Aqueous coating composition set, coating film, substrate with coating film, and method for manufacturing substrate with coating film

Abstract

The present invention addresses the problem of providing an aqueous coating composition set which is capable of providing an aqueous coating composition having excellent low-temperature drying curability and which is capable of forming a coating film having an excellent balance between initial water resistance and impact resistance. The present invention relates to an aqueous coating composition set, a coating film, a substrate with a coating film, and a method for producing a substrate with a coating film, the aqueous coating composition set being a multi-pack type aqueous coating composition set comprising a first agent containing an aqueous epoxy resin (A), a second agent containing an amine curing agent (B), a silane coupling agent (C), and water, the solid content of the silane coupling agent (C) in the aqueous coating composition is 0.05-0.60 parts by mass per 1 part by mass of water in the aqueous coating composition.

Description

Technical Field

[0001] This invention relates to a water-based coating composition kit, a coating film, a substrate with a coating film, and a method for manufacturing the substrate with a coating film. Background Technology

[0002] For purposes such as long-term use, organic solvent-based epoxy resin anti-corrosion coatings and other coating compositions have traditionally been applied to substrates such as ships, marine structures, factory equipment, bridges, and onshore storage tanks.

[0003] In recent years, with the strengthening of regulations on organic solvent emissions in consideration of the natural environment and coating operation environment, the production of coating compositions with low VOCs (volatile organic compounds) has been promoted. One method of this VOC reduction is the water-based formulation of coating compositions. Since water-based coating compositions mainly use water as a solvent and dispersion medium, they can significantly reduce VOCs compared to conventional organic solvent-based coating compositions while maintaining appropriate coating viscosity.

[0004] However, because water-based coating compositions contain water, a rusting phenomenon known as flash rust is prone to occur during the period from coating application to film drying.

[0005] As an example of a water-based coating composition capable of suppressing flash rust, Patent Document 1 discloses a water-based coating composition comprising a first agent containing a rust inhibitor and a second agent containing a flash rust inhibitor but not a rust inhibitor, and comprising a water-based resin.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2020-122114 Summary of the Invention

[0007] The problem that the invention aims to solve After in-depth research, the inventors of this invention discovered that although the water-based coating composition described in Patent Document 1 can suppress flash rust, there is still room for improvement in terms of drying and curing properties at low temperatures (e.g., 5°C) (low-temperature drying and curing properties). Due to the low low-temperature drying and curing properties, the initial water resistance of the resulting coating film is low. Specifically, it was found that after applying the water-based coating composition described in Patent Document 1 to a substrate outdoors in winter, when the substrate comes into contact with water due to rainfall, the resulting coating film may exhibit abnormalities such as blistering.

[0008] In addition, the coating film formed by the water-based coating composition on the substrate also needs to have impact resistance, etc.

[0009] The present invention was made in view of the above circumstances, and its purpose is to provide a water-based coating composition kit that can obtain a water-based coating composition with excellent low-temperature drying and curing properties, and can form a coating film with a good balance of initial water resistance and impact resistance.

[0010] Technical solutions for solving the problem After repeated and in-depth research on the method for solving the above-mentioned problems, the inventors of this invention discovered that the above-mentioned problems can be solved through the following configuration example, thereby completing this invention.

[0011] The structure of the present invention is described below.

[0012] [1] A waterborne coating composition kit, which is a multi-component waterborne coating composition kit, comprising: a first agent containing a waterborne epoxy resin (A); and The second agent containing amine curing agent (B), The aforementioned water-based coating composition kit also contains a silane coupling agent (C) and water. Relative to 1 part by mass of water in the above-mentioned waterborne coating composition, the solid content of silane coupling agent (C) in the above-mentioned waterborne coating composition is 0.05 to 0.60 parts by mass.

[0013] [2] The waterborne coating composition kit as described in [1], wherein, relative to 1 part by weight of the solid component of the waterborne epoxy resin (A) in the waterborne coating composition, the solid component content of the silane coupling agent (C) in the waterborne coating composition is 0.07 to 1.2 parts by weight.

[0014] [3] The waterborne coating composition kit as described in [1] or [2], wherein, relative to the total solid content of the waterborne epoxy resin (A) and the solid content of the amine curing agent (B) in the waterborne coating composition, the solid content of the silane coupling agent (C) in the waterborne coating composition is 0.05 to 0.80 parts by mass.

[0015] [4] The waterborne coating composition kit as described in any one of [1] to [3], wherein the solid content of the silane coupling agent (C) in the waterborne coating composition is 0.03 to 0.25 parts by mass relative to 1 part by mass of the non-volatile component in the waterborne coating composition.

[0016] [5] A water-based coating composition kit as described in any one of [1] to [4], wherein the water content in the water-based coating composition is 5 to 50% by mass.

[0017] [6] The water-based coating composition kit as described in any one of [1] to [5], wherein the content of the non-volatile component in the water-based coating composition is 40 to 95% by mass.

[0018] [7] A coating film, wherein the coating film is formed using any one of the water-based paint compositions described in [1] to [6].

[0019] [8] A substrate with a coating, comprising a substrate and the coating described in [7].

[0020] [9] A method for manufacturing a coated substrate, comprising the following steps I and II, Step I: The step of applying the water-based coating composition obtained by using any one of the water-based coating compositions described in [1] to [6] onto a substrate; Process II: The process of drying the water-based coating composition applied to the substrate to form a coating film.

[0021] Invention Effects According to the present invention, a waterborne coating composition with excellent low-temperature drying and curing properties can be obtained, which can form a coating film with a good balance of initial water resistance and impact resistance.

[0022] Moreover, according to the present invention, the composition of the present invention, which has excellent low-temperature drying and curing properties and a long pot life, can be easily obtained. Attached Figure Description

[0023] Figure 1 This is a schematic top view (Schematic Explanation Figure) of a glass plate with a coating formed, viewed from above on the coating side during the drying and curing test of the following embodiment.

[0024] Symbol Explanation 1: Coating; 2: Glass plate; 3: The traces left by the test needle; a: The starting position of the test needle movement; b: The location where the glass plate becomes invisible; c: The position where the test needle slides across the coating surface without leaving any test needle mark. Detailed Implementation

[0025] Waterborne Coating Composition Kit (Waterborne Coating Composition Kit) The waterborne coating composition (hereinafter also referred to as the "composition of the present invention") kit (hereinafter also referred to as the "kit of the present invention") of the present invention is a multi-component kit containing a first agent containing a waterborne epoxy resin (A) and a second agent containing an amine curing agent (B), and containing a silane coupling agent (C) and water, wherein the solid content of the silane coupling agent (C) in the composition of the present invention is 0.05 to 0.60 parts by weight relative to 1 part by weight of water in the composition of the present invention.

[0026] With this invention kit, the composition of the invention with excellent low-temperature drying curing properties can be obtained, and a coating film with a good balance of initial water resistance and impact resistance can be formed.

[0027] Furthermore, coating compositions with excellent low-temperature drying and curing properties typically have a short pot life. However, contrary to this common knowledge, the present invention kit allows for the easy acquisition of compositions that possess both excellent low-temperature drying and curing properties and a longer pot life. While the reason for achieving this effect with the present invention kit is not yet clear, the inventors speculate as follows.

[0028] Regarding the composition of the present invention, it can be considered that, within a short period of time from the preparation of the composition of the present invention, the silane coupling agent undergoes hydrolysis in the presence of water, followed by condensation of the hydrolysis products to oligomerize, but the condensation slows down when the oligomer reaches a certain molecular weight, which is step (i). It can also be considered that, by coating the composition of the present invention after step (i) has occurred, the specific surface area of ​​the composition increases, and a step (ii) that promotes water evaporation occurs. By promoting water evaporation in this way, the pH value of the composition of the present invention increases, the condensation of the silane coupling agent is accelerated again, and the reaction of functional groups (e.g., epoxy groups, amino groups) in the silane coupling agent that can react with organic matter is promoted.

[0029] It can also be considered that, by performing the above-described steps (i) and (ii), even under low-temperature conditions where the reaction between epoxy resin and amine curing agent is difficult to proceed, the drying and curing properties of the composition of the present invention are excellent. However, when stored in a container or the like (before step (ii), due to the small specific surface area of ​​the composition, moisture does not easily evaporate, making it difficult to accelerate the re-condensation of the silane coupling agent and to promote the reaction of functional groups (e.g., epoxy groups, amino groups) in the silane coupling agent that can react with organic matter. Therefore, the composition of the present invention with a long pot life can be obtained.

[0030] The composition of the present invention can be obtained by mixing the first agent, the second agent, and an nth agent (n is 3 or more) other than the first agent and the second agent, as used as appropriate.

[0031] The preferred formulation of the present invention is a two-component formulation containing the first agent and the second agent described above, or a three-component formulation containing the first agent, the second agent, and the third agent described above.

[0032] Typically, the first, second, and nth agents constituting the kit of the present invention are stored, transported, etc., in separate containers and mixed before use of the composition of the present invention.

[0033] The first agent described above is preferably prepared through the following step 1.

[0034] The second agent described above is preferably prepared through the following step 2.

[0035] The above-mentioned nth agent is preferably prepared by the following step 3.

[0036] <The Composition of the Invention> The composition of the present invention is obtained from the kit of the present invention.

[0037] The composition of the present invention can also form a coating film with excellent corrosion resistance. Therefore, one embodiment of the composition of the present invention is preferably a water-based anti-corrosion coating composition.

[0038] The compositions of the present invention have excellent coating workability and can therefore be coated by various known coating methods, but due to their excellent spraying workability, they are suitable for use as spraying compositions.

[0039] The content of non-volatile components in the composition of the present invention is preferably 40-95% by mass, more preferably 45-95% by mass, and even more preferably 50-90% by mass.

[0040] The compositions of the present invention with non-volatile components within the above-mentioned range tend to have excellent low-temperature drying and curing properties, are less prone to sagging during coating, can form a thick film in one coating, and have excellent coating workability.

[0041] The content of non-volatile components in the composition of the present invention can be a value calculated based on the solid composition of the raw materials used, or it can be a measured value.

[0042] Specifically, the following value can be cited as an example of this determination: 1 ± 0.1 g of the composition of the present invention (the composition immediately after mixing the first agent, the second agent (and the nth agent if present)) is measured in a flat dish, evenly spread using a metal wire of known mass, dried at 23°C for 24 hours, and then heated at 125°C for 1 hour (at normal pressure). The percentage of the mass of the non-volatile component (heat-residual component), calculated by subtracting the mass of the metal wire from the mass after heating (including the mass of the metal wire), is relative to the mass of the initially measured composition of the present invention.

[0043] In addition, in this specification, the components of the raw materials constituting the composition of the present invention other than the solvent and dispersion medium (e.g., water) in the first agent, second agent, and nth agent of the silane coupling agent (C) are referred to as "solid components".

[0044] The semi-curing time of the composition of the present invention (the time from the moment the coating is formed to the semi-curing time of the coating at a temperature of 5°C) is preferably 10 hours or less, more preferably 8 hours or less, and the lower limit is preferably 0.5 hours.

[0045] The compositions of the present invention with a semi-curing time within the above range can be considered to have excellent low-temperature drying curing properties.

[0046] The semi-curing time was determined by the method described in the drying and curing section of the following examples.

[0047] [Silane coupling agent (C)] The composition of the present invention contains a silane coupling agent (C).

[0048] The silane coupling agent (C) can be combined with the first agent, the second agent, the nth agent, or at least two formulations selected from the first to the nth agents.

[0049] The silane coupling agent (C) used in the composition of the present invention may be one or more.

[0050] There are no particular limitations on the silane coupling agent (C), and existing known compounds can be used, preferably compounds having at least two functional groups in the same molecule and capable of improving adhesion to the substrate and reducing the viscosity of the composition of the present invention.

[0051] The silane coupling agent (C) is preferably a compound represented by, for example, the following formula (1). Where n represents 0 or 1, X represents a functional group that can react with organic matter (e.g., amino, vinyl, epoxy, mercapto, halogen group, a group in which part of a hydrocarbon group is replaced by the above groups, or a group in which part of a hydrocarbon group is replaced by an ether bond, etc., and then a group in which part of the above groups is replaced), Me is methyl, and Y represents a hydrolyzable group (e.g., methoxy, ethoxy, etc. alkoxy).

[0052] When using silane coupling agents that are reactive with amine curing agent (B), such as epoxy-containing silane coupling agents, it is preferable to combine the silane coupling agent with the first agent or the nth agent.

[0053] Furthermore, when using silane coupling agents that are reactive with waterborne epoxy resin (A), such as amino-containing silane coupling agents, it is preferable to combine the silane coupling agent with a second agent or an nth agent.

[0054] In the silane coupling agent (C), it is preferred to use an epoxy-containing silane coupling agent, wherein the above-mentioned X is an epoxy group, a group in which part of a hydrocarbon group is replaced by an epoxy group, or a group in which part of a hydrocarbon group is replaced by an ether bond or the like and then replaced by an epoxy group.

[0055] Commercially available products can be used as silane coupling agents. Examples of such commercially available products include 3-epoxypropoxypropyltrimethoxysilane "KBM-403" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "Sila-Ace S-510" (manufactured by JNC Corporation), 3-aminopropyltrimethoxysilane "KBM-903" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and the hydrolysis product of 3-aminopropylsilane "Dynasylan Hydrosil 1153" (manufactured by Evonik Industries Co., Ltd.).

[0056] Relative to 1 part by weight of water in the composition of the present invention, the solid content of silane coupling agent (C) in the composition of the present invention is 0.05 to 0.60 parts by weight, preferably 0.06 to 0.60 parts by weight, more preferably 0.07 to 0.60 parts by weight, and particularly preferably 0.10 to 0.50 parts by weight.

[0057] When the content is within the above range, the composition of the present invention, which has excellent low-temperature drying curing properties and a long pot life, can be easily obtained, and a coating film with excellent initial water resistance can be easily formed.

[0058] Relative to 1 part by weight of the solid component of the aqueous epoxy resin (A) in the composition of the present invention, the solid component content of the silane coupling agent (C) in the composition of the present invention is preferably 0.07 to 1.2 parts by weight, more preferably 0.10 to 1.0 parts by weight, and particularly preferably 0.15 to 0.90 parts by weight.

[0059] When the content is within the above range, the composition of the present invention with particularly excellent low-temperature drying and curing properties can be easily obtained.

[0060] Relative to the total solid content of the aqueous epoxy resin (A) and the solid content of the amine curing agent (B) in the composition of the present invention, the solid content of the silane coupling agent (C) in the composition of the present invention is preferably 0.05 to 0.80 parts by mass, more preferably 0.10 to 0.80 parts by mass, and particularly preferably 0.12 to 0.60 parts by mass.

[0061] When the content is within the above range, the composition of the present invention with particularly excellent low-temperature drying and curing properties can be easily obtained.

[0062] Relative to 1 part by mass of the non-volatile component of the composition of the present invention, the solid content of the silane coupling agent (C) in the composition of the present invention is preferably 0.03 to 0.25 parts by mass, more preferably 0.04 to 0.20 parts by mass.

[0063] When the content is within the above range, the composition of the present invention, which has particularly excellent low-temperature drying and curing properties, can be easily obtained.

[0064] When using an amino-containing silane coupling agent as silane coupling agent (C), Y is preferred. M / Y B Less than 0.8, more preferably less than 0.7.

[0065] Among them, Y M Y is the value obtained by dividing the amount (mass%) of the solid component of the amino-containing silane coupling agent contained in the composition of the present invention by the active hydrogen equivalent of the solid component of the amino-containing silane coupling agent. B The value is obtained by dividing the amount (mass%) of the solid component of the amine curing agent (B) contained in the composition of the present invention by the active hydrogen equivalent of the solid component of the amine curing agent (B).

[0066] [water] The composition of this invention contains water.

[0067] The water can be combined with the first agent, the second agent, the nth agent, or at least two or more formulations selected from the first to the nth agents.

[0068] Preferably, at least one of the first agent and the second agent contains water; more preferably, the second agent contains water; and even more preferably, both the first agent and the second agent contain water.

[0069] The raw materials used in preparing the first agent, such as the aqueous epoxy resin (A), and the raw materials used in preparing the second agent, such as the amine curing agent (B), sometimes contain water. When using such water-containing raw materials, it is possible to omit the water other than that contained in the raw materials. However, from the viewpoint of making it easier to prepare the composition of the present invention and to obtain a composition of the present invention with better coating workability, it is preferable to use water in addition to the water that may be contained in these raw materials.

[0070] There are no particular restrictions on the water used for further applications, such as tap water, but ion-exchanged water or distilled water are preferred.

[0071] When the first agent contains water, from the viewpoint of the viscosity and anti-settling properties of the coating, the water content in the first agent (including water that may be contained in the raw materials such as the raw material of waterborne epoxy resin (A)) is preferably 4 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 50% by mass.

[0072] Furthermore, from the viewpoint that the desired composition of the present invention can be readily obtained, the water content in the first agent is preferably 50% by mass or more, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to the total mass of the dispersion medium and solvent in the first agent.

[0073] In addition, silane coupling agents are not considered dispersion media in this specification.

[0074] When the second agent contains water, from the viewpoint of easily obtaining the desired composition of the present invention, the water content in the second agent (including water that may be contained in the raw materials such as the raw material of the amine curing agent (B)) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass.

[0075] Furthermore, from the viewpoint that the desired composition of the present invention can be readily obtained, the water content in the second agent is preferably 50% by mass or more, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to the total mass of the dispersion medium and solvent in the second agent.

[0076] Water is preferably used in such a way that the content of non-volatile components in the composition of the present invention reaches the above-mentioned range. However, from the viewpoint that the desired composition of the present invention can be easily obtained, the water content in the composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 50% by mass.

[0077] Method for manufacturing the composition of the present invention The method for manufacturing the composition of the present invention (hereinafter also referred to as "the method of the present invention") includes: Step 1: Preparation of the first agent using waterborne epoxy resin (A); Step 2: Preparation of the second agent using amine curing agent (B); As required, step 3, the preparation of the nth agent; and Step 4 involves mixing the first agent prepared in step 1, the second agent prepared in step 2, and the nth agent prepared in step 3 as needed. In at least one of the above steps 1 to 3, a silane coupling agent (C) and water are used.

[0078] <Process 1> Step 1 above is the process of preparing the first agent using water-based epoxy resin (A).

[0079] Step 1 can use only waterborne epoxy resin (A) without any particular restrictions. Waterborne epoxy resin (A) itself can be used as the first agent (in which case it can be said that step 1 is a step using waterborne epoxy resin (A)), or it can be a step in which waterborne epoxy resin (A) is mixed with the other components described below, with the latter being preferred.

[0080] In the latter case, specifically, step 1 is the process of mixing (or kneading) the components that are combined with the first agent. During this mixing (or kneading), the components can be added and mixed all at once or in multiple batches.

[0081] When performing the above mixing (or kneading), existing and known equipment such as mixers, dispersers, and agitators can be used. Examples of such equipment include dispersers, mixing / dispersing mills, mortar mixers, roller mills, paint mixers, and homogenizers. In addition, the above mixing (or kneading) can be performed while heating or cooling, depending on the season, environment, etc.

[0082] [Waterborne epoxy resin (A)] As specific examples of waterborne epoxy resin (A), epoxy resins that use water or mainly water as a solvent or dispersion medium, or epoxy resins that are miscible with water (can be diluted with water), and more specifically, water-dispersible epoxy resins, water-soluble epoxy resins, and self-emulsifying epoxy resins, etc.

[0083] Furthermore, for example, when these aqueous epoxy resins (A) are mixed with other components that may be contained in the first agent, it is sometimes impossible to determine whether they are aqueous epoxy resins. However, even in this case, when aqueous epoxy resins (A) are used as raw materials in the preparation of the first agent, etc., it is considered that aqueous epoxy resins (A) are contained.

[0084] The aqueous epoxy resin (A) used in the composition of the present invention may be one type or two or more types.

[0085] There are no particular limitations on the aqueous epoxy resin (A) used as the raw material for the first agent, but epoxy resin emulsion or epoxy resin dispersant is preferred, and epoxy resin emulsion is more preferred.

[0086] In addition, examples of epoxy resin emulsions include emulsions in which oil droplets containing epoxy resin are uniformly dispersed in an aqueous medium.

[0087] Epoxy resin emulsions can be prepared by forcibly emulsifying epoxy resin in an aqueous medium, such as through phase inversion temperature emulsification or mechanical emulsification. Examples of emulsifiers used include alkyl or alkylphenol nonionic surfactants and anionic surfactants such as phosphate esters, alkylbenzene sulfonates, and sulfosuccinates. Furthermore, one or more of these emulsifiers can be used alone.

[0088] From the viewpoint of improving the water resistance of the formed coating and reducing the amount of emulsifier used, the epoxy resin described above can also be a modified epoxy resin. As an example of this modification, one can exemplify this by bonding the epoxy resin to other compounds, introducing emulsifying segments into the molecule, thus modifying it into a self-emulsifying epoxy resin. More specifically, one can exemplify this by introducing at least one group selected from polyoxyalkylene chains, hydroxyl groups, amino groups, and carboxyl groups into the epoxy resin. Furthermore, these modified epoxy resins can be used alone or in combination with two or more groups.

[0089] Examples of epoxy resins include bisphenol-type epoxy resins, phenolic varnish-type epoxy resins (e.g., phenolic varnish-type epoxy resins, cresol varnish-type epoxy resins), and alicyclic epoxy resins. Among these, bisphenol-type epoxy resins are preferred from the perspective of obtaining a coating with superior corrosion resistance.

[0090] Examples of bisphenol-type epoxy resins include copolymers obtained using compounds with a bisphenol backbone and epihaloalcohols, and more specifically, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD ​​type epoxy resins. Among these, bisphenol A type epoxy resins are preferred for obtaining coatings with superior corrosion resistance. Furthermore, these epoxy resins can be used alone or in combination with two or more other types.

[0091] Commercially available products can be used as epoxy resin emulsions. Examples of such products include YUKA RESIN NEP-1110 (manufactured by Yoshimura Oil Chemical Co., Ltd.), ADEKA RESIN EM-101-50 (manufactured by ADEKA Co., Ltd.), BECKOPOX C-200 EP, and BECKOPOX EP 384w / 53WAMP (all manufactured by Allnex Germany GmbH).

[0092] From the viewpoint that it can easily form a coating with excellent low-temperature drying curing properties and corrosion resistance, the epoxy equivalent of the unit solid component of the above-mentioned epoxy resin is preferably 100 to 6000, more preferably 150 to 5000, further preferably 300 to 3000, and particularly preferably 400 to 3000.

[0093] From the viewpoint of easily obtaining a composition of the present invention with superior ease of preparation and storage stability, the content of epoxy resin in 100% by mass of the aqueous epoxy resin (A) used as a raw material for preparing the composition of the present invention is preferably 35 to 100% by mass, more preferably 45 to 100% by mass.

[0094] The portion of the waterborne epoxy resin (A) other than the epoxy resin may contain water, and may also contain known components such as surfactants, if needed.

[0095] From the viewpoint that it is easy to form a coating with excellent corrosion resistance, the solid content of the waterborne epoxy resin (A) in the composition of the present invention is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, relative to 100% by mass of the non-volatile components of the composition of the present invention.

[0096] For the same reason, the solid content of the waterborne epoxy resin (A) in the first agent is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, relative to 100% by mass of the solid content of the first agent.

[0097] [Other ingredients] In step 1, as needed and within the scope that does not impair the effects of the present invention, other components other than the above-mentioned waterborne epoxy resin (A) such as silane coupling agent (C), water, flash rust inhibitor, pigment, dispersant, defoamer, viscosity modifier (anti-sagging agent, anti-settling agent, thixotropic agent), reactive diluent, non-reactive diluent, plasticizer, curing accelerator, dehydrating agent, film-forming aid, organic solvent, etc. may be used (the first agent may also contain the above-mentioned other components).

[0098] These other ingredients can be used in one or more ways.

[0099] The other ingredients mentioned above may be those that are already known or available.

[0100] As other ingredients mentioned above, commercially available products can be used. These commercially available products may be available in two forms: those for organic solvents and those for water. When the first agent is formulated into an aqueous preparation by combining water with the first agent, a commercially available product for water is preferred as one of the other ingredients used in the first agent. Similarly, when the first agent is formulated into an organic solvent-based preparation by combining an organic solvent with the first agent, a commercially available product for organic solvents is preferred as one of the other ingredients used in the first agent.

[0101] <Flash Rust Inhibitor> When the composition of the present invention is applied to a metal surface, in order to prevent rust from seeping from the metal surface to the coating surface and causing rust spots (flash rust), a flash rust inhibitor can be added to the composition of the present invention.

[0102] As a flash rust inhibitor, any component that can inhibit the aforementioned flash rust is acceptable; there are no particular restrictions, and existing known flash rust inhibitors can be used.

[0103] Examples of flash rust inhibitors include: nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite, and ammonium nitrite; benzoates such as sodium benzoate, potassium benzoate, calcium benzoate, and ammonium benzoate; phytates such as sodium phytate and potassium phytate; fatty acid salts such as sebacic acid and dodecanoic acid; phosphate derivatives such as alkyl phosphates and polyphosphates; tannins; metal sulfonate salts; and N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), and diethylenetriamine. Amine chelating agents such as pentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their alkali metal salts; addition reactants obtained using 4-methyl-γ-oxophenylbutyric acid and N-ethylmorpholine; interlayer compounds formed by the insertion of monoalkylamines, polyamines, and / or quaternary ammonium ions into layered phosphates such as aluminum dihydrogen triphosphate; and hydrazine derivatives such as acylhydrazides, aminourea compounds, and hydrazone compounds.

[0104] As the aforementioned flash rust inhibitor, commercially available products can be used. Examples of such commercially available products include "Cheleslite W-410", "Cheleslite W-16B" (both manufactured by Chelest Co., Ltd. / organic acid salt system) and "HALOX FLASH-X 150" (manufactured by ICL Additives-Hammond Co., Ltd. / nitrite and benzoate system).

[0105] When a flash rust inhibitor is incorporated into the composition of the present invention, from the viewpoint that a coating that further inhibits flash rust can be easily formed, the amount of flash rust inhibitor incorporated is preferably 0.01 to 5% by mass relative to 100% by mass of the non-volatile components of the composition of the present invention, more preferably 0.05 to 3% by mass.

[0106] Furthermore, when a flash rust inhibitor is incorporated into the first agent, the amount of the flash rust inhibitor is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, relative to 100% by mass of the solid components of the first agent.

[0107] <Pigment> As pigments, examples include extender pigments, coloring pigments, and rust-preventing pigments, which can be either organic or inorganic.

[0108] Examples of pigments that can be categorized as body pigments include talc, mica, (precipitating) barium sulfate, (potassium) feldspar, kaolin, bauxite, bentonite, wollastonite, clay, glass flakes, aluminum flakes, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silicon dioxide. Among these, talc, mica, silicon dioxide, (precipitating) barium sulfate, and (potassium) feldspar are particularly preferred.

[0109] When an extender pigment is incorporated into the composition of the present invention, the amount of the extender pigment incorporated is preferably 1 to 80% by mass relative to 100% by mass of the non-volatile components of the composition of the present invention, more preferably 5 to 70% by mass.

[0110] Examples of such coloring pigments include inorganic pigments such as carbon black, titanium dioxide (titanium white), iron oxide (iron oxide red), iron oxide yellow, flaky iron oxide, and ultramarine, as well as organic pigments such as cyanine blue and cyanine green. Among these, titanium white, carbon black, and iron oxide red are particularly preferred.

[0111] When a coloring pigment is incorporated into the composition of the present invention, the amount of the coloring pigment incorporated is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, relative to 100% by mass of the non-volatile components of the composition of the present invention.

[0112] Examples of the aforementioned rust-preventive pigments include zinc powder, zinc alloy powder, zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, zinc cyanamide compounds, borate compounds, nitro compounds, and composite oxides.

[0113] When a rust-preventive pigment is incorporated into the composition of the present invention, the amount of the rust-preventive pigment is preferably 0.5 to 20% by mass relative to 100% by mass of the non-volatile components of the composition of the present invention, more preferably 1 to 10% by mass.

[0114] When pigments are incorporated into the compositions of the present invention, it is preferable to use the pigment in such a way that the pigment mass concentration (PWC) in the compositions of the present invention reaches 20-80%, more preferably 30-75%.

[0115] When the PWC is within the above range, the composition of the present invention with excellent coating workability can be easily obtained, and a coating film with excellent adhesion to the substrate and corrosion resistance due to stress relief can be easily formed.

[0116] In the above-mentioned composition of the present invention, PWC refers to the concentration of the total mass of pigments relative to the mass of the non-volatile components of the composition of the present invention, which can be obtained by the following formula (2).

[0117] The percentage of PWC in the composition of the present invention is equal to the total mass of all pigments in 100% mass of the composition of the present invention × 100 / the content of non-volatile components in the composition of the present invention (mass%)... (2) The content (mass%) of non-volatile components in the above-described compositions of the present invention can be a measured value or a value calculated based on the solid composition of the raw materials used. This measured value is obtained by the method described in the above-described section of the compositions of the present invention.

[0118] The total mass of all pigments in 100% by mass of the composition of the present invention can be a measured value or a value calculated based on the raw materials used. For example, this measured value can be calculated by separating the pigments and other components from the non-volatile components of the composition of the present invention and measuring the mass of the separated pigments.

[0119] <Dispersant> The pigments described above are preferably dispersed in the composition of the present invention, and therefore it is preferable to include a dispersant in the formulation containing the pigments.

[0120] As dispersants, various known organic or inorganic pigment dispersants can be cited, such as pigment adsorption groups (pigment affinity groups) such as carboxyl groups, phosphate groups, amino groups, their salt groups, and ammonium salt groups, and copolymers with compatible chains such as fatty acids, polyamino groups, polyethers, polyesters, polyurethanes, and polyacrylates.

[0121] When a dispersant is incorporated into the composition of the present invention, from the viewpoint of being able to easily form a coating film with excellent smoothness and uniform pigment dispersion, the amount of solid component of the dispersant is preferably 0.1 to 5% by mass relative to 100% by mass of the non-volatile component of the composition of the present invention, more preferably 0.1 to 3% by mass.

[0122] <Defoamer> From the viewpoints of being able to suppress the generation of bubbles during the manufacture or coating of the compositions of the present invention, or to eliminate bubbles generated in the compositions of the present invention, and to easily form a coating with the desired physical properties, the compositions of the present invention preferably contain an antifoaming agent.

[0123] As a defoamer, commercially available products can be used. Examples of such commercially available products include "BYK-392", "BYK-066N", "BYK-1770", "BYK-1790" (all manufactured by BYK Chemicals Japan Co., Ltd.), "TEGO Airex 902W" (manufactured by Evonik Industries Co., Ltd.), and "Spectrasyn 40" (manufactured by ExxonMobil Chemical Company).

[0124] When an antifoaming agent is incorporated into the composition of the present invention, from the viewpoint of being able to sufficiently suppress the generation of bubbles and easily form a coating with the desired physical properties, the amount of solid component of the antifoaming agent incorporated is preferably 0.005 to 1% by mass relative to 100% by mass of the non-volatile component of the composition of the present invention, more preferably 0.01 to 0.5% by mass.

[0125] <Viscosity modifiers (anti-sagging agents, anti-settling agents, thixotropic agents)> As viscosity modifiers (also known as anti-sagging agents, anti-settling agents, or thixotropic agents, hereinafter collectively referred to as "viscosity modifiers"), existing known viscosity modifiers such as stearates of Al, Ca, and Zn, lecithin salts, alkyl sulfonates, etc., organoclay waxes, polyethylene waxes, amide-based viscosity modifiers, amide neutralized salt-based viscosity modifiers, mixtures of amide-based viscosity modifiers, urea-based viscosity modifiers, hydrogenated castor oil wax, mixtures of hydrogenated castor oil wax and amide waxes, synthetic micronized silica, and oxidized polyethylene waxes are preferred. Among these, amide waxes, synthetic micronized silica, oxidized polyethylene waxes, and organoclay waxes are preferred.

[0126] As a viscosity modifier, commercially available products can be used. Examples of such commercially available products include "Disparlon 305", "Disparlon 4200-20", and "Disparlon 6650" manufactured by Kusunoki Chemical Co., Ltd.; "ASA T-250F" manufactured by Ito Oil Co., Ltd.; "FLOWNON RCM-300" manufactured by Kyoeisha Chemical Co., Ltd.; and "BENTONE DE" and "BENTONE SD-2" manufactured by Elementis Specialties, Inc.

[0127] When a viscosity modifier is incorporated into the composition of the present invention, from the viewpoints of being able to adjust the viscosity of the composition of the present invention, being able to easily suppress the sedimentation of pigments, etc. during storage of the composition of the present invention, and being able to easily suppress sagging during coating, the amount of the solid component of the viscosity modifier is preferably 0.5 to 4 by mass relative to 100% by mass of the non-volatile components of the composition of the present invention.

[0128] <Non-reactive diluent> Non-reactive diluents can be incorporated into the compositions of this invention. From the viewpoint of improving the flexibility of the resulting coating, the incorporation of non-reactive diluents is preferred.

[0129] In addition, non-reactive diluents refer to compounds that do not contain functional groups that are reactive with epoxy or amino groups.

[0130] As the aforementioned non-reactive diluent, a wide range of existing and known diluents can be used, including liquid hydrocarbon resins such as low-boiling-point fractions obtained from the thermal decomposition of naphtha (including modified versions of such liquid hydrocarbon resins), cashew nut shell liquid and cashew nut nut derivatives prepared from cashew nut shell liquid, petroleum resins, xylene resins, benzofuran-indene resins, etc. Specifically, liquid hydrocarbon resins and flexible resins described in Japanese Patent Application Publication No. 2006-342360 can be cited as examples.

[0131] From the viewpoint of excellent compatibility with the above-mentioned waterborne epoxy resin (A), liquid hydrocarbon resin, cashew phenol and cashew phenol derivatives are preferred, and phenol-modified hydrocarbon resin, cashew phenol and cashew phenol derivatives are more preferred.

[0132] Examples of phenol-modified hydrocarbon resins include resins obtained by using dienes, monoolefins, or α-methylstyrene contained in petroleum or coal decomposition oil fractions and phenols (phenolic compounds), as described in Japanese Patent Application Publication No. 9-268209 and Japanese Patent Application Publication No. 7-196793.

[0133] More specifically, examples of the aforementioned phenol-modified hydrocarbon resins include C5-based (aliphatic) petroleum resins made from C5 fractions, C9-based (aromatic) petroleum resins made from C9 fractions, C5 / C9 copolymer petroleum resins, dicyclopentadiene resins made from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in C5 fractions, and resins obtained by reacting phenols with α-methylstyrene. Among these, resins obtained by addition polymerization of styrene, vinyltoluene, benzofuran, indene, or α-methylstyrene contained in petroleum or coal decomposition oil fractions with phenols are preferred.

[0134] The average molecular weight of the above-mentioned phenol-modified hydrocarbon resins is usually 200-1000, and the viscosity is usually 30-10000 mPa·s / 25℃.

[0135] As the aforementioned liquid hydrocarbon resin, commercially available products can be used, such as "Necires EPX-L", "Necires EPX-L2" (both are phenol-modified hydrocarbon resins manufactured by NEVCIN Corporation), and "Hirenol PL-1000S" (a phenol-modified hydrocarbon resin manufactured by Kolon Industries, Inc.).

[0136] Commercially available products can be used as cashew nut shell extract and cashew nut shell extract derivatives, such as "Cardolite NX-2026" (manufactured by Cardolite Corporation / cashew nut shell extract), "Cardolite Lite-2020", "Cardolite NX-7507", "Cardolite NX-7509", and "Cardolite NX-7512" (all manufactured by Cardolite Corporation / cashew nut shell extract derivatives).

[0137] When a non-reactive diluent is incorporated into the composition of the present invention, the amount of the non-reactive diluent is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, relative to 100% by mass of the non-volatile components of the composition of the present invention.

[0138] When the content of non-reactive diluent is within the above range, it is easier to form a coating with better crack resistance and other properties.

[0139] <Film-forming aids> Since the composition of the present invention may freeze in winter due to its water content, and from the viewpoint of improving film-forming properties at low temperatures and the finished appearance of the resulting coating, a film-forming aid may be incorporated into the composition of the present invention.

[0140] As film-forming aids, film-forming aids commonly used in water-based coating compositions, such as organic compounds with a boiling point of 180°C or higher under normal pressure, can be used. Examples include: straight-chain or branched aliphatic alcohols with 5 to 15 carbon atoms; alcohols with aromatic rings, such as benzyl alcohol; monoethers such as polyethylene glycol or propylene glycol; polyethylene glycol ether esters; and propylene glycol ether esters.

[0141] When a film-forming aid is incorporated into the composition of the present invention, from the viewpoint of being able to easily form a film with excellent film-forming properties and appearance at low temperatures, the amount of the film-forming aid incorporated is preferably 0.5 to 10% by mass relative to 100% by mass of the composition of the present invention, more preferably 1 to 8% by mass.

[0142] <Organic Solvents> The composition of the present invention is an aqueous coating composition containing water, but at least one of the first agent, the second agent and the nth agent can be an organic solvent-based formulation containing an organic solvent (but does not include cases where all formulations of the first agent, the second agent and the nth agent are organic solvent-based formulations).

[0143] As an organic solvent, it is preferred to have an organic solvent with a boiling point below 180°C under normal pressure. Examples include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), ether solvents such as butyl cellosolve, ester solvents such as butyl acetate, alcohol solvents such as isopropanol, isobutanol, n-butanol, and methoxypropanol, and aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, and methylcyclohexane.

[0144] When an organic solvent is used in the composition of the present invention, it is preferable to use the organic solvent in such a way that the content of the non-volatile component in the composition of the present invention reaches the above-mentioned range.

[0145] <Process 2> Step 2 above is the step of preparing the second agent using amine curing agent (B).

[0146] Step 2 can be performed using amine curing agent (B) without any particular restrictions. The amine curing agent (B) itself can be used as the second agent (in which case it can be said that step 2 is a step using amine curing agent (B)), or it can be a step in which the amine curing agent (B) is mixed with the other components described below. The latter is preferred.

[0147] In the latter case, specifically, step 2 is the process of mixing (or kneading) the components that are combined with the second agent. During this mixing (or kneading), the components can be added and mixed all at once or in multiple batches.

[0148] When performing the above mixing (or kneading), existing and known equipment such as mixers, dispersers, and agitators can be used. Examples of such equipment include dispersers, mixing / dispersing mills, mortar mixers, roller mills, paint mixers, and homogenizers. In addition, the above mixing (or kneading) can be performed while heating or cooling, depending on the season, environment, etc.

[0149] [Amine curing agent (B)] As an amine curing agent (B), existing known amine compounds that are used as curing agents for epoxy compounds can be cited.

[0150] The amine curing agent (B) used in the composition of the present invention may be one or more.

[0151] As specific examples of amine curing agents (B), water-soluble amine curing agents and non-water-soluble amine curing agents can be cited. From the viewpoint that they can easily form coatings with excellent low-temperature drying and curing properties, non-water-soluble amine curing agents are preferred.

[0152] Furthermore, in cases where water-soluble amine curing agents are used, for example, it is sometimes impossible to determine whether the water-soluble amine curing agent is water-soluble after being mixed with other components that may be contained in the second agent. However, even in such cases, when the water-soluble amine curing agent is used as a raw material in the preparation of the second agent, it is considered to contain the water-soluble amine curing agent in this invention. The same applies to non-water-soluble amine curing agents.

[0153] The water-soluble amine curing agent in this invention refers to a component containing an epoxy-curable amine compound dissolved in a dispersion medium including water (hereinafter also referred to as "aqueous medium"). Specifically, it refers to a component containing an amine compound that is transparent in appearance after mixing 30% by mass of water and 70% by mass of the amine compound constituting the amine curing agent at a temperature of 25°C and stirring thoroughly.

[0154] Examples of water-soluble amine curing agents include water-soluble compounds among the amine compounds used as curing agents for epoxy compounds, or amine compounds used as curing agents for epoxy compounds that are converted into water-soluble compounds by known methods.

[0155] As a method for converting it to water solubility, examples include the introduction of water-soluble groups such as carboxyl groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups, and hydroxyl groups, as well as the introduction of hydrophilic groups such as glycidyl ether addition modification of polyalkylene glycols.

[0156] The non-water-soluble amine curing agent in this invention refers to a component containing an epoxy-curable amine compound that is insoluble in aqueous media. Specifically, it refers to a component containing an amine compound such that, after mixing 30% by mass of water and 70% by mass of the amine compound constituting the amine curing agent at 25°C and stirring thoroughly, the resulting mixture is opaque, but rather translucent or white and turbid.

[0157] Examples of non-water-soluble amine curing agents include, for example, non-water-soluble compounds among the amine compounds used as curing agents for epoxy compounds. Alternatively, examples include: compounds among the amine compounds used as curing agents for epoxy compounds that are emulsified and dispersed in a relatively large amount in an aqueous medium (hereinafter also referred to as "water-dilution"); water-dilution components containing hydrophilic amine compounds obtained by reacting the amine compounds used as curing agents for epoxy compounds with glycidyl ethers of polyalkylene glycols or polyoxyalkylene amines; water-dilution components containing amine compounds with amide structures obtained using fatty acids and aliphatic amine compounds; or water-dilution components obtained by forcibly dispersing amine compounds that have been given emulsifying ability by neutralizing the amine compounds used as curing agents for epoxy compounds with an acid or mixing them with an emulsifier in water.

[0158] The amine compound used as a curing agent for the epoxy compound is any amine compound other than tertiary amines (amine compounds containing only tertiary amino groups) and flash rust inhibitors, without particular limitation. Examples of amine compounds containing two or more amino groups in one molecule are included, and amine compounds of aliphatic, alicyclic, aromatic, heterocyclic, etc. are preferred.

[0159] Examples of the aforementioned aliphatic amine compounds include, for example, alkylene polyamines, polyalkylene polyamines, and alkylaminoalkylamines.

[0160] Examples of the aforementioned alkylene polyamines include, for example, the formula: "H2N-R" 1 The compound shown is -NH2”, wherein R 1 It is a divalent hydrocarbon group with 1 to 12 carbon atoms. Specific examples include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and trimethylhexamethylenediamine.

[0161] Examples of the aforementioned polyalkylene polyamines include, for example, the formula: "H2N-(C m H 2m NH) n The compound indicated by "H" is wherein m is an integer from 1 to 10, and n is an integer from 2 to 10, preferably an integer from 2 to 6. Specific examples include diethylenetriamine, dipropyltriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0162] Examples of alkylaminoalkylamines, such as the one described above, can be given by formula: "R" 2 2N-(CH2) p The compound shown is -NH2”, wherein R 2 Independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but with at least one R 2 It is an alkyl group having 1 to 8 carbon atoms, and p is an integer from 1 to 6. Specific examples include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0163] Examples of aliphatic amine curing agents other than these include tetra(aminomethyl)methane, tetra(2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, tri(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylene polyamines (especially diethylene glycol bis(3-aminopropyl) ether), bis(aminomethyl)cyclohexane, isophorone diamine (IPDA), methylbenzene diamine (MDA), o-phenylenediamine, m-phenylenediamine (MXDA), p-phenylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), and 1-[2'-(2''-aminoethylamino)ethyl]piperazine.

[0164] Specific examples of the aforementioned alicyclic amine curing agents include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4′-methylenebicyclohexylamine), 4,4′-isopropylidenedicyclohexylamine, norbornenediamine, and 2,4-bis(4-aminocyclohexylmethyl)aniline.

[0165] Examples of aromatic polyamine compounds that can be used as curing agents for the aforementioned aromatic amines include, for instance, aromatic polyamine compounds having two or more primary amino groups bonded to aromatic rings such as benzene or naphthalene rings.

[0166] Specific examples of this aromatic amine curing agent include phenylenediamine, naphthylenediamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and diethylmethylphenylenediamine.

[0167] Specific examples of the aforementioned heterocyclic amine curing agents include 1,4-diazacycloheptane, 1,11-diazacycloeicosane, and 1,15-diazacyclooctadecane.

[0168] Examples of amine compounds used as curing agents for epoxy compounds include modified versions of the aforementioned amine compounds, such as modified alicyclic polyamines, modified aliphatic polyamines, fatty acid modifiers such as polyamide amines, amine adducts with epoxy compounds, Mannich-modified amines (e.g., Mannich-modified amines with a phenolic backbone (phenolic amines, phenolic amides, etc.)), Michael adducts, ketimines, and aldolimines. Among these, modified alicyclic polyamines, modified aliphatic polyamines, polyamide amines, amine adducts with epoxy compounds, and Mannich-modified amines with a phenolic backbone are preferred.

[0169] From the viewpoint that it can easily form a coating with excellent low-temperature drying curing properties and corrosion resistance, the active hydrogen equivalent of the solid component of the amine curing agent (B) is preferably 20 to 200, more preferably 30 to 190.

[0170] From the viewpoint that it is possible to easily form a coating with excellent corrosion resistance, coating strength and low-temperature drying curing properties, it is preferable to use an amount of amine curing agent (B) with a reaction ratio calculated by the following formula (3) preferably of 0.3 to 1.5, more preferably of 0.4 to 1.2.

[0171] Reaction ratio = {(Amount of solid component of amine curing agent (B) / Active hydrogen equivalent of solid component of amine curing agent (B)) + (Amount of solid component of component that reacts with waterborne epoxy resin (A) / Functional group equivalent of solid component of component that reacts with waterborne epoxy resin (A)} / {(Amount of solid component of waterborne epoxy resin (A) / Epoxy equivalent of solid component of waterborne epoxy resin (A)) + (Amount of solid component of component that reacts with amine curing agent (B) / Functional group equivalent of solid component of component that reacts with amine curing agent (B)} ... (3) Among them, the "component that is reactive with amine curing agent (B)" and "component that is reactive with waterborne epoxy resin (A)" in the above formula (3) can be exemplified by the above-mentioned silane coupling agent (C).

[0172] As the silane coupling agent (C) mentioned above, a silane coupling agent having an amino or epoxy group as a reactive group can be used. Therefore, it is necessary to determine whether the silane coupling agent (C) is reactive with the amine curing agent (B) or with the waterborne epoxy resin (A) based on the type of reactive group, and to calculate the reaction ratio.

[0173] The “functional group equivalent” of the above components means the mass (g) of each mol of functional group obtained by dividing the mass of 1 mol of these components by the number of moles (mol) of functional groups contained therein.

[0174] The amount of solid component of the amine curing agent (B) in step 2 is preferably an amount that satisfies the above formula (3). From the viewpoint that it is possible to easily form a coating film with excellent corrosion resistance and low-temperature drying curing properties, it is more preferably an amount that reaches the following range.

[0175] The amount of solid component of amine curing agent (B) is preferably 1 to 30% by mass relative to 100% by mass of the non-volatile component of the composition of the present invention, more preferably 2 to 20% by mass.

[0176] The amount of solid component of amine curing agent (B) is preferably 5 to 99% by mass relative to 100% by mass of the solid component of the second agent, and more preferably 7 to 99% by mass.

[0177] [Other ingredients] In step 2, as needed, other components other than the amine curing agent (B) may be used within the scope that does not impair the effects of the present invention, such as silane coupling agent (C), water, flash rust inhibitor, pigment, dispersant, defoamer, viscosity modifier (anti-sagging agent, anti-settling agent, thixotropic agent), non-reactive diluent, plasticizer, curing accelerator, dehydrating agent, film-forming aid, polycarboxylic acid with 2 or more elements, curing catalyst, organic solvent, etc. (the second agent may also contain the above-mentioned other components).

[0178] These other ingredients can be used individually or in combination with two or more.

[0179] The other components mentioned above may be existing known components, such as flash rust inhibitors, pigments, dispersants, defoamers, viscosity modifiers (anti-sagging agents, anti-settling agents, thixotropic agents), non-reactive diluents, film-forming aids, and organic solvents, and may include components that are the same as those described in the first agent section above.

[0180] As other ingredients mentioned above, commercially available products may also be used. In this case, commercially available products may be available in both organic solvent-based and water-based forms. When the second agent is formulated into an aqueous formulation by combining water with the second agent, a commercially available water-based product is preferred as another ingredient in the second agent. When the second agent is formulated into an organic solvent-based formulation by combining an organic solvent with the second agent, a commercially available organic solvent-based product is preferred as another ingredient in the second agent.

[0181] From the viewpoint of being able to easily obtain a composition with better flash rust resistance, it is preferable to add a flash rust inhibitor to the second agent. In this case, the amount of flash rust inhibitor added is preferably 0.01 to 5% by mass relative to 100% by mass of the solid component of the second agent, more preferably 0.03 to 5% by mass.

[0182] Furthermore, from the viewpoint of being able to easily form a film with excellent film-forming properties at low temperatures, it is preferable to incorporate a film-forming aid into the second agent. In this case, the amount of the film-forming aid is preferably 0.05 to 50% by mass relative to 100% by mass of the solid component of the second agent, and more preferably 1 to 35% by mass.

[0183] <Process 3> Step 3 described above is performed as needed (when the kit of the present invention is a kit with three or more components), and is the step of preparing the aforementioned nth agent. Alternatively, for example, when the kit of the present invention is a kit with four components, step 3 is the step of preparing the third and fourth agents separately.

[0184] Step 3 can be performed appropriately depending on the components used in the nth agent, preferably using the silane coupling agent (C) itself as the nth agent (at this point, it can be said that step 3 is a step using the silane coupling agent (C).

[0185] In addition, in step 3, the other components and water described in parts of steps 1 and 2 can be used together with the silane coupling agent (C), or the other components and water can be used without using the silane coupling agent (C).

[0186] When using two or more ingredients in step 3, the ingredients to be combined can be mixed (or kneaded) in the same way as in steps 1 and 2.

[0187] <Process 4> Step 4 above is a process of mixing the first agent prepared in step 1, the second agent prepared in step 2, and the nth agent prepared in step 3 as needed.

[0188] The compositions of the present invention can be prepared by mixing (or kneading) these first agents, second agents, and nth agents as needed. This mixing (or kneading) can be performed either by mixing the formulations all at once or by mixing them in multiple stages.

[0189] When the nth agent is used in step 4, there are no particular restrictions on the mixing order of the first agent, the second agent, and the nth agent.

[0190] When performing the above-mentioned mixing (kneading), existing and known equipment such as mixers, dispersers, and agitators can be used. Examples of such equipment include dispersers, mixing / dispersing mills, mortar mixers, roller mills, paint mixers, and homogenizers. Furthermore, the above-mentioned mixing (kneading) can be carried out simultaneously with heating or cooling, depending on the season and environment.

[0191] Coated Films and Coated Substrates The coating of the present invention (hereinafter also referred to as "the coating of the present invention") is formed using the kit of the present invention, specifically, formed from the composition of the present invention obtained from the kit of the present invention or the composition of the present invention manufactured by the method of the present invention.

[0192] The coating of the present invention is preferably used on a coated substrate comprising a substrate and the coating of the present invention (hereinafter also referred to as "the coated substrate of the present invention"). The coated substrate of the present invention is a laminate having the coating of the present invention and a substrate.

[0193] The coating film of the present invention described above can be a film formed from a single layer (e.g., a coating film formed by a single coating as described below), or a film comprising two or more layers (e.g., a coating film formed by two or more coatings as described below). This film comprising two or more layers can be formed without changing the composition of the composition of the present invention when forming the film, or it can be formed by changing the composition of the composition of the present invention when forming the film.

[0194] There are no particular restrictions on the materials used as the base material. Examples include iron (iron, steel, ferroalloys, carbon steel, low carbon steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, galvanized, sprayed zinc, etc.), and stainless steel (SUS304, SUS410, etc.).

[0195] In addition, when using low carbon steel (SS400, etc.) as the above-mentioned substrate, it is preferable to perform substrate adjustment in advance as needed, such as grinding the substrate surface by sandblasting (for example, adjusting the arithmetic mean roughness (Ra) to about 30 to 75 μm).

[0196] The aforementioned substrate can also be a substrate that has undergone further pretreatment such as cleaning or sandblasting to remove rust, dirt, paint (old coating) and other substances attached to the substrate.

[0197] There are no particular limitations on the above-mentioned substrates, and they can be used without restriction. However, from the viewpoint of further maximizing the effect of using the composition of the present invention, a substrate that requires corrosion resistance is preferred, and (steel) structures such as ships, marine structures, factory equipment, bridges, storage tanks, and containers are more preferred.

[0198] The dry film thickness of the coating of the present invention is not particularly limited, but from the viewpoint of being able to easily obtain a coating with excellent corrosion resistance, it is preferably 10 to 500 μm, and more preferably 15 to 400 μm.

[0199] The substrate with coating of the present invention is a laminate containing the coating of the present invention and the substrate, which may have a primer coating (base coat) for improving adhesion to the substrate and corrosion resistance, an intermediate coat for improving corrosion resistance, and a topcoat for weather resistance and aesthetics.

[0200] Specifically, when the composition of the present invention is used as a substitute for zinc primer, an intermediate paint film or a topcoat film can be formed on the coating film of the present invention.

[0201] Examples of primer films include those formed from various primer compositions such as epoxy resins. Examples of intermediate paint films include those formed from various intermediate paint compositions such as (meth)acrylic resins, epoxy resins, and urethane resins. Examples of topcoat films include those formed from various topcoat compositions such as (meth)acrylic resins, (meth)acrylic silicone resins, urethane resins, silicone resins, and fluoropolymers. Furthermore, the composition of the present invention can be modified to form primer films, intermediate paint films, and topcoat films.

[0202] <Method for manufacturing a coated substrate> The method for manufacturing the coated substrate of the present invention includes the following steps I and II.

[0203] Step 1: The step of applying the composition of the present invention obtained using the kit of the present invention or the composition of the present invention manufactured by the method of the present invention onto a substrate.

[0204] Step II: The step of drying the composition of the present invention coated on the substrate to form the coating film of the present invention.

[0205] <Process I> There are no particular limitations on the coating method used in step I described above, and existing known methods such as airless spraying, air spraying, brushing, and roller coating can be used as examples. However, from the viewpoint that it is easier to achieve the effects of the present invention and that it is easier to coat large-area substrates such as the aforementioned structures, spraying is preferred.

[0206] The above spraying conditions can be adjusted appropriately according to the desired dry film thickness. For example, in the case of airless spraying, the preferred primary (air) pressure is about 0.3 to 0.6 MPa, the secondary (coating) pressure is about 10 to 15 MPa, and the spray gun moving speed is about 50 to 120 cm / second.

[0207] The coating process described above is preferably performed in a manner that ensures the dried film thickness of the coating film of the present invention formed in step II reaches the aforementioned range. In this case, the desired film thickness of the coating film of the present invention can be formed either by a single coating (one-coat layer) or by two or more coatings (two or more coating layers).

[0208] In addition, double coating means that after performing steps I and II, steps I and II are performed on the coating obtained in step II.

[0209] When applying the composition of the present invention to a substrate, in order to remove rust, grease, moisture, dust, salt, etc. from the substrate, and to improve the adhesion of the obtained coating to the substrate, it is preferable to treat the surface of the substrate as needed (e.g., sandblasting (ISO 8501-1 Sa2 1 / 2), or degreasing to remove oil and dust). Additionally, for the purpose of initial rust prevention, a shop primer may also be applied to the substrate.

[0210] <Process II> There are no particular restrictions on the drying conditions in step II above. They can be set appropriately according to the coating formation method, the type of substrate, the application, the coating environment, etc. Under normal temperature drying conditions, the drying temperature is usually 10 to 35°C. Under forced drying conditions using a hot air dryer or the like, the temperature is usually above 30°C and below 100°C, and more preferably 40 to 80°C.

[0211] Furthermore, since the compositions of the present invention exhibit excellent low-temperature drying and curing properties, from the viewpoint of further enhancing the effects of the present invention, drying is preferably performed at a low temperature, specifically 0–10°C, more preferably 5–10°C. According to the compositions of the present invention, even with such low-temperature drying, the compositions can be sufficiently dried and cured.

[0212] The drying time varies depending on the drying method of the coating. Under low temperature or room temperature drying conditions, it takes about 1 to 7 days. Under forced drying conditions, it takes about 5 to 60 minutes.

[0213] Example The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0214] [Examples 1-24 and Comparative Examples 1-4] Add the ingredients listed in the "First Agent" column of Table 1 or Table 2 to a container in the amounts (numerical values, mass parts) recorded in Table 1 or Table 2, and stir for 30 minutes at room temperature (23°C) using a high-speed disperser to prepare the first agent.

[0215] In addition, the components listed in the second agent column of Table 1 or Table 2 are added to another container in the amounts (numerical values, mass parts) recorded in Table 1 or Table 2, and stirred using a high-speed disperser until the temperature reaches 45-50°C to prepare the second agent.

[0216] The prepared first agent, second agent, and third agent listed in the third agent column of Table 1 or Table 2 are mixed at the mixing ratio (mass%) as described in Table 1 or Table 2 to prepare an aqueous coating composition with the total amount shown in Table 1 or Table 2.

[0217] Table 3 shows descriptions of the components listed in Tables 1 and 2.

[0218] <Drying and Curing Properties> Using a coating applicator, the above-mentioned water-based coating compositions were applied to a 348mm×25mm×2mm (thickness) glass plate to achieve a dry film thickness of 150μm.

[0219] Using an RC-type drying time recorder (manufactured by Coating Tester Co., Ltd.), the test probe of the RC-type drying time recorder was moved slowly across the coating at a constant speed (the measurement time was set to 24 hours) at a temperature of 5°C. The state of the coating was determined based on the trace left by the test probe, and the time from the formation of the coating to its semi-curing (semi-curing time) was determined. The results are shown in Tables 1 and 2.

[0220] In addition, the semi-curing time is as follows.

[0221] Figure 1 This is a schematic top view (schematic illustration) of the glass plate 2 with the coating 1 formed, viewed from above on the side of the coating 1.

[0222] Position a is the position where the test needle is positioned in contact with the coating 1 formed on the glass plate 2, causing the test needle to begin moving. Position b is the position where the glass plate 2 with the coating 1 is invisible (due to the coating 1) when viewed from above from the side of the coating 1. Position c is the position where the test needle slides across the surface of the coating 1 without leaving any trace of the test needle on the surface of the coating 1.

[0223] The time required for the test needle to move from position a to position b is taken as the semi-curing time (the time required for the test needle to move from position a to position c is taken as the full curing time).

[0224] <Initial water resistance> Prepare a 150mm × 70mm × 2.3mm (thickness) SS400 sandblasted steel plate (arithmetic mean roughness (Ra): 30~75μm). Use an applicator to apply the above-mentioned water-based coating compositions to the surface of the steel plate in such a way that the dried film thickness reaches 100μm.

[0225] The steel plates coated with the above-mentioned water-based coating compositions were dried immediately at 5°C and 70% RH for 24 hours to form a coating film, and then immersed in water at 23±3°C for 3 hours. The coating films after immersion in water for 3 hours were visually evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.

[0226] (Evaluation Criteria) 5: No bubbles were found in the coating on the steel plate.

[0227] 4: Bubbling was found in less than 3% of the total coating area on the steel plate.

[0228] 3: Bubbling was found in areas covering more than 3% but less than 15% of the total coating area on the steel plate.

[0229] 2: Bubbling is found in areas where the total coating area on the steel plate is more than 15% but less than 50%.

[0230] 1: Bubbling was found in more than 50% of the total coating area on the steel plate.

[0231] 0: The coating on the steel plate peels off from the steel plate.

[0232] Impact resistance test Using an applicator, the above-mentioned water-based coating compositions were applied to tin-plated iron plates (150mm×70mm×0.3mm (thickness)) with a dry film thickness of 75μm. After drying at 25°C and 50%RH for 1 day, the plates were dried at 50°C for 7 days to form a coating film on one side (front side) of the tin-plated iron, thus producing a test coated plate.

[0233] For the back side (the side without coating) of each prepared test coated plate, a drop hammer test was conducted according to the DuPont method of JIS K 5600-5-3:1999 (drop height 200 mm, hammer mass 1000 ± 1 g, hammer radius 1 / 4 inch (6.35 mm)). On the front side of each test coated plate opposite to the drop point (opposite to the drop point), a cutter blade was inserted between the tinplate and the coating. The cutter blade was positioned approximately horizontally to the tinplate surface, centered on the drop point, and moved in a manner that peeled the coating away from the tinplate. The impact resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.

[0234] (Evaluation Criteria) ○: The part of the coating peeled off is within 1 / 2 inch (12.7 mm) of the center point of the drop of the weight.

[0235] ×: The portion of the coating that has peeled off is more than 1 / 2 inch (12.7 mm) away from the center of the point where the hammer falls.

[0236] [Table 1] [Table 2] [Table 3]

Claims

1. A water-based coating composition kit, characterized in that: The water-based coating composition kit is a multi-component water-based coating composition kit, comprising: The first agent containing waterborne epoxy resin (A); and The second agent containing amine curing agent (B), The water-based coating composition kit contains a silane coupling agent (C) and water. The solid content of the silane coupling agent (C) in the water-based coating composition is 0.05 to 0.60 parts by weight relative to 1 part by weight of water in the water-based coating composition.

2. The water-based coating composition kit as described in claim 1, characterized in that: The solid content of the silane coupling agent (C) in the waterborne coating composition is 0.07 to 1.2 parts by mass relative to 1 part by mass of the solid component of the waterborne epoxy resin (A) in the waterborne coating composition.

3. The water-based coating composition kit as described in claim 1, characterized in that: Relative to 1 part by mass of the total solid content of the waterborne epoxy resin (A) and the solid content of the amine curing agent (B) in the waterborne coating composition, the solid content of the silane coupling agent (C) in the waterborne coating composition is 0.05 to 0.80 parts by mass.

4. The water-based coating composition kit as described in claim 1, characterized in that: Relative to 1 part by weight of the non-volatile component in the water-based coating composition, the solid content of the silane coupling agent (C) in the water-based coating composition is 0.03 to 0.25 parts by weight.

5. The water-based coating composition kit as described in claim 1, characterized in that: The water content in the water-based coating composition is 5-50% by mass.

6. The water-based coating composition kit as described in claim 1, characterized in that: The content of non-volatile components in the water-based coating composition is 40-95% by mass.

7. A coating film, characterized in that: The coating is formed using the aqueous coating composition according to any one of claims 1 to 6.

8. A substrate with a coating, characterized in that: It comprises a substrate and the coating as described in claim 7.

9. A method for manufacturing a coated substrate, characterized in that: Includes the following processes I and II, Step 1: Applying the water-based coating composition obtained using any one of claims 1 to 6 onto a substrate; Process II: The process of drying the water-based coating composition applied to the substrate to form a coating film.

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