA), methylhexahydrophthalic anhydride (MHHPA), and combinations thereof.

S200 chain extension step: mixing the components in a ratio of 0.05: mixing the ester-based emulsifier (A) and a bifunctional epoxy resin at an equivalent ratio of 1 to perform a chain extension reaction, wherein the reaction conditions of the chain extension step are that the reaction is performed at a temperature of 110 to 130 ℃ for 1 hour, and then at a temperature of 130 to 150 ℃ for 2 hours to obtain a polymer intermediate (B) having a chemical formula:

R₀is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group; wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring.

Difunctional epoxy resin means that the resin has two or more epoxy groups in one molecule, for example epoxy groups formed via oxidation of olefins, glycidyl etherification of hydroxyl groups, glycidyl amination of primary or secondary amines, or glycidyl esterification of carboxylic acids. The difunctional epoxy resin of the present invention has the following chemical formula:

wherein n is a natural number, n is 1-10, and R is₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

For example, the difunctional epoxy resin may be selected from the group consisting of diglycidyl ethers of the bisphenol type, branched or linear aliphatic glycidyl ethers, epoxy novolac resins, or cycloaliphatic epoxy resins.

Further, the diglycidyl ether of a dihydric phenol can be produced, for example, by reacting an epihalohydrin with a dihydric phenol in the presence of a base. For example, the dihydric phenol may be selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane (bisphenol-A), 2-bis (4-hydroxy-3-t-butylphenyl) propane, 1-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) isobutane, bis (2-hydroxy-1-naphthyl) methane, 1, 5-dihydroxynaphthalene and 1, 1-bis (4-hydroxy-3-alkylphenyl) ethane.

The aliphatic glycidyl ether may be selected from the diglycidyl ethers of 1, 4-butanediol, neopentyl glycol, cyclohexanedimethanol, hexanediol, polypropylene glycol, and similar diols, the triglycidyl ethers of trimethylolethane and trimethylolpropane. Examples of cycloaliphatic epoxy resins are: 3, 4-epoxycyclohexylmethyl- (3, 4-epoxy) cyclohexanecarboxylate, a di-alicyclic diether diepoxy [2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) -cyclohexane-m-dioxane ], bis (3, 4-epoxy-cyclohexylmethyl) adipate, bis (3, 4-epoxy-cyclohexyl) adipate, and vinylcyclohexene dioxide [4- (1, 2-epoxyethyl) -1, 2-epoxycyclohexane ].

S300 reacting the polymer intermediate (B) with a polyamine compound in a ratio of 0.2: 1 equivalent ratio and reacted at a temperature of 70 ℃ for 4 hours to obtain a hardener (C) having the formula:

wherein m is 1-100, n is 1-15, X and Y are each independently selected from H, methyl, ethyl, hydroxymethyl; r₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen, up to an average of 4 secondary or tertiary nitrogen atoms; r₂And R₃Each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or R₂And R₃Bonded to each other to form a substituted or unsubstituted ring; r₀Is a C6 to C30 hydrocarbon group substituted or unsubstituted with an oxygen atom, a nitrogen atom, a sulfur atom, and having at least one aromatic ring, or a C6 to C17 aliphatic hydrocarbon group.

More specifically, the polyamine compound is selected from the group consisting of m-xylylenediamine, 1, 3-bis (aminomethyl) cyclohexane, 2-methyl-1, 5-pentanediamine, 1, 3-pentanediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, polypropylenediamine oxide, 2(4), 4-trimethyl-1, 6-hexanediamine, isophoronediamine, 2, 4-toluenediamine, 1, 6-hexanediamine, 1, 2-diaminocyclohexane and diaminodicyclohexylmethane (PACM).

In addition, optionally, an S400 capping step is further performed, in which the hardener (C) is reacted with the monofunctional epoxy compound at a temperature of 70 ℃ for 2 hours, then cooled to 60 ℃, stirred and mixed with deionized water at a speed of 200rpm for 1 hour to obtain a hardener (D):

wherein R is_XAs shown in the formula (R)₀And R₅As described above), R₁Is a C2 to C18 aliphatic, alicyclic or aromatic radical substituted or unsubstituted with a non-reactive oxygen atom, up to an average of 4 secondary or tertiary nitrogen atoms; r₃Is selected from the group consisting of branched or linear alkyl, alicyclic, polyoxyalkyl or alkenyl groups of 2 to 100 carbon atoms.

More specifically, the monofunctional epoxy compound may be an aliphatic, alicyclic or aromatic compound attached to the epoxy functional group as a terminal capping agent. Reacting the primary amine hydrogen reduces the chance of carbamate formation from atmospheric temperature reaction with the primary amine hydrogen. In addition to alleviating the blush phenomenon by reacting some or all of the primary amine groups consumed on the substituted aryl amido polyamines, reacting the amido polyamines with epoxy functional groups has the advantage of leaving one free aminic hydrogen reactive with the epoxy groups. However, reacting the primary amine with the epoxy functionality on the amido polyamine compound leaves behind a secondary aminic hydrogen that is more reactive with the epoxy resin. Thus, the dual advantage is obtained of maintaining sufficient reactivity to cure the system without an extrinsic catalyst at room temperature while mitigating the whitening phenomenon. Reaction with monofunctional epoxy compounds also forms hydroxyl groups, which can also be used to react with the epoxy component.

The monofunctional epoxy compound is selected from the group consisting of 1, 2-hexenylated oxide, 1, 2-heptenylated oxide, isoheptenylated oxide, 1, 2-octenylated oxide, 1, 2-dodecene monooxide, 1, 2-pentadecene oxide, butadiene monooxide, isoprene monooxide, styrenated oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, benzyl glycidyl ether, glycidoxypropyltrimethoxy silane, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and o-tolyl glycidyl ether.

The hardener composition of the present invention further provides a preferred application, and specifically, the present invention provides a hardener coating comprising, based on 100 wt% of the hardener coating: 10 to 30 weight percent of a waterborne epoxy resin, 1 to 10 weight percent of a hardener composition as previously described, 0.1 to 5 weight percent of a dispersant, 1 to 5 weight percent of a rheological agent, 1 to 10 weight percent of a film former, 5 to 30 weight percent of a solvent, and 10 to 70 weight percent of a metal powder.

More preferably, the aqueous epoxy resin may be 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 11 to 30 wt%, 11 to 25 wt%, 11 to 20 wt%, 11 to 15 wt%, 12 to 30 wt%, 12 to 25 wt%, 12 to 20 wt%, 12 to 15 wt%, 13 to 30 wt%, 13 to 25 wt%, 13 to 20 wt%, 13 to 15 wt%, 14 to 30 wt%, 14 to 25 wt%, 14 to 20 wt%, 14 to 15 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 16 to 30 wt%, 16 to 25 wt%, 16 to 20 wt%, 17 to 30 wt%, 17 to 25 wt%, 17 to 20 wt%, 18 to 30 wt%, 18 to 25 wt%, 18 to 20 wt%, 19 to 30 wt%, 19 to 25 wt%, or a combination thereof, 19 to 20 weight%, 20 to 30 weight%, 20 to 25 weight%, 21 to 30 weight%, 21 to 25 weight%, 22 to 30 weight%, 22 to 25 weight%, 23 to 30 weight%, 24 to 25 weight%, 25 to 30 weight%, 26 to 30 weight%, 27 to 30 weight%, 28 to 30 weight%, or 29 to 30 weight%.

More preferably, the solvent may be 5 to 30 wt%, 10 to 20 wt%, or 15 to 20 wt%.

More preferably, the hardener composition as previously described can be 1 to 10 weight percent, 2 to 10 weight percent, 3 to 10 weight percent, 4 to 10 weight percent, 5 to 10 weight percent, 6 to 10 weight percent, 7 to 10 weight percent, 8 to 10 weight percent, or 9 to 10 weight percent.

In one embodiment of the present invention, the metal powder is selected from the group consisting of zinc powder, aluminum powder and magnesium powder, and mixtures of the foregoing metal powders, and includes alloys and intermetallic mixtures thereof in an amount of 10 to 70 wt%. In more detail, the metal powder may be in the form of powder, granules or flakes, dispersed in the powder or paste. Metal powders are generally of a particle size such that all particles pass through a 100 mesh screen ("mesh" as used herein is the U.S. standard sieve series).

In particular, the aqueous epoxy resin may be selected from commercially available resins such as HuntsmanPZ 3901, 3921, 3961-1, Hexion EPI-REZ Resin 3520, EPIKOTE 6520-WH-53, and combinations thereof.

In one embodiment of the present invention, the film forming agent is propylene glycol monomethyl ether or dipropylene glycol butyl ether, or a combination thereof.

In one embodiment of the present invention, the dispersing agent and rheological agent may be selected from commercially available products, such as BYK-190, and rheological agents, such as BYK-425.

Preparation example

Preparation of the esteramine-containing terminal adducts of the invention

100 g of polyethylene glycol PEG6000 and 5.3 g of methylhexahydrophthalic anhydride (MHHPA) were mixed under a nitrogen atmosphere and reacted at a temperature of 120 ℃ for 3 hours to cause esterification reaction, to obtain 105.3 g of an ester-based emulsifier (A).

105 g of the ester-based emulsifier (A) was mixed with 258 g of south Asia plastics to produce epoxy resin NPEL-136 to carry out a chain extension reaction, and reacted at a temperature of 120 ℃ for 1 hour and then at a temperature of 140 ℃ for 2 hours to obtain a polymer intermediate (B).

175 g of the polymeric intermediate (B) were mixed with an excess of Diethylenetriamine (DETA) and reacted at a temperature of 70 ℃ for 4 hours to remove the excess DETA and obtain the esteramine-containing terminal adduct (C).

Then adding 55.6 g of n-Butyl Glycidyl Ether (BGE) for end-capping reaction, reacting at 70 ℃ for 2 hours, cooling to 60 ℃, adding 280 g of deionized water, and stirring at a constant speed of 200rpm for 1 hour to obtain the end-capped terminal addition product (D) containing the esteramine.

Examples 1 to 3

Preparation of the hardener composition of the invention

The blocked terminal adduct (D) containing an esteramine terminal group, oleylamine, polyamine compound and silane compound, which were prepared according to the mixing preparation example in the following Table 1, were added with an appropriate amount of propylene glycol methyl ether as a solvent, and mechanically stirred at a high speed of 200rpm for 60 minutes to obtain a hardener composition of the present invention.

TABLE 1

The hardener composition prepared in table 1 was prepared as a coating (wt%) according to the preparation of table 2:

TABLE 2

Coating material	Weight (g)	wt％
			Hardener composition of example 1	7.90	5.22
Dispersant BYK-190	0.62	0.41
			Rheological agent BYK-425	2.52	1.66
Zinc powder	83.81	55.37
			Film-forming agent (propylene glycol monomethyl ether, PM)	3.15	2.08
Film-forming agent (dipropylene glycol butyl ether, DPNB)	2.00	1.32
			Aqueous epoxy resin	26.36	17.42
Deionized water	25.00	16.52

Aqueous epoxy resin:

HuntsmanPZ 3901、3921、3961-1

Hexion EPI-REZ Resin 3520

EPIKOTE 6520-WH-53

advantageous effects of the embodiments

One of the benefits of the present invention is that the hardening compound provided by the present invention can reduce the complexity and cost of the manufacturing process and further improve the salt spray resistance, corrosion resistance and impact resistance of the product by using the technical scheme of the present invention with a specific ratio.

The above disclosure is only a preferred embodiment of the present invention, and is not intended to limit the scope of the claims, so that the present invention can be practiced in any way.