Method for producing corrosion-resistant coating composition

Abstract

To provide a method for producing a high-solid corrosion-resistant coating composition capable of forming a corrosion-resistant coating film with excellent corrosion resistance, while also offering excellent workability during application, and to provide a kit for the corrosion-resistant coating composition.SOLUTION: There is provided a method for producing corrosion-resistant coating composition with VOC content of 100 g / L or less, the method including a step 1 of preparing a first agent using an aqueous epoxy compound (A) and the following steps 2 and 3, or the following steps 2a, 2b and 3', wherein component (B) is a dispersion in which amine compounds other than tertiary amines are dispersed in an aqueous medium, and component (C) is a non-aqueous amine compound. The step 2 is a step for preparing a second agent, using a water dilution component (B) containing an amine compound, and a non-aqueous component (C) containing an amine compound, and the step 3 is a step for mixing the first agent and second agent. The step 2a is a step for preparing a 2a agent using the water dilution component (B) containing an amine compound, the step 2b is a step for preparing a 2b agent using the non-aqueous component (C) containing an amine compound, and the step 3' is a step for mixing the first agent, the 2a agent and the 2b agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an anticorrosion coating composition, a kit for an anticorrosion coating composition, an anticorrosion coating film, a substrate with an anticorrosion coating film, and a method for producing a substrate with an anticorrosion coating film. [Background technology]

[0002] BACKGROUND ART Solvent-based epoxy resin anticorrosive paints are applied to substrates such as ships, marine structures, plants, bridges, and land-based tanks in order to ensure their long-term use.

[0003] In recent years, with the strengthening of organic solvent emission regulations aimed at considering the natural environment and the painting work environment, efforts are being made to reduce the VOC (volatile organic compound) content of solvent-based paints such as those mentioned above. One method of reducing VOCs is to make paints water-based. Because water-based anticorrosion paints use water primarily as the solvent and dispersion medium, it is possible to significantly reduce VOCs compared to conventional solvent-based paints while maintaining appropriate paint viscosity.

[0004] As such water-based anticorrosive coating materials, for example, Patent Document 1 discloses a water-based epoxy resin composition containing an epoxy resin emulsion and a water-soluble amine curing agent, and Patent Document 2 discloses a water-based epoxy resin coating composition containing a water-soluble amine resin and a hydrophobic liquid epoxy resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-247958 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-221256 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the anticorrosion coating films formed from the conventional anticorrosion paints described in Patent Documents 1 and 2 above do not have sufficient anticorrosion performance, and there is room for improvement in this respect.

[0007] Furthermore, increasing the solidity of paints is an effective way to improve the efficiency of painting work, such as by reducing the number of coats required to form a corrosion-resistant coating of a predetermined thickness, but with the conventional corrosion-resistant paints, the increased viscosity associated with increasing the solidity reduces painting workability. In other words, with conventional corrosion-resistant paints, there is a trade-off between high solidity and painting workability, and it has been difficult to achieve both.

[0008] The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing an anticorrosion coating composition that is capable of forming an anticorrosion coating film with excellent corrosion resistance, and that has high solidity and excellent coating workability, and a kit for use with said anticorrosion coating composition. [Means for solving the problem]

[0009] As a result of extensive research into methods for solving the above problems, the present inventors have found that the above problems can be solved by the following configuration example, and have thus completed the present invention. An example of the configuration of the present invention is as follows.

[0010] <1> Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2: preparing a second agent using a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound; Step 3 of mixing the first agent and the second agent; Including, the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A method for producing an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0011] <2> Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2a: preparing a second agent (2a) using a water-dilutable component (B) containing an amine compound; Step 2b: preparing a second agent b using a non-aqueous component (C) containing an amine compound; a step 3' of mixing the first agent, the second agent a, and the second agent b; Including, the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A method for producing an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0012] <3> The viscosity of the anticorrosion coating composition measured at 23°C is 7,000 mPa s or less. <1> or <2> A method for producing the anticorrosion coating composition according to claim 1.

[0013] <4> the anticorrosion coating composition further contains a pigment, and the pigment volume concentration (PVC) in the anticorrosion coating composition is 25 to 45%; <1> ~ <3> 1. A method for producing the anticorrosion coating composition according to any one of the preceding claims.

[0014] <5> The non-aqueous amine compound is an amine compound having a cyclic structure and a molecular weight of 3,000 or less. <1> ~ <4> 1. A method for producing the anticorrosion coating composition according to any one of the preceding claims.

[0015] <6> The first agent further contains a silane coupling agent. <1> ~ <5> 1. A method for producing the anticorrosion coating composition according to any one of the preceding claims.

[0016] <7> a first agent containing a non-aqueous epoxy compound (A); A second agent containing a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound. Contains the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A kit for an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0017] <8> a first agent containing a non-aqueous epoxy compound (A); A second agent (a) containing a water-dilutable component (B) containing an amine compound; A second agent (b) containing a non-aqueous component (C) containing an amine compound; Contains the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A kit for an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0018] <9> <7> or <8> A corrosion-resistant coating film formed from the corrosion-resistant coating composition kit described in 1. <10> Substrate and <9> and a substrate with a corrosion-resistant coating film, comprising the corrosion-resistant coating film according to claim 1.

[0019] <11> A method for producing a substrate with a corrosion-resistant coating, comprising the following steps [1] and [2]: [1] The substrate is <1> ~ <6> An anticorrosion coating composition produced by the production method described in any one of the above items, or <7> or <8> a step of applying the anticorrosion coating composition obtained from the anticorrosion coating composition kit described in [2] A step of drying the anticorrosion coating composition applied to the substrate to form an anticorrosion coating film. [Effects of the Invention]

[0020] According to the present invention, it is possible to obtain an anticorrosion coating composition which is capable of forming an anticorrosion coating film having excellent anticorrosion properties, and which has high solidity and excellent coating workability. In particular, the present invention provides an anticorrosion coating composition that has excellent drying properties, is less likely to sag during application, can form a thick film with a single application, and has little adverse effect on the natural environment or painting workers, yet is capable of forming an anticorrosion coating film with excellent corrosion resistance. DETAILED DESCRIPTION OF THE INVENTION

[0021] <Anti-corrosion paint composition kit> The kit for an anticorrosive coating composition according to the present invention (hereinafter also referred to as "the kit") is a kit for an anticorrosive coating composition (hereinafter also referred to as "the composition") having a volatile organic compound (VOC) content of 100 g / L or less, a first agent containing a non-aqueous epoxy compound (A); A second agent containing a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound. A kit containing the above (hereinafter also referred to as "Kit 1"), or a first agent containing a non-aqueous epoxy compound (A); A second agent (a) containing a water-dilutable component (B) containing an amine compound; A second agent (b) containing a non-aqueous component (C) containing an amine compound; This is a kit containing the above (hereinafter also referred to as "Kit 2"). The water-dilutable component (B) containing the amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, and the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound.

[0022] The present composition can be obtained by mixing the first agent and the second agent with the present kit 1, and by mixing the first agent, the second agent a, and the second agent b with the present kit 2. In the case of Kit 1, an nth agent (n is 3 or more) other than Agent 1 and Agent 2 may be used if necessary when obtaining the composition, and in the case of Kit 2, an nth agent (n is 3 or more) other than Agent 1, Agent 2a, and Agent 2b may be used if necessary when obtaining the composition, but it is preferable not to use said nth agent. In other words, Kit 1 is preferably a kit for use with the two-component composition, and Kit 2 is preferably a kit for use with the three-component composition.

[0023] The first agent, second agent, second agent a, second agent b, etc. that make up this kit are usually stored, preserved, transported, etc. in separate containers, and are mixed together immediately before use of the composition.

[0024] The first agent is preferably prepared by the following step 1. The first agent in the present kit 1 and the first agent in the present kit 2 may be different agents, but are preferably the same agents. The second agent is preferably prepared in the following step 2, the second agent 2a is preferably prepared in the following step 2a, and the second agent 2b is preferably prepared in the following step 2b. A mixture of the second agent 2a and the second agent 2b is preferably the second agent.

[0025] <Method for producing anticorrosion coating composition> The production method according to the present invention (hereinafter also referred to as "the present method") is a method for producing the present composition, Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2: preparing a second agent using a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound; Step 3 of mixing the first agent and the second agent; A manufacturing method (hereinafter also referred to as "Method 1") comprising: Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2a: preparing a second agent (2a) using a water-dilutable component (B) containing an amine compound; Step 2b: preparing a second agent b using a non-aqueous component (C) containing an amine compound; a step 3' of mixing the first agent, the second agent a, and the second agent b; This is a production method (hereinafter also referred to as "method 2") comprising the steps of: The water-dilutable component (B) containing the amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, and the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound.

[0026] The method may also include a step of preparing an nth agent (n is 3 or more), in which case step 3 may be a step of mixing the first agent, the second agent, and the nth agent, and step 3' may be a step of mixing the first agent, the second agent, the second agent, and the nth agent.

[0027] <Process 1> The step 1 is a step of preparing a first agent using a non-aqueous epoxy compound (A). Step 1 is not particularly limited as long as a non-aqueous epoxy compound (A) is used. The non-aqueous epoxy compound (A) itself may be used as the first agent (in this case, step 1 is a step using the non-aqueous epoxy compound (A)), or step 1 may be a step of mixing the non-aqueous epoxy compound (A) with other components described below, but the latter is preferred.

[0028] Specifically, step 1 is a step of mixing (kneading) each component to be blended into the first agent, and during this mixing (kneading), each component may be added and mixed at once, or may be added and mixed in multiple batches. The mixing (kneading) can be carried out using a conventionally known device such as a mixer, disperser, or stirrer, and examples of such devices include a disperser, a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. The mixing (kneading) may be carried out while heating or cooling depending on the season, environment, etc.

[0029] Water may or may not be used in step 1. In other words, the first agent may or may not contain water. When the first agent contains water, the content of the water is preferably less than the amount that enables the first agent to become an emulsion of the non-aqueous epoxy compound (A); specifically, the content of water is preferably 35% by mass or less, more preferably 25% by mass or less, relative to 100% by mass of the non-aqueous epoxy compound (A) in the first agent.

[0030] [Non-aqueous epoxy compound (A)] One feature of this method is that a non-aqueous epoxy compound (A) is used as the first agent. The non-aqueous epoxy compound (A) contained in the first agent may be one type or two or more types.

[0031] The term "non-aqueous" in the non-aqueous epoxy compound (A) refers to a state in which the compound is not freely miscible with water and is substantially insoluble in water. Specifically, an epoxy compound is mixed with water at 23°C so that the epoxy compound is 3% by mass, the mixture is thoroughly stirred, and the mixture is allowed to stand at 23°C for 1 hour. If the resulting mixture is not homogeneous and 90% by mass or more of the epoxy compound mixed with water separates, precipitates, or floats, the epoxy compound is considered to be a non-aqueous epoxy compound (A).

[0032] In the mixed solution, if more than 10% by mass of the epoxy compound mixed with water is stably present in water and the mixed solution is maintained in an emulsion state, the epoxy compound is considered to be a water-dilutable epoxy compound.In addition, if more than 10% by mass of the epoxy compound mixed with water is stably present in water and the epoxy compound mixed with water has an average particle size of less than 10 nm as measured with a laser diffraction particle size distribution analyzer (e.g., Mastersizer 3000 (Spectris Co., Ltd.)), the epoxy compound is considered to be a water-soluble epoxy compound.

[0033] The nonaqueous epoxy compound (A) is preferably a liquid epoxy compound that is liquid at room temperature (e.g., 15 to 25° C.) Such a liquid epoxy compound is preferred because it allows the first agent to have a relatively small amount of solvent, and can be easily dispersed uniformly in the first agent even when the agent contains components other than the nonaqueous epoxy compound (A), and also has good reactivity with the water-dilutable component (B) and nonaqueous component (C) described below.

[0034] Examples of the non-aqueous epoxy compound (A) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, novolac type epoxy resins, cresol type epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, epoxidized oil-based epoxy resins, alkyl monoglycidyl ethers, alkyl monoglycidyl esters, alkyl diglycidyl ethers, alkyl diglycidyl esters, alkylphenol monoglycidyl ethers, polyglycol monoglycidyl ethers, and polyglycol diglycidyl ethers. Suitable examples of the alkyl group include alkyl groups having 3 to 15 carbon atoms, and specific examples include alkyl groups such as neopentyl and 2-ethylhexyl groups.

[0035] As the non-aqueous epoxy compound (A), bisphenol A or bisphenol F epoxy resins are preferred, since they can easily form an anticorrosive coating film that has excellent anticorrosion properties and adhesion to the substrate.

[0036] The number average molecular weight of the non-aqueous epoxy compound (A) is preferably 500 or less, more preferably 400 or less, from the viewpoint that an anticorrosion coating composition that is high solid yet has excellent coating workability can be easily obtained.

[0037] The non-aqueous epoxy compound (A) may be a compound synthesized by a conventionally known method, or a commercially available product. Examples of commercially available products that are liquid at room temperature (e.g., 15 to 25°C) include "E-028" (manufactured by Ohtake Meishin Chemical Co., Ltd.), "jER 828" (manufactured by Mitsubishi Chemical Corporation), "Cardura E10P" (manufactured by Hexion), and "ADEKA Resin EP-4901" (manufactured by ADEKA Corporation).

[0038] The amount of the non-aqueous epoxy compound (A) used in step 1 is preferably an amount such that the solid content falls within the following range. The solid content of the non-aqueous epoxy compound (A) is preferably 15 to 35 mass %, more preferably 20 to 30 mass %, relative to 100 mass % of the nonvolatile content of the composition. The solid content of the non-aqueous epoxy compound (A) is preferably 20 to 40 mass %, more preferably 25 to 30 mass %, relative to 100 mass % of the solid content of the first agent. When the content of the non-aqueous epoxy compound (A) is within the above range, a corrosion-resistant coating film that is excellent in corrosion resistance and adhesion to the substrate can be easily formed.

[0039] [Other ingredients] In step 1, if desired, other components such as a silane coupling agent, pigment, pigment dispersant, anti-sagging agent (anti-settling agent, thixotropic agent), flash rust inhibitor, plasticizer, antifoaming agent, dehydrating agent, film-forming aid, and organic solvent may be used within a range that does not impair the effects of the present invention. These other components may each be used alone or in combination of two or more.

[0040] As the other components, commercially available products may be used. In this case, the commercially available products may be available for both solvent-based and water-based systems. When using a commercially available product for solvent-based systems, it is preferable to blend it into the first agent or the second b agent, and when using a commercially available product for water-based systems, it is preferable to blend it into the second agent or the second a agent.

[0041] <Silane coupling agent> By using a silane coupling agent, it is possible to further improve the adhesion of the obtained anticorrosion coating film to the substrate, and also to improve the corrosion resistance, such as water resistance and saltwater resistance, and heat resistance, of the obtained anticorrosion coating film.

[0042] The silane coupling agent is not particularly limited, and any conventionally known compound can be used, but it is preferable that the silane coupling agent is a compound that has at least two functional groups in the same molecule and can contribute to improving adhesion to the substrate and reducing the viscosity of the anticorrosion coating composition.

[0043] The silane coupling agent is, for example, a compound represented by the formula: X-SiMe n Y 3-n " [n is 0 or 1, X is a functional group capable of reacting with an organic substance (e.g., an amino group, a vinyl group, an epoxy group, a mercapto group, a halogeno group, a group in which a hydrocarbon group is partially substituted with any of these groups, or a group in which a hydrocarbon group is partially substituted with an ether bond or the like and is partially substituted with any of these groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or an ethoxy group).] is preferred.

[0044] Among these, an epoxy group-containing silane coupling agent in which X is an epoxy group, a group in which a hydrocarbon group is partly substituted with an epoxy group, or a group in which a hydrocarbon group is partly substituted with an ether bond or the like and partly substituted with an epoxy group is preferred. When producing the present composition containing an epoxy group-containing silane coupling agent, the silane coupling agent is preferably blended in the first agent.

[0045] Commercially available silane coupling agents may be used, such as 3-glycidoxypropyltrimethoxysilane "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.) and "Sila-Ace S-510" (manufactured by JNC Corporation).

[0046] When producing the present composition containing a silane coupling agent, it is preferable to use the silane coupling agent so that the content of the silane coupling agent is preferably 0.1 to 10 mass%, more preferably 0.3 to 5 mass%, relative to 100 mass% of the nonvolatile content of the present composition. When the content of the silane coupling agent is within the above range, the viscosity of the composition can be reduced, thereby improving not only the ease of application but also the adhesion to the substrate, corrosion resistance, and heat resistance of the obtained anticorrosion coating film.

[0047] Pigments The composition may contain a pigment, and preferably does contain a pigment. Examples of the pigment include extender pigments, color pigments, and anti-rust pigments, and may be either organic or inorganic.

[0048] Examples of the extender pigment include talc, mica, (precipitated) barium sulfate, (potassium) feldspar, kaolin, alumina white, bentonite, wollastonite, clay, glass flakes, aluminum flakes, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silica, with talc, mica, silica, (precipitated) barium sulfate, and (potassium) feldspar being particularly preferred.

[0049] When producing the present composition containing an extender pigment, it is preferable to use the extender pigment so that the content of the extender pigment is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, relative to 100 mass % of the nonvolatile content of the present composition.

[0050] Examples of the color pigment include inorganic pigments such as carbon black, titanium dioxide (titanium white), iron oxide (red iron oxide), yellow iron oxide, scaly iron oxide, and ultramarine, and organic pigments such as cyanine blue and cyanine green. Titanium white, carbon black, and red iron oxide are particularly preferred.

[0051] When producing the present composition containing a coloring pigment, it is preferable to use the coloring pigment so that the content of the coloring pigment is preferably 0.1 to 30 mass %, more preferably 1 to 20 mass %, relative to 100 mass % of the nonvolatile content of the present composition.

[0052] Examples of the rust-preventive pigment 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.

[0053] When producing the present composition containing an anti-rust pigment, it is preferable to use the anti-rust pigment so that the content of the anti-rust pigment is preferably 0.5 to 20 mass %, more preferably 1 to 10 mass %, relative to 100 mass % of the non-volatile content of the present composition.

[0054] When producing the present composition containing a pigment, it is preferable to use the pigment so that the pigment volume concentration (PVC) in the present composition is preferably 25 to 45%, more preferably 30 to 40%. When the PVC is within the above range, an anticorrosion coating composition having excellent coating workability can be easily obtained, and an anticorrosion coating film having excellent adhesion to the substrate and excellent corrosion resistance due to stress relaxation can be easily formed.

[0055] The PVC refers to the volume concentration of the total pigment relative to the volume of the nonvolatile content of the composition, and can be calculated using the following formula: PVC [%] = Total volume of all pigments in the composition × 100 / Volume of non-volatile matter in the composition

[0056] The volume of the nonvolatile content of the composition can be calculated from the mass and true density of the nonvolatile content of the composition. The mass and true density of the nonvolatile content may be measured values ​​or values ​​calculated from the raw materials used. The volume of the pigment can be calculated from the mass and true density of the pigment used. The mass and true density of the pigment may be measured values ​​or values ​​calculated from the raw materials used. For example, the volume can be calculated by separating the pigment from other components from the nonvolatile content of the composition and measuring the mass and true density of the separated pigment.

[0057] <Anti-sagging agent> The anti-sagging agent is not particularly limited, but is preferably a material that can suppress sedimentation of pigments and the like in the present composition and improve its storage stability, or a material that can improve the anti-sagging properties of the present composition during or after application.

[0058] As the anti-sagging agent, conventionally known agents can be used, such as stearate salts of Al, Ca, and Zn, lecithin salts, organic clay waxes such as alkylsulfonates, polyethylene wax, amide wax, hydrogenated castor oil wax, a mixture of hydrogenated castor oil wax and amide wax, synthetic finely powdered silica, and oxidized polyethylene wax. Of these, amide wax, synthetic finely powdered silica, oxidized polyethylene wax, and organic clay wax are preferred.

[0059] Commercially available products may be used as such anti-sagging agents. Examples of such commercially available products include "Disparlon 305," "Disparlon 4200-20," "Disparlon 6650," and "Disparlon AQ600" manufactured by Kusumoto Chemical Co., Ltd., "ASA T-250F" manufactured by Ito Oil Milling Co., Ltd., "Flonon RCM-300" manufactured by Kyoeisha Chemical Co., Ltd., "RHEOBYK 420" manufactured by BYK Japan K.K., "Benton SD-2" manufactured by Elementis Specialties, Inc., "Aerosil R972" manufactured by Nippon Aerosil Co., Ltd., and "Crayvallc Optima" manufactured by Arkema Coating Resins Co., Ltd.

[0060] When producing the present composition containing an anti-sagging agent, it is preferable to use the anti-sagging agent so that the solid content of the anti-sagging agent is preferably 0.1 to 10 mass % relative to 100 mass % of the non-volatile content of the present composition.

[0061] <Flash rust inhibitor> The flash rust inhibitor is not particularly limited, but is preferably a material that can suppress rusting caused by the elution of iron ions from the surface of an active steel material or the like during the drying process immediately after application of the composition, and also suppresses flash rust, which is the appearance of such rust on the surface of the coating film.

[0062] Examples of the flash rust inhibitor 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; phosphoric acid derivatives such as alkyl phosphates and polyphosphoric acids; tannates; sulfonic acid metal salts; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), Examples of suitable chelating agents include amine-based chelating agents such as diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; addition reaction products of 4-methyl-γ-oxo-benzenebutanoic acid and N-ethylmorpholine; intercalation compounds obtained by intercalating monoalkylamines, polyamines, quaternary ammonium ions, etc. into layered phosphates such as aluminum dihydrogen tripolyphosphate; and hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds.

[0063] Commercially available products may be used as the flash rust inhibitor, and examples of such commercially available products include "Killesrite W-410" and "Killesrite W-16B" (both manufactured by Chelest Co., Ltd. / organic acid salt type), and "HALOX FLASH-X 150" (manufactured by ICL Advanced Additives-Hammond / nitrite, benzoate type).

[0064] When producing the present composition containing a flash rust inhibitor, it is preferable to use the flash rust inhibitor so that the solid content of the flash rust inhibitor is preferably 0.01 to 5 mass %, more preferably 0.05 to 3 mass %, relative to 100 mass % of the non-volatile content of the present composition.

[0065] <Plasticizer> The present composition may contain a plasticizer in order to improve the flexibility of the resulting anticorrosion coating film. The plasticizer can be a wide variety of known plasticizers, including liquid hydrocarbon resins such as low-boiling fractions obtained by thermal decomposition of naphtha, petroleum resins that are solid at room temperature, xylene resins, coumarone-indene resins, etc. Specific examples include the liquid hydrocarbon resins and flexibility-imparting resins described in JP-A-2006-342360.

[0066] Among these, liquid hydrocarbon resins are preferred, and phenol-modified hydrocarbon resins are more preferred, from the viewpoint of good compatibility with the non-aqueous epoxy compound (A). Examples of the phenol-modified hydrocarbon resin include resins obtained by copolymerizing diolefins, monoolefins, or α-methylstyrene contained in petroleum or coal cracked oil fractions with phenols (phenolic compounds), as described in, for example, JP-A-9-268209 and JP-A-7-196793.

[0067] More specifically, the phenol-modified hydrocarbon resins include resins obtained by reacting phenols with C5 (aliphatic) petroleum resins made from C5 fractions, C9 (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 α-methylstyrene. Among these, resins obtained by addition polymerization of phenols with styrene, vinyltoluene, coumarone, indene, α-methylstyrene, etc., contained in petroleum or coal cracked oil fractions, are preferred.

[0068] The phenol-modified hydrocarbon resin usually has an average molecular weight of 200 to 1000 and a viscosity of 30 to 10,000 mPa·s / 25°C.

[0069] As the liquid hydrocarbon resin, commercially available products may be used, and examples of such commercially available products include "Nesiles EPX-L" and "Nesiles EPX-L2" (both manufactured by NEVCIN / phenol-modified hydrocarbon resins) and "Hirenol PL-1000S" (manufactured by Kolon Industries, Inc. / phenol-modified hydrocarbon resin).

[0070] When producing the present composition containing a plasticizer, it is preferable to use the plasticizer so that the solid content of the plasticizer is preferably 1 to 15 mass %, more preferably 3 to 10 mass %, relative to 100 mass % of the non-volatile content of the present composition. When the content of the plasticizer is within the above range, a corrosion-resistant coating film having excellent crack resistance and the like can be easily formed.

[0071] <Antifoaming agent> The present composition preferably contains an antifoaming agent, since this can suppress the generation of bubbles during the production or application of the composition, or can break up bubbles that have generated in the composition, thereby making it possible to easily form a corrosion-protective coating film having the desired physical properties.

[0072] The defoaming agent may be a commercially available product, and examples of the commercially available product include "BYK-392," "BYK-066N," and "BYK-1790" (all manufactured by BYK Japan K.K.), "TEGO Airex 902W" (manufactured by Evonik), and "Spectrasyn 40" (manufactured by Exxonmobil Chemical Company).

[0073] When producing the present composition containing an antifoaming agent, the antifoaming agent is preferably used so that the solid content of the antifoaming agent is preferably 0.005 to 1 mass %, more preferably 0.01 to 0.5 mass %, relative to 100 mass % of the nonvolatile content of the present composition. When the content of the antifoaming agent is within the above range, the generation of bubbles can be sufficiently suppressed, and a corrosion-protective coating film having the desired physical properties can be easily formed.

[0074] <Film-forming agent> Since the present composition contains water, the composition may freeze in winter, and from the viewpoint of improving film-forming properties at low temperatures and the finished appearance of the obtained corrosion-protective coating film, it is preferable to include a film-forming aid.

[0075] The film-forming aid may be an organic compound having a boiling point of 180°C or higher under normal pressure, which is typically used in aqueous coating compositions. Examples include linear or branched aliphatic alcohols having 5 to 15 carbon atoms; alcohols having an aromatic ring, such as benzyl alcohol; monoethers, such as (poly)ethylene glycol or (poly)propylene glycol; (poly)ethylene glycol ether esters; and (poly)propylene glycol ether esters.

[0076] When producing the present composition containing a coalescent, it is preferable to use the coalescent so that the content of the coalescent is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, relative to 100 mass % of the nonvolatile content of the present composition. When the content of the film-forming aid is within the above range, a corrosion-protective coating film that is excellent in film-forming properties at low temperatures and in appearance can be easily formed.

[0077] <Organic solvent> The organic solvent is not particularly limited as long as it has a boiling point of less than 180°C under normal pressure, and examples thereof 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, isobutyl alcohol, n-butanol, and methoxypropanol, and aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, and methylcyclohexane.

[0078] When producing the present composition containing an organic solvent, it is preferable to use an organic solvent so that the VOC content in the present composition falls within the following range. When preparing a first agent containing an organic solvent, it is preferable to use the organic solvent so that the content of the organic solvent is preferably 12% by mass or less, more preferably 10% by mass or less, relative to 100% by mass of the first agent.

[0079] <Step 2, Step 2a, and Step 2b> Step 2 is a step of preparing a second agent using a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound. Step 2a is a step of preparing a second agent using a water-dilutable component (B) containing an amine compound. Step 2a is not particularly limited as long as a water-dilutable component (B) containing an amine compound is used, and the water-dilutable component (B) containing an amine compound itself may be used as the second agent. In this case, step 2a is a step of using a water-dilutable component (B) containing an amine compound. Step 2b is a step of preparing agent 2b using a non-aqueous component (C) containing an amine compound. Step 2b is not particularly limited as long as a non-aqueous component (C) containing an amine compound is used, and the non-aqueous component (C) containing an amine compound itself may be used as agent 2b. In this case, step 2b is a step of using a non-aqueous component (C) containing an amine compound. In Step 2, Step 2a, and Step 2b, the following other components may also be used.

[0080] Specifically, step 2, step 2a, and step 2b are steps of mixing (kneading) the components to be blended into each agent, and during this mixing (kneading), the components may be added and mixed all at once, or may be added and mixed in multiple batches. The mixing (kneading) can be carried out using a conventionally known device such as a mixer, disperser, or stirrer, and examples of such devices include a disperser, a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. The mixing (kneading) may be carried out while heating or cooling depending on the season, environment, etc.

[0081] In the present invention, the term "water-dilutable component (B) containing an amine compound" refers to a component containing an epoxy-curable amine compound that is emulsified and dispersed in a relatively large amount in a water-containing dispersion medium (hereinafter also referred to as "aqueous medium"). Specifically, a component containing an amine compound is mixed with water to a solids content of 50% by mass at 23°C, or the mixture is volatilized, thoroughly stirred, and allowed to stand at 23°C for 1 hour. When the resulting mixture contains 80% or more by mass of the solids of the components mixed with water and remains in an emulsion state, the component is considered to be the water-dilutable component (B). Note that a component containing an amine compound with a solids content of less than 50% by mass can be adjusted to a solids content of 50% by mass using an evaporator or the like.

[0082] Furthermore, the non-aqueous component (C) containing an amine compound refers to a component containing an epoxy-curing amine compound that is not freely miscible with water, i.e., a component containing an epoxy-curing amine compound that is substantially insoluble in water. Specifically, when a component containing an amine compound is mixed with water so that the solids content is 3% by mass at 23°C, the mixture is thoroughly stirred, and the mixture is allowed to stand at 23°C for 1 hour. If the resulting mixture is not homogeneous and 50% or more by mass of the solids of the component mixed with water separates, precipitates, or floats, the component is considered to be non-aqueous component (C). In the mixed solution, if 90 mass% or more of the solid content of the component mixed with water is stably present in water and the solid content of the component mixed with water is present in a state in which the average particle size of the component measured with a laser diffraction particle size distribution analyzer (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)) is less than 10 nm, then the component is defined as a water-soluble component in this specification. In addition, in this specification, components containing an amine compound other than the water-dilutable component (B), the non-aqueous component (C), and the water-soluble component are referred to as other amine components.

[0083] From the viewpoint of easily forming an anticorrosion coating film that is excellent in anticorrosion properties, coating strength, and drying properties, it is desirable to use the water-dilutable component (B) and the non-aqueous component (C) in amounts such that the reaction ratio calculated by the following formula (2) is preferably 0.3 to 1.5, more preferably 0.4 to 1.2.

[0084] Reactivity ratio = {(amount of solid content of water-dilutable component (B) / active hydrogen equivalent of solid content of water-dilutable component (B)) + (amount of solid content of non-aqueous component (C) / active hydrogen equivalent of solid content of non-aqueous component (C)) + (amount of solid content of component reactive with non-aqueous epoxy compound (A) / functional group equivalent of solid content of component reactive with non-aqueous epoxy compound (A))} / {(amount of solid content of non-aqueous epoxy compound (A) / epoxy equivalent of solid content of non-aqueous epoxy compound (A)) + (amount of solid content of component reactive with water-dilutable component (B) or non-aqueous component (C) / functional group equivalent of solid content of component reactive with water-dilutable component (B) or non-aqueous component (C))} (2)

[0085] Here, examples of the "component reactive with the water-dilutable component (B) or the non-aqueous component (C)" and the "component reactive with the non-aqueous epoxy compound (A)" in the formula (2) include the silane coupling agents. As the silane coupling agent, a silane coupling agent having an amino group or an epoxy group as a reactive group can be used. Therefore, depending on the type of the reactive group, it is necessary to determine whether the silane coupling agent is reactive with the water-dilutable component (B) or the non-aqueous component (C), or whether it is reactive with the non-aqueous epoxy compound (A), and then calculate the reactivity ratio.

[0086] The "functional group equivalent" of each component means the mass (g) per 1 mol of functional group obtained by dividing the mass of 1 mol of that component by the number of moles of the functional group contained therein.

[0087] [Water-dilutable component (B)] The water-dilutable component (B) is not particularly limited as long as it satisfies the above definition and contains an amine compound. The water-dilutable component (B) used in step 2 or step 2a may be one type or two or more types.

[0088] The active hydrogen equivalent of the solid content of the water-dilutable component (B) is preferably 50 to 200, more preferably 60 to 190, from the viewpoint of being able to easily form an anticorrosion coating film that is excellent in curability and anticorrosion properties.

[0089] The amount of water-dilutable component (B) used in step 2 or step 2a is preferably an amount such that the solid content satisfies the above formula (2), and more preferably an amount such that it falls within the following range. The solid content of the water-dilutable component (B) is preferably 4 to 20 mass %, more preferably 5 to 15 mass %, based on 100 mass % of the nonvolatile content of the composition. The solid content of the water-dilutable component (B) is preferably 45 to 85% by mass, and more preferably 50 to 80% by mass, relative to 100% by mass of the solid content of the second part. The solid content of the water-dilutable component (B) is preferably 85 to 100 mass %, more preferably 90 to 100 mass %, relative to 100 mass % of the solid content of the second agent a. When the content of the water-dilutable component (B) is within the above range, a corrosion-preventing coating film having excellent corrosion prevention properties and drying properties can be easily formed.

[0090] Specific examples of the water-dilutable component (B) include a component containing a hydrophilic amine compound obtained by reacting a conventionally known amine compound used as a curing agent for epoxy compounds with a glycidyl ether of a polyalkylene glycol or a polyoxyalkylene amine; a component containing an amine compound having an amide structure obtained by using a fatty acid and an aliphatic amine compound; or a component obtained by forcibly dispersing in water an amine compound that has been given emulsifying ability by neutralizing a conventionally known amine compound used as a curing agent for epoxy compounds with an acid or by mixing with an emulsifier.

[0091] The amine compound used as a curing agent for the epoxy compound is not particularly limited as long as it is an amine compound other than a tertiary amine (an amine compound having only a tertiary amino group), but examples thereof include amine compounds containing two or more amino groups in one molecule, and aliphatic, alicyclic, aromatic, and heterocyclic amine compounds are preferred.

[0092] Examples of the aliphatic amine compounds include alkylene polyamines, polyalkylene polyamines, and alkylamino alkyl amines.

[0093] Examples of the alkylene polyamine include those represented by the formula: "H2N-R 1 -NH2" (R 1 is a divalent hydrocarbon group having 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.

[0094] Examples of the polyalkylene polyamine include those of the formula: "HN-(C m H 2m NH) n Specific examples include compounds represented by the formula (III) (H) (where m is an integer of 1 to 10, and n is an integer of 2 to 10, preferably an integer of 2 to 6), such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0095] Examples of the alkylaminoalkylamine include those represented by the formula: 2 2N-(CH2) p -NH2" (R 2 are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (provided that at least one R 2 is an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 6. Specific examples include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0096] Other aliphatic amine curing agents include, for example, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylenepolyamines (particularly, diethylene glycol bis(3-aminopropyl)ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), menthenediamine (MDA), o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), and 1-[2'-(2''-aminoethylamino)ethyl]piperazine.

[0097] Specific examples of the alicyclic amine curing agent include cyclohexanediamine, diaminodicyclohexylmethane (particularly, 4,4'-methylenebiscyclohexylamine), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0098] Examples of the aromatic amine curing agent include aromatic polyamine compounds having two or more primary amino groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Specific examples of the aromatic amine curing agent include phenylenediamine, naphthalenediamine, 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 diethylmethylbenzenediamine.

[0099] Specific examples of the heterocyclic amine curing agent include 1,4-diazacycloheptane, 1,4-bis(3-aminopropyl)piperazine, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0100] Further examples of the amine compound used as a curing agent for the epoxy compound include modified products of the above-mentioned amine compounds, such as fatty acid modified products such as polyamidoamine, amine adducts with epoxy compounds, Mannich-modified amines (e.g., Mannich-modified amines having a phenol-derived skeleton (phenalkamine, phenalkamide, etc.)), Michael adducts, ketimines, and aldimines. Among these, polyamidoamines, amine adducts with epoxy compounds, and Mannich-modified amines having a phenol-derived skeleton are preferred.

[0101] As the water-dilutable component (B), it is preferable to use a component (B1) containing polyamidoamine b1 in combination with a component (B2) containing at least one amine b2 selected from amine adducts of epoxy compounds and Mannich-modified amines having a phenol-derived skeleton, in order to easily form a corrosion-resistant coating film with superior corrosion resistance. However, in this case, it is not preferable to use two or more components (B3) containing polyamidoamine b1 and amine b2, in order to further enhance the effect. In other words, it is preferable that at least one of components (B1) and (B2) is not component (B3), and it is more preferable that neither is component (B3).

[0102] The water-dilutable component (B) may be one obtained by a conventionally known method or a commercially available product.

[0103] The active hydrogen equivalent of the solid content of the component (B2) is preferably 140 to 200, more preferably 150 to 190, from the viewpoint of being able to easily form an anticorrosion coating film that is excellent in curability and anticorrosion properties.

[0104] When the component (B2) is used in step 2 or step 2a, the amount of the component (B2) used in step 2 or step 2a is preferably an amount such that the solid content satisfies the formula (2), and more preferably an amount such that the solid content falls within the following range: The solid content of component (B2) is preferably 2 to 20 mass %, more preferably 3 to 15 mass %, based on 100 mass % of the nonvolatile content of the composition. The solid content of component (B2) is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, relative to 100 mass % of the solid content of the second part. The solid content of component (B2) is preferably 50 to 80 mass %, more preferably 55 to 75 mass %, relative to 100 mass % of the solid content of the second agent a. When the content of component (B2) is within the above range, a corrosion-preventing coating film that is excellent in corrosion prevention and drying properties can be easily formed.

[0105] Examples of the amine adduct with the epoxy compound include an addition reaction product of an amine compound used as a curing agent for the epoxy compound with an epoxy compound listed in the section for the non-aqueous epoxy compound (A). Examples of the Mannich-modified amine having a phenol-derived skeleton include Mannich-modified amine compounds formed by a Mannich condensation reaction between a phenol such as cardanol, an aldehyde such as formaldehyde, and an amine compound used as a curing agent for the epoxy compound.

[0106] The component (B2) may be one obtained by a conventionally known method or a commercially available product. Examples of commercially available products include "Epilink 701" (manufactured by Evonik) and "Cardolite NX-8401" (manufactured by Cardolite).

[0107] The active hydrogen equivalent of the solid content of the component (B1) is preferably smaller than the active hydrogen equivalent of the solid content of the component (B2), preferably 50 to 130, more preferably 60 to 120, in order to improve the miscibility of the water-dilutable component (B) with the non-aqueous component (C).

[0108] When the component (B1) is used in step 2 or step 2a, the amount of the component (B1) used in step 2 or step 2a is preferably an amount such that the solid content satisfies the formula (2), and more preferably an amount such that the solid content falls within the following range: The solid content of component (B1) is preferably 1 to 10 mass %, more preferably 2 to 5 mass %, based on 100 mass % of the nonvolatile content of the composition. The solid content of component (B1) is preferably 10 to 40 mass %, more preferably 15 to 35 mass %, relative to 100 mass % of the solid content of the second part. The solid content of component (B1) is preferably 15 to 45 mass %, more preferably 20 to 40 mass %, relative to 100 mass % of the solid content of the second agent a. When the content of component (B1) is within the above range, a corrosion-preventing coating film that is excellent in corrosion prevention and drying properties can be easily formed.

[0109] Examples of the component (B1) include compounds formed by a condensation reaction between an amine compound used as a curing agent for the epoxy compound and a fatty acid such as a dimer acid.

[0110] The component (B1) may be one obtained by a conventionally known method or a commercially available product. An example of such a commercially available product is "Jointmide 3506" (manufactured by Yun Teh Industrial Co., Ltd.).

[0111] The water-dilutable component (B) may be a dispersion (amine emulsion) in which an amine compound is dispersed in an aqueous medium, or may be the amine compound itself (100% amine compound).

[0112] The aqueous medium may contain water, and may also contain a medium other than water whose boiling point is lower than 180° C. under normal pressure. Examples of the medium other than water having a boiling point of less than 180°C under normal pressure include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol monopropyl ether. These may be used alone or in combination.

[0113] The amine emulsion can be prepared by emulsifying an amine compound with one or more surfactants to form an emulsion.

[0114] [Non-aqueous component (C)] The non-aqueous component (C) is not particularly limited as long as it is a component that satisfies the above definition and contains an amine compound. Specific examples include amine compounds that satisfy the above definition and are used as curing agents for the epoxy compounds. The non-aqueous component (C) used in step 2 may be one type or two or more types.

[0115] The non-aqueous component (C) preferably has a molecular weight of 3,000 or less, more preferably 2,500 or less, and desirably contains an amine compound having a cyclic structure, and more desirably is an amine compound, from the viewpoints of being able to easily form an anticorrosive coating film with excellent anticorrosive properties and being able to easily obtain an anticorrosive coating composition with a low viscosity.

[0116] The active hydrogen equivalent of the solid content of the non-aqueous component (C) is preferably 30 to 200, more preferably 40 to 150, from the viewpoint of being able to easily form an anticorrosion coating film that is excellent in curability and anticorrosion properties.

[0117] The amount of non-aqueous component (C) used in step 2 is preferably an amount such that the solid content satisfies the above formula (2), and more preferably an amount such that the solid content falls within the following range. The solid content of the non-aqueous component (C) is preferably 1 to 10 mass %, more preferably 2 to 7 mass %, relative to 100 mass % of the nonvolatile content of the composition. The solid content of the non-aqueous component (C) is preferably 15 to 55 mass %, more preferably 20 to 50 mass %, relative to 100 mass % of the solid content of the second part. The solid content of the non-aqueous component (C) is preferably 85 to 100 mass %, more preferably 90 to 100 mass %, relative to 100 mass % of the solid content of the second agent b. When the content of the non-aqueous component (C) is within the above range, a corrosion-preventing coating film that is excellent in corrosion prevention and drying properties can be easily formed.

[0118] The non-aqueous component (C) may be one obtained by a conventionally known method or a commercially available product. Examples of commercially available products include "Ancamine 2280" (manufactured by Evonik) and "ETHACURE 100plus" (manufactured by Albemarle).

[0119] [Other ingredients] The second agent is not particularly limited as long as it contains a water-dilutable component (B) and a non-aqueous component (C), the second agent a is not particularly limited as long as it contains a water-dilutable component (B), and the second agent b is not particularly limited as long as it contains a non-aqueous component (C), and may contain other components, such as water (D), a water-soluble component containing an amine compound, other amine components, pigments, pigment dispersants, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, antifoaming agents, curing accelerators, curing catalysts, and organic solvents, as desired, within the range that does not impair the effects of the present invention. These other components may each be used alone or in combination of two or more. The other components may be conventionally known components, such as pigments, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, defoamers, and organic solvents, which are similar to the components listed in the first agent column.

[0120] <Water (D)> Water may be contained in the water-dilutable component (B). In this case, water (D) other than the water contained in the water-dilutable component (B) may be used. However, from the viewpoints of facilitating the preparation of the present composition and easily obtaining an anticorrosion coating composition that is superior in storage stability and coating workability, it is preferable to further incorporate water (D) in the second part and second a part in addition to the water that may be contained in the water-dilutable component (B). The water (D) is not particularly limited, and tap water or the like may be used, but it is preferable to use ion-exchanged water or the like.

[0121] The content of water in the second part (including water that may be contained in the water-dilutable component (B) etc.) is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass. The water content in the second agent (including water that may be contained in the water-dilutable component (B) and the like) is not particularly limited, but is preferably 25 to 80% by mass, more preferably 30 to 75% by mass. The agent 2b may or may not contain water, but preferably does not contain water. When the agent 2b contains water, the content of the water is not particularly limited, but is preferably 0 to 5 mass %, more preferably 0 to 2 mass %. Furthermore, the content of water in the second agent and the second agent a is preferably 50% by mass or more, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to 100% by mass of the total amount of the dispersion medium and solvent in the second agent and the second agent a, in order to facilitate the production of the desired anticorrosion coating composition.

[0122] <Step 3 and Step 3'> Step 3 is a step of mixing the first agent and the second agent prepared in steps 1 and 2, respectively, and step 3' is a step of mixing the first agent, the second agent a, and the second agent b prepared in steps 1, 2a, and 2b, respectively. The present composition can be produced by mixing (kneading) the first agent, the second agent, and the optionally used n-th agent, or by mixing (kneading) the first agent, the second agent, the second agent, the second agent, and the optionally used n-th agent. The mixing (kneading) can be carried out using a conventionally known device such as a mixer, disperser, or stirrer, and examples of such devices include a disperser, a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. The mixing (kneading) may be carried out while heating or cooling depending on the season, environment, etc.

[0123] <Present composition> The nonvolatile content of the present composition is 70% by volume or more, preferably 72% by volume or more, more preferably 74% by volume or more, and the upper limit is not particularly limited, but is, for example, 85% by volume. The nonvolatile content (vol %) of the composition can be calculated in accordance with ISO3233:1998. A composition having a nonvolatile content within the above range can be said to be a high-solids composition. When the nonvolatile content of the composition is within the above range, it is possible to easily obtain an anticorrosion coating composition that has excellent drying properties, is less likely to sag during application, can form a thick film with a single application, and has excellent application workability.

[0124] The viscosity of the composition measured at 23°C is preferably 7000 mPa·s or less, more preferably 5500 mPa·s or less, and even more preferably 5000 mPa·s or less. There is no particular lower limit, but the viscosity is preferably 1500 mPa·s or more, more preferably 2000 mPa·s or more, and even more preferably 2500 mPa·s or more. According to this method, it is possible to easily obtain an anticorrosion coating composition having a viscosity within the above range and a nonvolatile content within the above range. When the viscosity is within the above range, it is possible to easily obtain an anticorrosion coating composition having excellent handling properties and anti-sagging properties, which is not limited by the coating method, can be applied by various desired coating methods, and has excellent coating workability. Although the present composition may be diluted with a solvent or dispersion medium (e.g., water) before use depending on the coating method, etc., according to the present invention, the viscosity is within the above range even without dilution with a solvent or dispersion medium, so coating is possible without dilution with a solvent or dispersion medium. Each explanation in this specification is about the composition before dilution with a solvent or dispersion medium.

[0125] The VOC content of the present composition is preferably 100 g / L or less, more preferably 80 g / L or less, and even more preferably 60 g / L or less, in order to provide an anticorrosion coating composition that has little impact on the natural environment and the coating work environment.

[0126] The VOC content in the composition can be calculated from the following formula (1) using the specific gravity of the composition, the heating residue rate (mass ratio of non-volatile content), and the moisture content. The specific gravity of the composition, the heating residue rate, and the moisture content may be measured values ​​as described below, or may be values ​​calculated from the raw materials used. VOC content (g / L) = Composition specific gravity x 1000 x (100 - heating residual fraction - moisture percentage) / 100 (1)

[0127] Paint specific gravity (g / cm 3 ): The value calculated by filling a 100 ml density cup with this composition (the composition immediately after mixing Agent 1 and Agent 2 (and Agent n if Agent n is included), or Agent 1, Agent 2a, and Agent 2b (and Agent n if Agent n is included)) at a temperature of 23°C and measuring the mass of the composition.

[0128] Heat residue (mass %): 1±0.1 g of this composition (the composition immediately after mixing Agent 1 and Agent 2 (and Agent n if Agent n is included), or Agent 1, Agent 2a, and Agent 2b (and Agent n if Agent n is included)) is weighed out onto a flat-bottom dish, spread evenly using a wire of known mass, dried at 23°C for 24 hours, and then heated at a heating temperature of 125°C for 1 hour (atmospheric pressure). The mass percentage is calculated by measuring the heat residue (non-volatile content) and the mass of the wire. In addition, among the components (e.g., non-aqueous epoxy compound (A)) that are the raw materials that make up the first and second agents, the components other than the solvent and dispersion medium (e.g., water) that have a boiling point of less than 180°C under normal pressure in the first, second, seconda, and secondb agents are referred to as "solids."

[0129] Moisture content (mass%): The mass percentage of water contained in 100% by mass of the composition, measured by the Karl Fischer method.

[0130] <Anti-corrosion coating, substrate with anti-corrosion coating> The corrosion-protective coating film according to the present invention (hereinafter also referred to as "the coating film") is formed from the kit, and specifically, from the composition obtained from the kit or the composition produced by the method. The present coating film is preferably used as a substrate with a corrosion-protective coating film (hereinafter also referred to as "substrate with the present coating film") comprising a substrate and the present coating film. The substrate with the present coating film is a laminate having the present coating film and a substrate.

[0131] The material of the substrate is not particularly limited, and examples thereof include steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, zinc plating, zinc thermal spraying, etc.), and stainless steel (SUS304, SUS410, etc.). Furthermore, when mild steel (SS400, etc.) is used as the substrate, it is desirable to adjust the surface of the substrate (e.g., adjust the arithmetic mean roughness (Ra) to about 30 to 75 μm) by polishing the surface of the substrate by grit blasting, etc., as necessary. The substrate may be a substrate that has been subjected to pretreatment such as cleaning or blasting to remove rust, dirt, paint (old paint film), and the like adhering to the substrate.

[0132] The substrate is not particularly limited, and can be used without limitation on substrates that require corrosion resistance. However, in terms of the effects of using the present composition being more pronounced, preferred examples include (steel) structures such as ships, marine structures, plants, bridges, tanks, and containers.

[0133] The dry film thickness of the coating is not particularly limited, but is usually 10 to 400 μm, preferably 15 to 300 μm, in order to obtain a coating having sufficient anticorrosion properties.

[0134] The substrate with the coating film of the present invention is a laminate comprising the coating film of the present invention and a substrate, and may be formed with an undercoat coating film (primer coating film) for the purpose of improving adhesion to the substrate and corrosion resistance, an intermediate coating film for the purpose of improving corrosion resistance, and a topcoat coating film that is excellent in weather resistance, aesthetics, etc. Specifically, when the present composition is used as a substitute for a zinc primer, an intermediate coating film and a top coating film may be formed on the present coating film. Examples of the undercoat coating film include coating films formed from various primer compositions such as epoxy resin-based ones. Examples of the intermediate coating film include coating films formed from various intermediate coating compositions such as (meth)acrylic resin-based, epoxy resin-based, and urethane resin-based ones. Examples of the topcoat coating film include coating films formed from various topcoat coating compositions such as (meth)acrylic resin-based, (meth)acrylic silicone resin-based, urethane resin-based, silicone resin-based, and fluororesin-based ones. Furthermore, the composition of the present composition may be changed to form the undercoat coating film, intermediate coating film, and topcoat coating film using the present composition.

[0135] <Manufacturing method for substrate with anticorrosion coating> The method for producing a substrate with a corrosion-protective coating according to the present invention includes the following steps [1] and [2]. Step [1]: A step of applying the present composition obtained from the present kit or the present composition produced by the present method to a substrate. Step [2]: A step of drying the composition applied to the substrate to form the coating film.

[0136] <Process [1]> The coating method in the step [1] is not particularly limited, and examples thereof include conventionally known methods such as spray coating such as airless spray coating and air spray coating, brush coating, roller coating, etc. Among these, spray coating is preferred because it allows for easy coating of large-area substrates such as the structure. In such coating, it is preferable to coat the resulting coating so that the dry film thickness falls within the above range.

[0137] The spray coating conditions may be adjusted as appropriate depending on the desired dry film thickness. For example, in the case of airless spray coating, it is preferable that the primary (air) pressure is about 0.3 to 0.6 MPa, the secondary (paint) pressure is about 10 to 15 MPa, and the gun movement speed is about 50 to 120 cm / sec.

[0138] The coating is preferably carried out so that the dry thickness of the main coating film formed in step [2] falls within the above range. In this case, the main coating film of the desired thickness may be formed by one coating (single coating), or by two or more coatings (two or more coatings). Note that two coats refers to performing steps [1] and [2], and then performing step [1] on the main coating film obtained in step [2].

[0139] When applying the composition to a substrate, it is preferable to treat the surface of the substrate as needed (for example, by blasting (ISO8501-1 Sa2 1 / 2) or degreasing to remove oil and dust) in order to remove rust, oil, moisture, dust, salt, etc. from the substrate and to improve the adhesion of the resulting coating to the substrate. The substrate may also be coated with a shop primer or the like for primary rust prevention.

[0140] <Process [2]> The drying conditions in step [2] are not particularly limited and may be set appropriately depending on the coating film formation method, the type of substrate, the intended use, the coating environment, etc., but the drying temperature is usually 5 to 35°C in the case of drying at room temperature, and usually 30 to less than 100°C, more preferably 40 to 80°C, in the case of forced drying using a hot air dryer or the like. The present composition can be dried and cured even by drying at room temperature. The drying time varies depending on the drying method of the coating film, and is, for example, about 1 to 7 days when drying at room temperature, and about 5 to 60 minutes when forced drying is used. [Example]

[0141] The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

[0142] [Example 1] As shown in Table 1, 28 parts by weight of non-aqueous epoxy compound (Note 1), 4 parts by weight of methoxypropanol, 4 parts by weight of benzyl alcohol, 3 parts by weight of red iron oxide (Note 4), 36.8 parts by weight of potassium feldspar (Note 5), 10 parts by weight of talc (Note 6), 12 parts by weight of barium sulfate (Note 7), 1 part by weight of silane coupling agent (Note 8), 0.9 parts by weight of anti-sagging agent (Note 9), and 0.3 parts by weight of anti-foaming agent (Note 10) were placed in a container and stirred at room temperature (23°C) using a high-speed disperser until uniform, then dispersed at 55-60°C for 30 minutes.The mixture was then cooled to below 30°C to prepare the first part.

[0143] In addition, 55 parts by mass of a water-dilutable component containing an amine compound (Note 11), 15 parts by mass of a non-aqueous component containing an amine compound (Note 15), and 30 parts by mass of ion-exchanged water were placed in a separate container and stirred using a high-speed disperser until uniform, to prepare a second agent.

[0144] The prepared first and second parts were mixed in the mixing ratio (mass ratio) shown in Table 1 before application to prepare anticorrosion coating compositions. The description of each component listed in Table 1 is shown in Table 2.

[0145] [Examples 2 to 9 and Comparative Examples 1 to 8] Anticorrosion coating compositions were prepared in the same manner as in Example 1, except that the components shown in Table 1 were used in the amounts (parts by mass) shown in Table 1.

[0146] The viscosity of each anticorrosion coating composition at 23° C. immediately after preparation in the examples and comparative examples was measured using a Rion viscometer (VT-04F, manufactured by Rion Co., Ltd.). The results are shown in Table 1.

[0147] [Table 1]

[0148] [Table 2]

[0149] [Preparation of substrate (test plate) with anticorrosion coating] An SS400 sandblasted steel plate (arithmetic mean roughness (Ra): 30 to 75 μm) measuring 150 mm × 70 mm × 2.3 mm (thickness) was prepared. The anticorrosion coating composition prepared as described above was applied to the surface of this steel plate using an air spray to a dry film thickness of 70 μm. The anticorrosion coating composition applied to the steel plate was then dried at 60°C for 40 minutes, after which a water-based acrylic resin top coat paint (EKOMATE FINISH (manufactured by Chugoku Toryo Co., Ltd.)) was applied using an air spray to a dry film thickness of 40 μm. The applied water-based acrylic resin top coat paint was then dried at 60°C for 30 minutes and then dried at 23°C for 7 days to produce test plate 1.

[0150] The anticorrosion coating composition prepared as described above was also applied to the surface of the same steel plate as that used for test plate 1 using an air spray so as to give a dry film thickness of 80 μm. The anticorrosion coating composition applied to the steel plate was then dried at 60°C for 30 minutes, and then dried at 23°C for 7 days to produce test plate 2.

[0151] <Salt spray test> In accordance with JIS K 5600-7-1:1999, a salt spray test was conducted by holding Test Plate 1 and Test Plate 2 in a salt spray tester under salt spray conditions of 5% by mass salt water, 35°C temperature, and 98% relative humidity for 400 hours, and evaluating the corrosion resistance according to the evaluation criteria described below. The results are shown in Table 3. Regarding corrosion resistance, if the salt spray test score is 3 or higher, it can be said that there is no problem in practical use. (Evaluation criteria) 5: No rust or blisters 4: No blisters have occurred, but the area of ​​rust on the surface of the substrate beneath the coating is less than 0.03% of the entire surface of the substrate beneath the coating. 3: A very small amount of small blisters have occurred, and the area of ​​rust on the surface of the substrate under the paint film is 0.03% or more but less than 0.1% of the entire surface of the substrate under the paint film. 2: Blisters have occurred, and the area of ​​rust on the surface of the substrate under the coating is 0.1% or more but less than 0.3% of the entire surface of the substrate under the coating. 1: Blisters have occurred and the area of ​​rust on the surface of the substrate under the coating is 0.3% or more of the entire surface of the substrate under the coating.

[0152] <Combined cycle test> A 25-cycle test was performed in accordance with ASTM D2803 using the test panels 1 and 2. The appearance of the test panels after the test was evaluated according to the same evaluation criteria as in the salt spray test. The results are shown in Table 3. Regarding corrosion resistance, if the combined cycle test score is 3 or higher, it can be said that there is no problem in practical use.

[0153] [Table 3]

Claims

1. Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2: preparing a second agent using a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound; Step 3 of mixing the first agent and the second agent; Including, the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A method for producing an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

2. Step 1: preparing a first agent using a non-aqueous epoxy compound (A); Step 2a: preparing a second agent (a) using a water-dilutable component (B) containing an amine compound; Step 2b: preparing a second agent b using a non-aqueous component (C) containing an amine compound; a step 3' of mixing the first agent, the second agent a, and the second agent b; Including, the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A method for producing an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

3. 3. The method for producing an anticorrosion coating composition according to claim 1, wherein the viscosity of the anticorrosion coating composition measured at 23°C is 7,000 mPa·s or less.

4. The method for producing an anticorrosion coating composition according to any one of claims 1 to 3, wherein the anticorrosion coating composition further contains a pigment, and the pigment volume concentration (PVC) in the anticorrosion coating composition is 25 to 45%.

5. The method for producing an anticorrosion coating composition according to any one of claims 1 to 4, wherein the non-aqueous amine compound is an amine compound having a cyclic structure and a molecular weight of 3,000 or less.

6. The method for producing an anticorrosion coating composition according to any one of claims 1 to 5, wherein the first agent further contains a silane coupling agent.

7. a first agent containing a non-aqueous epoxy compound (A); a second agent containing a water-dilutable component (B) containing an amine compound and a non-aqueous component (C) containing an amine compound; Contains the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A kit for an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

8. a first agent containing a non-aqueous epoxy compound (A); a second agent (a) containing a water-dilutable component (B) containing an amine compound; a second agent b containing a non-aqueous component (C) containing an amine compound; Contains the water-dilutable component (B) containing an amine compound is a dispersion in which an amine compound other than a tertiary amine is dispersed in an aqueous medium, The non-aqueous component (C) containing an amine compound is a non-aqueous amine compound. A kit for an anticorrosion coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

9. A corrosion-preventive coating film formed from the corrosion-preventive coating composition kit according to claim 7 or 8.

10. A substrate with a corrosion-protective coating, comprising a substrate and the corrosion-protective coating according to claim 9.

11. A method for producing a substrate with a corrosion-resistant coating, comprising the following steps [1] and [2]: [1] A step of coating a substrate with an anticorrosive coating composition produced by the production method according to any one of claims 1 to 6, or an anticorrosive coating composition obtained from the anticorrosive coating composition kit according to claim 7 or 8. [2] A step of drying the anticorrosion coating composition applied to the substrate to form an anticorrosion coating film.

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