Method for producing anticorrosive paint 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 anticorrosive coating composition, a kit for an anticorrosive coating composition, an anticorrosive coating film, a substrate with an anticorrosive coating film, and a method for producing a substrate with an anticorrosive coating film. [Background technology]

[0002] Solvent-based epoxy resin anticorrosive coatings are applied to the substrates of ships, offshore structures, plants, bridges, and onshore tanks, with the aim of ensuring their long-term use.

[0003] In recent years, with the strengthening of regulations on the emission of organic solvents aimed at considering the natural environment and the painting work environment, there has been progress in reducing the VOC (volatile organic compound) content of solvent-based paints as described above. One method of reducing VOCs is to make paints water-based. Water-based anticorrosive paints mainly use water as a solvent and dispersion medium, so it is possible to significantly reduce VOCs compared to conventional solvent-based paints while maintaining an appropriate paint viscosity.

[0004] As examples of the water-based anticorrosive coatings mentioned above, Patent Document 1 discloses an aqueous epoxy resin composition containing an epoxy resin emulsion and a water-soluble amine curing agent, and Patent Document 2 discloses an aqueous 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 Publication No. 2008-247958 [Patent Document 2] Japanese Patent Publication No. 2009-221256 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the corrosion-resistant coatings formed from conventional corrosion-resistant paints described in Patent Documents 1 and 2, etc., do not have sufficient corrosion resistance, and there was room for improvement in this respect.

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

[0008] The present invention has been made in view of the above, and aims to provide a method for producing a corrosion-resistant coating composition that is highly solid yet has excellent paintability, capable of forming a corrosion-resistant coating film with excellent corrosion resistance, and a kit for the corrosion-resistant coating composition. [Means for solving the problem]

[0009] As a result of the inventor's diligent efforts to find a way to solve the aforementioned problems, the inventor discovered that the problems can be solved by the following configuration example, and thus completed the present invention. The following are examples of the configuration of the present invention.

[0010] <1> Step 1 involves preparing the first agent using a non-aqueous epoxy compound (A), Step 2 involves 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 involves mixing the first agent and the second agent. Includes, The aqueous 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. The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound. A method for producing a corrosion-preventive coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0011] <2> Step 1 of preparing the first agent using a non-aqueous epoxy compound (A); <3> Step 2a of preparing the second agent a using a water-dilutable component (B) containing an amine compound; <4> Step 2b of preparing the second agent b using a non-aqueous component (C) containing an amine compound; <5> Step 3' of mixing the first agent, the second agent a, and the second agent b; and 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, the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A method for producing a corrosion-resistant paint composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0012] <3> The method for producing a corrosion-resistant paint composition according to <1> or <2>, wherein the viscosity of the corrosion-resistant paint composition measured at 23°C is 7,000 mPa·s or less.

[0013] <4> The method for producing a corrosion-resistant paint composition according to any one of <1> to <3>, wherein the corrosion-resistant paint composition further contains a pigment, and the pigment volume concentration (PVC) in the corrosion-resistant paint composition is 25 to 45%.

[0014] <5> The method for producing a corrosion-resistant paint composition according to any one of <1> to <4>, wherein the non-aqueous amine compound is an amine compound having a cyclic structure with a molecular weight of 3,000 or less.

[0015] <6> The method for producing a corrosion-resistant paint composition according to any one of <1> to <5>, wherein the first agent further contains a silane coupling agent.

[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 and 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, The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A kit for a corrosion preventive paint 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 water-dilutable component (B) containing an amine compound, A second agent b containing a non-aqueous component (C) containing an amine compound and containing, 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, The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A kit for a corrosion preventive paint composition having a volatile organic compound (VOC) content of 100 g / L or less.

[0018] <9> A corrosion preventive coating film formed from the kit for a corrosion preventive paint composition according to <7> or <8>. <10> A substrate with a corrosion preventive coating film including a substrate and the corrosion preventive coating film according to <9>.

[0019] <11> A method for producing a substrate with a corrosion preventive coating film, including the following steps [1] and [2]. [1] A step of coating a substrate with a corrosion preventive paint composition produced by the production method according to any one of <1> to <6>, or a corrosion preventive paint composition obtained from the kit for a corrosion preventive paint composition according to <7> or <8> [2] A step of drying the corrosion preventive paint composition applied on the substrate to form a corrosion preventive coating film [Advantages of the Invention]

[0020] According to the present invention, it is possible to obtain a corrosion preventive paint composition that forms a corrosion preventive coating film excellent in corrosion prevention performance, is high solid, and has excellent coating workability. In particular, according to the present invention, it is possible to obtain a corrosion-resistant coating composition that has excellent drying properties, is less prone to dripping during application, can form a thick film in a single application, and has minimal adverse effects on the natural environment and painters, while still being able to form a corrosion-resistant coating film with excellent corrosion resistance. [Modes for carrying out the invention]

[0021] ≪Corrosion-preventive coating composition kit≫ The anticorrosion coating composition kit according to the present invention (hereinafter also referred to as "this kit") is a kit for an anticorrosion coating composition (hereinafter also referred to as "this composition") having a volatile organic compound (VOC) content of 100 g / L or less. The first component contains a non-aqueous epoxy compound (A), A second agent comprising a water-dilutable component (B) containing an amine compound, and a non-aqueous component (C) containing an amine compound. A kit containing (hereinafter also referred to as "Kit 1"), or The first component contains a non-aqueous epoxy compound (A), Agent 2a contains a water-dilutable component (B) containing an amine compound, The second b agent contains a non-aqueous component (C) containing an amine compound and This is a kit containing (hereinafter also referred to as "Kit 2"). Furthermore, the aqueous 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] This composition can be obtained by mixing the first agent and the second agent in Kit 1, and by mixing the first agent, the second a agent, and the second b agent in Kit 2. In the case of Kit 1, when obtaining the composition, an nth agent (n is 3 or more) other than the first and second agents may be used as needed, and in the case of Kit 2, when obtaining the composition, an nth agent (n is 3 or more) other than the first, seconda, and secondb agents may be used as needed, but it is preferable not to use the nth agent. In other words, Kit 1 is preferably a kit for a two-component composition, and Kit 2 is preferably a kit for a three-component composition.

[0023] The components of this kit, such as the first agent, second agent, seconda agent, and secondb agent, are usually stored, transported, etc., in separate containers, and mixed immediately before use.

[0024] The first agent is preferably prepared in step 1 below. Note that the first agent in kit 1 and the first agent in kit 2 may be different agents, but it is preferable that they be the same agent. The second agent is preferably prepared in step 2 below, the seconda agent is preferably prepared in step 2a below, and the secondb agent is preferably prepared in step 2b below. It is preferable that the second agent is a mixture of the seconda agent and the secondb agent.

[0025] ≪Method for producing anticorrosive paint composition≫ The manufacturing method according to the present invention (hereinafter also referred to as "this method") is a method for manufacturing the composition, Step 1 involves preparing the first agent using a non-aqueous epoxy compound (A), Step 2 involves 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 involves mixing the first agent and the second agent. A manufacturing method including (hereinafter also referred to as "Method 1"), or Step 1 involves preparing the first agent using a non-aqueous epoxy compound (A), Step 2a involves preparing agent 2a using a water-dilutable component (B) containing an amine compound, Step 2b involves preparing agent 2b using a non-aqueous component (C) containing an amine compound, Step 3' involves mixing the first agent, the second a agent, and the second b agent. This is a manufacturing method that includes (hereinafter also referred to as "Method 2"). Furthermore, the aqueous 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] Furthermore, this method may include a step of preparing an nth agent (where 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 seconda agent, the secondb agent and the nth agent.

[0027] <Process 1> Step 1 is a step of preparing the 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, and the non-aqueous epoxy compound (A) itself may be used as the first agent (in this case, Step 1 is the step of using the non-aqueous epoxy compound (A)), or it may be the step of mixing the non-aqueous epoxy compound (A) with the other components listed below, but the latter is preferred.

[0028] Step 1 is specifically the step of mixing (kneading) each component to be included in the first agent. During this mixing (kneading), each component may be added and mixed all at once, or added and mixed in multiple stages. During the mixing (kneading) process, conventionally known devices such as mixers, dispersers, and agitators can be used. Examples of such devices include dispersers, mixing / dispersing mills, mortar mixers, rolls, paint shakers, and homogenizers. Furthermore, the mixing (kneading) process may be carried out while heating or cooling the mixture, depending on the season, environment, etc.

[0029] In step 1, water may or may not be used. In other words, the first agent may or may not contain water. If the first agent contains water, the amount of water is preferably less than the amount that would allow the first agent to become an emulsion of the non-aqueous epoxy compound (A). Specifically, the amount of water is preferably 35% by mass or less, and 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 characteristic of this method is that it uses a non-aqueous epoxy compound (A) 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] In the context of non-aqueous epoxy compounds (A), "non-aqueous" means a state in which the substance is not freely miscible with water and is substantially insoluble in water. Specifically, if, at 23°C, an epoxy compound and water are mixed so that the epoxy compound makes up 3% by mass, the mixture is thoroughly stirred, and the mixture is left to stand at 23°C for 1 hour, and the resulting mixture is not homogeneous, and 90% or more by mass of the epoxy compound mixed with water is separated, precipitated, or suspended, then the epoxy compound is designated as non-aqueous epoxy compound (A).

[0032] Furthermore, if, in the aforementioned mixture, more than 10% by mass of the epoxy compound mixed with water is stably present in the water, and the mixture is maintained in an emulsion state, then the epoxy compound shall be a water-dilutable epoxy compound. Also, if, in the aforementioned mixture, more than 10% by mass of the epoxy compound mixed with water is stably present in the water, and the epoxy compound mixed with water is present in a state where the average particle size measured by a laser diffraction particle size distribution analyzer (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)) is less than 10 nm, then the epoxy compound shall be a water-soluble epoxy compound.

[0033] The non-aqueous epoxy compound (A) is preferably a liquid epoxy compound that is liquid at room temperature (e.g., 15-25°C). Such a liquid epoxy compound is preferred because it is easy to uniformly disperse it in the first agent even if the first agent is an agent with a relatively small amount of solvent and contains components other than the non-aqueous epoxy compound (A), and it also has good reactivity with the water-dilutable component (B) and the non-aqueous component (C) described later.

[0034] Examples of non-aqueous epoxy compounds (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, epoxidized oil-based epoxy resin, alkyl monoglycidyl ether, alkyl monoglycidyl ester, alkyl diglycidyl ether, alkyl diglycidyl ester, alkylphenol monoglycidyl ether, polyglycol monoglycidyl ether, and polyglycol diglycidyl ether. Preferred examples of the alkyl group include alkyl groups having 3 to 15 carbon atoms, specifically, alkyl groups such as neopentyl group and 2-ethylhexyl group.

[0035] As the non-aqueous epoxy compound (A), bisphenol A type or bisphenol F type epoxy resin is preferred because it can easily form a corrosion-resistant coating with excellent corrosion resistance 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 a corrosion-resistant coating composition with excellent paintability despite being high-solid 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 may be used. Examples of commercially available products that are liquid at room temperature (e.g., 15-25°C) include "E-028" (manufactured by Ohtake Meishin Chemical Co., Ltd.), "jER 828" (manufactured by Mitsubishi Chemical Corporation), "Cardura E10P" (manufactured by Hexion Corporation), and "Adeka Resin EP-4901" (manufactured by ADEKA Corporation).

[0038] The amount of non-aqueous epoxy compound (A) used in step 1 is preferably such that its solid content falls within the following range. The solid content of the non-aqueous epoxy compound (A) is preferably 15 to 35% by mass, more preferably 20 to 30% by mass, based on 100% by mass of the non-volatile content of the composition. Furthermore, the solid content of the non-aqueous epoxy compound (A) is preferably 20 to 40% by mass, more preferably 25 to 30% by mass, relative to 100% by 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 with excellent corrosion resistance and adhesion to the substrate can be easily formed.

[0039] [Other ingredients] In step 1, other components such as silane coupling agents, pigments, pigment dispersants, anti-sagging agents (settling inhibitors, throttling agents), flash rust inhibitors, plasticizers, defoaming agents, dehydrating agents, film-forming aids, and organic solvents may be used as desired, provided that they do not impair the effects of the present invention. These other components may be used individually or in combination of two or more types.

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

[0041] <Silane coupling agent> By using a silane coupling agent, not only can the adhesion of the resulting anticorrosive coating to the substrate be further improved, but the corrosion resistance, saltwater resistance, and other corrosion resistance properties, as well as heat resistance, of the resulting anticorrosive coating can also be improved.

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

[0043] Silane coupling agents include, for example, those with the formula: "X-SiMe n Y 3-n It is preferable that the compound is represented by "[n is 0 or 1, X is a functional group that can react with organic matter (e.g., amino group, vinyl group, epoxy group, mercapto group, halogeno group, a group in which part of a hydrocarbon group is substituted with one of these groups, or a group in which part of a hydrocarbon group is substituted with an ether bond, etc., and part of that group is substituted with one of these groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., alkoxy groups such as methoxy and ethoxy groups)].

[0044] Among these, it is preferable that the epoxy group-containing silane coupling agent is one in which X is an epoxy group, a group in which part of a hydrocarbon group is substituted with an epoxy group, or a group in which part of a hydrocarbon group is substituted with an ether bond or the like and part of that group is substituted with an epoxy group. When preparing this composition containing an epoxy group-containing silane coupling agent, it is preferable to incorporate the silane coupling agent into the first agent.

[0045] Commercially available silane coupling agents may be used, and examples of such commercially available products include "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.), which is 3-glycidoxypropyltrimethoxysilane, and "Sylace 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 such that its content is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, based on 100% by mass of the non-volatile content of the present composition. When the silane coupling agent content is within the aforementioned range, the viscosity of the composition can be reduced, which not only improves the paintability but also enhances the adhesion, corrosion resistance, and heat resistance of the resulting anticorrosive coating to the substrate.

[0047] <Pigments> This composition may contain a pigment, and it is preferable that it contains a pigment. Examples of such pigments include extender pigments, coloring pigments, and rust-preventive pigments, and they may be organic or inorganic.

[0048] Examples of the aforementioned extender pigments include talc, mica, (precipitating) barium sulfate, (potassium) feldspar, kaolin, alumina white, bentonite, wollastonite, clay, glass flakes, aluminum flakes, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silica. Talc, mica, silica, (precipitating) barium sulfate, and (potassium) feldspar are particularly preferred.

[0049] When producing this composition containing an extender pigment, it is preferable to use the extender pigment such that its content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, relative to 100% by mass of the non-volatile content of this composition.

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

[0051] When producing this composition containing a coloring pigment, it is preferable to use the coloring pigment such that its content is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on 100% by mass of the non-volatile content of this composition.

[0052] Examples of the 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 complex oxides.

[0053] When producing this composition containing a rust-preventive pigment, it is preferable to use the rust-preventive pigment such that its content is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the non-volatile content of the composition.

[0054] When producing this composition containing a pigment, it is preferable to use the pigment such that the pigment volume concentration (PVC) in the composition is preferably 25-45%, more preferably 30-40%. When the PVC is within the aforementioned range, a corrosion-resistant coating composition with excellent paintability can be easily obtained, and a corrosion-resistant coating film with excellent adhesion to the substrate due to stress relaxation and corrosion resistance can be easily formed.

[0055] The aforementioned PVC refers to the total volume concentration of the pigments relative to the volume of the non-volatile components of this composition. Specifically, PVC can be calculated using the following formula. PVC[%] = Total volume of all pigments in this composition × 100 / Volume of non-volatile components in this 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, it can be calculated by separating the pigment from other components from the non-volatile content of the composition and measuring the mass and true density of the separated pigment.

[0057] <Drip stopper> The aforementioned anti-sagging agent is not particularly limited, but it is preferable that it is a material that can suppress the settling of pigments and the like in the composition and improve its storage stability, or a material that can improve the anti-sagging properties of the composition during or after painting.

[0058] As the anti-sagging agent, conventionally known substances can be used, such as organic clay waxes including stearate salts, lecithin salts, and alkyl sulfonates of Al, Ca, and Zn; polyethylene wax; amide wax; hydrogenated castor oil wax; mixtures of hydrogenated castor oil wax and amide wax; synthetic fine silica; and oxidized polyethylene wax. Among these, amide wax, synthetic fine silica, oxidized polyethylene wax, and organic clay wax are preferred.

[0059] Commercially available anti-slip agents may be used, and examples of such commercially available products include "Disparlon 305," "Disparlon 4200-20," "Disparlon 6650," and "Disparlon AQ600" from Kusumoto Chemical Co., Ltd., "ASA T-250F" from Ito Seiyu Co., Ltd., "Flonon RCM-300" from Kyoeisha Chemical Co., Ltd., "RHEOBYK 420" from Big Chemie Japan Co., Ltd., "Benton SD-2" from Elementis Specialties, Inc., "Aerosil R972" from Nippon Aerosil Co., Ltd., and "Crayvallc Optima" from Arkema Coating Resins Co., Ltd.

[0060] When manufacturing this composition containing an anti-dripping agent, it is preferable to use the anti-dripping agent such that the solid content of the anti-dripping agent is preferably 0.1 to 10% by mass relative to 100% by mass of the non-volatile content of this composition.

[0061] <Flash last suppressant> The flash rust inhibitor is not particularly limited, but it is preferable that it is a material that can suppress rust formation caused by the elution of iron ions from the surface of the steel material, etc., and flash rust, which occurs when the composition is applied to an active steel material surface, etc., from immediately after application to the drying process, and when the rust etc. rises to the surface of the coating film.

[0062] Examples of the aforementioned flash last 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; phytes such as sodium phytate and potassium phytate; fatty acid salts such as sebaciate and dodecanoic acid; phosphoric acid derivatives such as alkyl phosphate and polyphosphate; tannates; metal sulfonates; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), Examples of chelating agents include amine-based chelating agents such as diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their alkali metal salts; addition reaction products of 4-methyl-γ-oxobenzenebutanoic 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 last inhibitors, and examples of such commercial products include "Kireslight W-410" and "Kireslight W-16B" (both manufactured by Kirest Co., Ltd. / organic acid salt type) and "HALOX FLASH-X 150" (manufactured by ICL Advanced Additives-Hammond / nitrite and benzoate type).

[0064] When producing the present composition containing a flash last suppressant, it is preferable to use the flash last suppressant such that the solid content of the flash last suppressant is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on 100% by mass of the non-volatile content of the present composition.

[0065] <Plasticizer> This composition may contain a plasticizer, for example, to improve the flexibility of the resulting anticorrosive coating. The aforementioned plasticizers can be a wide range of conventionally known materials, including liquid hydrocarbon resins such as low-boiling fractions obtained by thermal decomposition of naphtha, solid petroleum resins at room temperature, xylene resins, coumarone indene resins, and the like. Specifically, examples include the liquid hydrocarbon resins and flexibility-imparting resins described in Japanese Patent Application Publication No. 2006-342360.

[0066] Among these, liquid hydrocarbon resins are preferred, and phenol-modified hydrocarbon resins are more preferred, due to their good compatibility with the non-aqueous epoxy compound (A). Examples of the phenol-modified hydrocarbon resins include resins obtained by copolymerizing diolefins, monoolefins, or α-methylstyrene contained in the cracked oil fractions of petroleum and coal with phenols (phenol compounds), as described in Japanese Patent Publication No. 9-268209, Japanese Patent Publication No. 7-196793, etc.

[0067] More specifically, the 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 the C5 fraction; α-methylstyrene; and resins obtained by reacting these with phenols. Among these, resins obtained by addition polymerization of styrene, vinyltoluene, coumarone, indene, and α-methylstyrene, which are contained in the cracked oil fractions of petroleum and coal, with phenols are preferred.

[0068] The average molecular weight of the phenol-modified hydrocarbon resin is typically 200 to 1000, and its viscosity is typically 30 to 10,000 mPa·s / 25℃.

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

[0070] When producing this composition containing a plasticizer, it is preferable to use the plasticizer such that the solid content of the plasticizer is preferably 1 to 15% by mass, more preferably 3 to 10% by mass, based on 100% by mass of the nonvolatile content of this composition. When the plasticizer content is within the aforementioned range, a corrosion-resistant coating with superior crack resistance and other properties can be easily formed.

[0071] <Antifoaming agent> It is preferable that the composition contains an antifoaming agent, as this can suppress the generation of bubbles during the manufacturing or application of the composition, or break bubbles that have been generated in the composition, and easily form a corrosion-resistant coating with desired physical properties.

[0072] Commercially available products may be used as the antifoaming agent, and examples of such products include "BYK-392", "BYK-066N", "BYK-1790" (all manufactured by Bic Chemie Japan Co., Ltd.), "TEGO Airex 902W" (manufactured by Evonik), and "Spectrasyn 40" (manufactured by Exxonmobil Chemical Company).

[0073] When manufacturing this composition containing an antifoaming agent, it is preferable to use the antifoaming agent such that the solid content of the antifoaming agent is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on 100% by mass of the nonvolatile content of this composition. When the antifoaming agent content is within the aforementioned range, foam generation can be sufficiently suppressed, and a corrosion-resistant coating with the desired physical properties can be easily formed.

[0074] <Membrane-forming aid> Because this composition contains water, it may freeze in winter. Therefore, it is preferable to include a film-forming aid to improve film-forming properties at low temperatures and the finished appearance of the resulting anticorrosive coating.

[0075] As the aforementioned film-forming aid, organic compounds with a boiling point of 180°C or higher under normal pressure, which are commonly used in water-based paint compositions, can be used. Examples include linear or branched aliphatic alcohols having 5 to 15 carbon atoms; alcohols having aromatic rings 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 film-forming aid, it is preferable to use the film-forming aid in such a way that its content is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, relative to 100% by mass of the non-volatile content of the present composition. When the content of the film-forming aid is within the aforementioned range, a corrosion-resistant coating with excellent film-forming properties and appearance at low temperatures can be easily formed.

[0077] <Organic solvents> The aforementioned organic solvent is not particularly limited as long as it is an organic solvent with a boiling point of less than 180°C at normal pressure, but 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, 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 this composition containing an organic solvent, it is preferable to use an organic solvent such that the VOC content in the composition falls within the following range. When preparing the first agent containing an organic solvent, it is preferable to use the organic solvent such that its content is preferably 12% by mass or less, and more preferably 10% by mass or less, relative to 100% by mass of the first agent.

[0079] <Process 2, Process 2a, and Process 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 agent 2a 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 agent 2a, in which 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 the amine compound itself may be used as agent 2b, in which case step 2b is a step of using a non-aqueous component (C) containing an amine compound. In steps 2, 2a, and 2b, the following other components may also be used.

[0080] Steps 2, 2a, and 2b are specifically steps in which the components to be incorporated into each preparation are mixed (kneaded). During this mixing (kneading), the components may be added and mixed all at once, or they may be added and mixed in multiple steps. During the mixing (kneading) process, conventionally known devices such as mixers, dispersers, and agitators can be used. Examples of such devices include dispersers, mixing / dispersing mills, mortar mixers, rolls, paint shakers, and homogenizers. Furthermore, the mixing (kneading) process may be carried out while heating or cooling the mixture, depending on the season, environment, etc.

[0081] In this invention, the 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 dispersion medium containing water (hereinafter also referred to as "aqueous medium"). Specifically, if a mixture is obtained by mixing a component containing an amine compound with water at 23°C so that the solid content is 50% by mass, or by volatilizing the solvent / dispersion medium, stirring thoroughly, and letting it stand at 23°C for 1 hour, and if 80% or more of the solid content of the component mixed with water is stably present in the water, and the mixture is maintained in an emulsion state, then the component is defined as water-dilutable component (B). Note that components containing an amine compound with a solid content of less than 50% by mass are adjusted to have a solid content of 50% by mass using an evaporator or the like.

[0082] Furthermore, a non-aqueous component (C) containing an amine compound refers to a component containing an epoxy-curable amine compound that is not freely miscible with water, and is substantially insoluble in water. Specifically, if a mixture obtained by mixing a component containing an amine compound with water at 23°C so that the solid content is 3% by mass, stirring thoroughly, and letting it stand at 23°C for 1 hour is not homogeneous, and 50% or more of the solid content of the component mixed with water is separated, precipitated, or suspended, then that component is considered a non-aqueous component (C). In the aforementioned mixture, if 90% or more by mass of the solid content of the component mixed with water is stably present in the water, and the average particle size of the component mixed with water, as measured by a laser diffraction particle size distribution analyzer (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)), is less than 10 nm, then in this specification, the component shall be considered a water-soluble component. Furthermore, in this specification, components containing amine compounds 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 a corrosion-resistant coating with excellent corrosion resistance, 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] Reaction ratio = {(Amount of solids of water-dilutable component (B) / Equivalent of active hydrogen in the solids of water-dilutable component (B)) + (Amount of solids of non-aqueous component (C) / Equivalent of active hydrogen in the solids of non-aqueous component (C)) + (Amount of solids of component reactive with non-aqueous epoxy compound (A) / Equivalent of functional groups in the solids of component reactive with non-aqueous epoxy compound (A))} / {(Amount of solids of non-aqueous epoxy compound (A) / Equivalent of epoxy in the solids of non-aqueous epoxy compound (A)) + (Amount of solids of component reactive with water-dilutable component (B) or non-aqueous component (C) / Equivalent of functional groups in the solids of component reactive with water-dilutable component (B) or non-aqueous component (C))} ... (2)

[0085] Here, the "component that is reactive to the water-dilutable component (B) or the non-aqueous component (C)" and the "component that is reactive to the non-aqueous epoxy compound (A)" in formula (2) above include, for example, the silane coupling agent. 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 reactive group, it is necessary to determine whether the silane coupling agent is reactive with a water-dilutable component (B) or a non-aqueous component (C), or with a non-aqueous epoxy compound (A), and to calculate the reaction ratio.

[0086] The "functional group equivalent" of each component refers to the mass (g) per mole of functional group obtained by dividing the mass of 1 mole of these components by the number of moles of functional groups contained within it.

[0087] [Water-dilutable component (B)] The water-dilutable component (B) is not particularly limited as long as it is a component that 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 that it is possible to easily form an anticorrosive coating film with excellent curability and corrosion resistance.

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

[0090] Specific examples of water-dilutable components (B) include components containing hydrophilic amine compounds obtained by reacting conventionally known amine compounds used as curing agents for epoxy compounds with glycidyl ethers of polyalkylene glycols or polyoxyalkyleneamines, etc., components containing amine compounds having an amide structure obtained using fatty acids and aliphatic amine compounds, or components obtained by forcibly dispersing amine compounds in water, which have been given the ability to emulsify by neutralizing conventionally known amine compounds used as curing agents for epoxy compounds with acid or by mixing with emulsifiers.

[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 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 alkylaminoalkylamines.

[0093] Examples of the alkylene polyamine include those with the formula: "H2N-R 1 -NH2" (R 1 A is a divalent hydrocarbon group having 1 to 12 carbon atoms. Examples of compounds represented by () 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 a compound represented by the formula: “H2N-(C m H 2m NH) n H” (where m is an integer of 1 to 10, n is an integer of 2 to 10, preferably an integer of 2 to 6). Specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenetetramine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0095] Examples of the alkylaminoalkylamine include a compound represented by the formula: “R 2 2N-(CH2) p -NH2” (where R 2 are each 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, polyoxyalkylene polyamines (especially diethylene glycol bis(3-aminopropyl) ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), mensendiamine (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 agents include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0098] Examples of the aromatic amine curing agents include aromatic polyamine compounds having two or more primary amino groups bonded to aromatic rings such as benzene rings or naphthalene rings. Specific examples of these aromatic amine curing agents include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 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 agents include 1,4-diazacycloheptane, 1,4-bis(3-aminopropyl)piperazine, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0100] The amine compounds used as curing agents for the epoxy compound mentioned above can also include modified versions of the aforementioned amine compounds, such as fatty acid modified products like polyamidoamines, 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 in combination a component (B1) containing polyamidoamine b1 and a component (B2) containing at least one amine b2 selected from amine adducts with epoxy compounds and Mannich-modified amines having a phenol-derived skeleton, in order to easily form a corrosion-resistant coating with superior corrosion resistance. However, in this case, it is preferable not to use two or more components (B3) containing polyamidoamine b1 and amine b2, in order to better exhibit this 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 of them is component (B3).

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

[0103] The active hydrogen equivalent of the solid content of component (B2) is preferably 140 to 200, more preferably 150 to 190, from the viewpoint that it is possible to easily form a corrosion-resistant coating film with excellent curability and corrosion resistance.

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

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

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

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

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

[0109] Examples of the aforementioned 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 dimer acid.

[0110] The aforementioned component (B1) may be one obtained by conventionally known methods 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 in which an amine compound is dispersed in an aqueous medium (amine emulsion), or it may be the amine compound itself (100% amine compound).

[0112] The aqueous medium may contain water, or it may contain a medium other than water with a boiling point of less than 180°C under normal pressure. Examples of media other than water with a boiling point of less than 180°C at 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. One or more of these can be used.

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

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

[0115] The non-aqueous component (C) is preferably 3,000 or less, more preferably 2,500 or less, and contains an amine compound having a cyclic structure, and more preferably is an amine compound, in terms of being able to easily form a corrosion-resistant coating film with excellent corrosion resistance and to easily obtain a low-viscosity corrosion-resistant coating composition.

[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 that it is possible to easily form a corrosion-resistant coating film with excellent curability and corrosion resistance.

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

[0118] The non-aqueous component (C) may be one obtained by conventionally known methods or a commercially available product. Examples of such 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 a agent is not particularly limited as long as it contains a water-dilutable component (B), and the second b agent is not particularly limited as long as it contains a non-aqueous component (C).Optionally, other components such as water (D), a water-soluble component containing an amine compound, other amine components, pigments, pigment dispersants, anti-sagging agents (settling inhibitors, throttling agents), flash rust inhibitors, plasticizers, defoamers, curing accelerators, curing catalysts, and organic solvents may be included, to the extent that the effects of the present invention are not impaired. These other components may be used individually or in combination of two or more types. The aforementioned other components can be conventionally known components, and examples of pigments, anti-sagging agents (settling inhibitors, throttling agents), flash rust inhibitors, plasticizers, defoaming agents, and organic solvents include components similar to those listed in the first component section.

[0120] <Water (D)> The water-dilutable component (B) may contain water. In this case, water (D) other than the water contained in the water-dilutable component (B) may be used, but it is preferable to further incorporate water (D) in the second agent and the second a agent, in addition to the water that may be contained in the water-dilutable component (B), in order to make the preparation of this composition easier and to easily obtain a corrosion-resistant coating composition that is superior in storage stability and paintability. There are no particular restrictions on the water (D), and tap water may be used, but it is preferable to use deionized water or the like.

[0121] The water content in the second agent (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), etc.) is not particularly limited, but is preferably 25 to 80% by mass, more preferably 30 to 75% by mass. The second b agent may or may not contain water, but it is preferable that it does not contain water. If the second b agent contains water, the amount of water is not particularly limited, but is preferably 0 to 5% by mass, more preferably 0 to 2% by mass. Furthermore, the water content in the second agent and the second a agent is preferably 50% by mass or more, more preferably 70-100% by mass, and particularly preferably 80-100% by mass, based on 100% by mass of the total amount of dispersion medium and solvent in the second agent and the second a agent, in order to easily obtain the desired anticorrosive 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 a agent and the second b agent prepared in steps 1, 2a and 2b, respectively. This composition can be manufactured by mixing (kneading) these first agent, second agent, and nth agent, which may be used as needed, or by mixing (kneading) these first agent, seconda agent, secondb agent, and nth agent, which may be used as needed. During the mixing (kneading) process, conventionally known devices such as mixers, dispersers, and agitators can be used. Examples of such devices include dispersers, mixing / dispersing mills, mortar mixers, rolls, paint shakers, and homogenizers. Furthermore, the mixing (kneading) process may be carried out while heating or cooling the mixture, depending on the season, environment, etc.

[0123] <This composition> The non-volatile content of this composition is 70% by volume or more, preferably 72% by volume or more, more preferably 74% by volume or more, and there is no particular upper limit, but for example it is 85% by volume. The non-volatile content (volume %) of this composition can be calculated in accordance with ISO 3233:1998. A composition whose non-volatile content falls within the aforementioned range can be described as a high-solids composition. When the non-volatile content of this composition falls within the aforementioned range, it is possible to easily obtain a corrosion-resistant coating composition that has excellent drying properties, is less prone to dripping during application, can form a thick film in a single application, and has excellent paintability.

[0124] The viscosity of this composition, as 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. The lower limit is not particularly limited, but 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, a corrosion-preventive coating composition can be easily obtained in which the viscosity is within these ranges and the non-volatile content is within the aforementioned range. When the viscosity is within the aforementioned range, a corrosion-preventive coating composition with excellent handling and anti-sagging properties, no restrictions on the coating method, and the ability to be applied by various desired coating methods can be easily obtained. Although this composition may be diluted with a solvent or dispersion medium (e.g., water) depending on the coating method, according to the present invention, the viscosity is within the aforementioned range even without dilution with a solvent or dispersion medium, so coating is possible without dilution with a solvent or dispersion medium. Each description in this specification refers to the composition before dilution with a solvent or dispersion medium.

[0125] The VOC content of this 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 a corrosion-preventive coating composition that has little impact on the natural environment and the painting work environment.

[0126] The VOC content in this composition can be calculated using the following formula (1), based on the composition's specific gravity, heat residue percentage (mass ratio of non-volatile components), and moisture content. The composition's specific gravity, heat residue percentage, and moisture content may be measured values ​​as shown below, or 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 is calculated by filling a 100 ml specific gravity cup with the composition (the composition immediately after mixing the first agent, the second agent, and (the nth agent if it contains the nth agent), or the first agent, the seconda agent, the secondb agent, and (the nth agent if it contains the nth agent) under a temperature of 23°C, and weighing the mass of the composition.

[0128] Heating residue percentage (mass%): This is the mass percentage calculated by measuring the heating residue (non-volatile content) and the mass of the wire after measuring the heat residue (non-volatile content) and the mass of the wire when 1 ± 0.1 g of the composition (the composition immediately after mixing the first agent, the second agent and (if the nth agent is included, the nth agent) or the first agent, the second a agent and the second b agent and (if the nth agent is included, the nth agent) are weighed onto a flat-bottomed 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 (under normal pressure). Furthermore, in each component that makes up the first agent, second agent, etc. (e.g., non-aqueous epoxy compound (A)), the components other than the solvent and dispersion medium (e.g., water) with a boiling point of less than 180°C at normal pressure in the first agent, second agent, seconda agent, and secondb agent are referred to as "solids."

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

[0130] <<Corrosion-resistant coatings, substrates with corrosion-resistant coatings>> The anticorrosion coating film according to the present invention (hereinafter also referred to as "the coating film") is formed from the kit, and more specifically, from the composition obtained from the kit or the composition manufactured by the method. The coating film is preferably used as a substrate with a corrosion-resistant coating (hereinafter also referred to as "substrate with coating") which includes the substrate and the coating film. The substrate with coating is a laminate having the coating film and the substrate.

[0131] The material of the base material is not particularly limited and includes, for example, iron and steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, galvanized, zinc sprayed, etc.), and stainless steel (SUS304, SUS410, etc.). Furthermore, when using, for example, mild steel (SS400, etc.) as the substrate, it is desirable to prepare the surface of the substrate by polishing it with grit blasting or the like (e.g., adjusting it so that the arithmetic mean roughness (Ra) is about 30 to 75 μm) as necessary. The aforementioned substrate may also be a substrate that has undergone pretreatment such as cleaning or blasting to remove rust, dirt, paint (old paint film), etc., adhering to the substrate.

[0132] The aforementioned substrate is not particularly limited and can be used without restriction on any substrate requiring corrosion resistance. However, from the standpoint of exhibiting the effects of using this composition, (steel) structures such as ships, offshore structures, plants, bridges, tanks, and containers are preferred.

[0133] The dry film thickness of this coating is not particularly limited, but it is usually 10 to 400 μm, preferably 15 to 300 μm, in order to obtain a coating with sufficient corrosion resistance.

[0134] The coated substrate is a laminate comprising the coated substrate and the substrate, and may have an undercoat (primer coating) for the purpose of improving adhesion to the substrate and corrosion resistance, an intermediate coating for the purpose of improving corrosion resistance, and a topcoat for excellent weather resistance and aesthetics. Specifically, when this composition is used as a substitute for zinc primer, an intermediate coating or a topcoat may be formed on this coating. Examples of the aforementioned undercoat coating include coatings formed from various primer compositions such as epoxy resins. Examples of the aforementioned intermediate coating include coatings formed from various intermediate coating paint compositions such as (meth)acrylic resins, epoxy resins, and urethane resins. Examples of the aforementioned topcoat coating include coatings formed from various topcoat paint compositions such as (meth)acrylic resins, (meth)acrylic silicone resins, urethane resins, silicone resins, and fluororesin-based paints. Furthermore, the composition of this composition may be changed to form the undercoat coating, intermediate coating, and topcoat coating.

[0135] ≪Method for manufacturing substrates with anticorrosion coating≫ The method for producing a substrate with a corrosion-resistant coating according to the present invention comprises the following steps [1] and [2]. Step [1]: A step of coating a substrate with the composition obtained from this kit or the composition manufactured by this method. Step [2]: A step of drying the composition applied to the substrate to form the coating film.

[0136] <Process [1]> The painting method in step [1] is not particularly limited, and examples include conventionally known methods such as spray painting including airless spray painting and air spray painting, brush painting, and roller painting. Among these, spray painting is preferred because it can easily paint large surface areas of substrates such as structures. When performing such painting, it is preferable to paint the coating so that the dry film thickness of the resulting coating falls within the aforementioned range.

[0137] The conditions for the spray coating described above can be adjusted as appropriate depending on the desired dry film thickness. For example, in the case of airless spray coating, a primary (air) pressure of approximately 0.3 to 0.6 MPa, a secondary (paint) pressure of approximately 10 to 15 MPa, and a gun travel speed of approximately 50 to 120 cm / second are preferred.

[0138] The aforementioned coating is preferably applied in such a way that the dry film thickness of the coating formed in step [2] falls within the aforementioned range. In this case, the coating may be formed with the desired film thickness in one coat (single coat), or it may be formed with two or more coats (two or more coats). Note that two-coat application refers to performing steps [1] and [2], and then applying step [1] on the main coating obtained in step [2].

[0139] When applying this composition to a substrate, it is preferable to treat the substrate surface as necessary (for example, by blasting (ISO8501-1 Sa2 1 / 2), 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 film to the substrate. In addition, a shop primer or the like may be applied to the substrate for primary rust prevention.

[0140] <Process [2]> The drying conditions in step [2] above are not particularly limited and can be set appropriately depending on the method of forming the coating film, the type of substrate, the application, the painting environment, etc. However, the drying temperature is usually 5 to 35°C when drying at room temperature, and usually 30°C or more and less than 100°C, more preferably 40 to 80°C when forced drying is performed using a hot air dryer or the like. With this composition, the composition can be dried and cured even with such room temperature drying. The drying time varies depending on the drying method of the coating. For room temperature drying, it takes about 1 to 7 days, for example, while for forced drying, it takes about 5 to 60 minutes. [Examples]

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

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

[0143] In addition, the second agent was prepared by placing 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 into a separate container and stirring with a high-speed disperser until homogeneous.

[0144] The first and second components prepared were mixed in the mixing ratio (mass ratio) shown in Table 1 before application to prepare the anticorrosive coating composition. Table 2 shows a description of each component listed in Table 1.

[0145] [Examples 2-9 and Comparative Examples 1-8] A corrosion-preventive coating composition was prepared in the same manner as in Example 1, except that each component listed in Table 1 was used in the amounts (parts by mass) listed in Table 1.

[0146] The viscosity of each anticorrosive coating composition prepared in the examples and comparative examples was measured at 23°C 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 substrates (test panels) with anticorrosion coating] A sandblasted SS400 steel plate with dimensions of 150 mm x 70 mm x 2.3 mm (thickness) (arithmetic mean roughness (Ra): 30-75 μm) was prepared. The anticorrosive coating composition prepared as described above was applied to the surface of this steel plate using an air spray to achieve a dry film thickness of 70 μm. Next, the anticorrosive coating composition applied to the steel plate was dried at 60°C for 40 minutes, and then a water-based acrylic resin topcoat (EKOMATE FINISH (manufactured by Chugoku Marine Paints Ltd.)) was applied using an air spray to achieve a dry film thickness of 40 μm. After that, the applied water-based acrylic resin topcoat was dried at 60°C for 30 minutes, and then dried at 23°C for 7 days to prepare test plate 1.

[0150] Furthermore, the anticorrosive coating composition prepared as described above was applied to the surface of a steel plate similar to that used in test plate 1, using an air sprayer, to a dry film thickness of 80 μm. Next, the anticorrosive coating composition applied to the steel plate was dried at 60°C for 30 minutes, and then dried at 23°C for 7 days to prepare test plate 2.

[0151] <Salt spray test> Based on JIS K 5600-7-1:1999, a salt spray test was conducted by holding test plates 1 and 2 for 400 hours in a salt spray tester under salt spray conditions of 5% by mass, 35°C, and 98% relative humidity. The corrosion resistance was evaluated according to the evaluation criteria described below. The results are shown in Table 3. Furthermore, regarding corrosion resistance, a rating of 3 or higher in this salt spray test indicates that there are no practical problems. (Evaluation Criteria) 5: No rust or blistering has occurred. 4: Although no blistering has occurred, the area of ​​rust on the substrate surface beneath the coating is less than 0.03% of the total surface area of ​​the substrate beneath the coating. 3: A very small amount of small blisters occur, and the area of ​​rust on the substrate surface beneath the coating is between 0.03% and 0.1% of the total surface area of ​​the substrate beneath the coating. 2: Blistering occurs, and the area of ​​rust on the substrate surface beneath the coating is 0.1% or more but less than 0.3% of the total surface area of ​​the substrate beneath the coating. 1: Blistering occurs, and the area of ​​rust on the substrate surface beneath the coating is 0.3% or more of the total surface area of ​​the substrate beneath the coating.

[0152] <Combined cycle testing> A 25-cycle test was conducted using test plates 1 and 2 in accordance with ASTM D2803. The appearance of the test plates after the test was evaluated according to the same evaluation criteria as the salt spray test. The results are shown in Table 3. Furthermore, regarding corrosion resistance, a rating of 3 or higher in this combined cycle test indicates that there are no practical problems.

[0153] [Table 3]

Claims

1. Step 1 involves preparing the first agent using a non-aqueous epoxy compound (A), Step 2 involves 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 involves mixing the first agent and the second agent. Includes, The aqueous 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. The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound. A method for producing a corrosion-preventive coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

2. Step 1 involves preparing the first agent using a non-aqueous epoxy compound (A), Step 2a involves preparing agent 2a using a water-dilutable component (B) containing an amine compound, Step 2b involves preparing the second b agent using a non-aqueous component (C) containing an amine compound, Step 3' involves mixing the first agent, the second a agent, and the second b agent. Includes, The aqueous 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. The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound. A method for producing a corrosion-preventive coating composition having a volatile organic compound (VOC) content of 100 g / L or less.

3. A method for producing the anticorrosive coating composition according to claim 1 or 2, wherein the viscosity of the anticorrosive coating composition measured at 23°C is 7,000 mPa·s or less.

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

5. A method for producing an anticorrosive 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 with a molecular weight of 3,000 or less.

6. A method for producing a corrosion-preventive coating composition according to any one of claims 1 to 5, wherein the first agent further contains a silane coupling agent.

7. The first agent contains a non-aqueous epoxy compound (A), A second agent comprising a water-dilutable component (B) containing an amine compound, and a non-aqueous component (C) containing an amine compound. It contains, The aqueous 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. The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound. A kit for anticorrosive coating compositions with a volatile organic compound (VOC) content of 100 g / L or less.

8. The first agent contains a non-aqueous epoxy compound (A), Agent 2a contains a water-dilutable component (B) containing an amine compound, The second b agent contains a non-aqueous component (C) containing an amine compound and It contains, The aqueous 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. The non-aqueous component (C) containing the amine compound is a non-aqueous amine compound. A kit for anticorrosive coating compositions with a volatile organic compound (VOC) content of 100 g / L or less.

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

10. A substrate with a corrosion-resistant coating, comprising a base material and the corrosion-resistant coating described in claim 9.

11. A method for manufacturing 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 manufactured by the manufacturing method described in any one of claims 1 to 6, or an anticorrosive coating composition obtained from the anticorrosive coating composition kit described in claim 7 or 8. [2] A process of drying the anticorrosive coating composition applied to the substrate to form an anticorrosive coating film.

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