Method for producing anticorrosive coating composition

Abstract

To provide a method for producing an anticorrosive coating composition which can form an anticorrosive coating film excellent in anticorrosive properties and can exhibit excellent painting work while being in a high solid state, and a kit for the anticorrosive coating composition.SOLUTION: There is provided a method for producing an anticorrosive coating composition whose non-volatile component is 70 volume% or greater, the method including a step 1 for preparing a first agent using a non aqueous epoxy compound (A), and the following steps 2 and 3 or the following steps 2a, 2b, and 3'. 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 second a agent using the water dilution component (B) containing an amine compound, the step 2b is a step for preparing a second b agent using the non-aqueous component (C) containing an amine compound, and the step 3' is a step for mixing the first agent, the second a agent and the second b agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an anticorrosive paint composition, a kit for an anticorrosive paint composition, an anticorrosive paint film, a substrate with an anticorrosive paint film, and a method for producing a substrate with an anticorrosive paint film.

Background Art

[0002] Substrates such as ships, offshore structures, plants, bridges, and onshore tanks are painted with solvent-based epoxy resin anticorrosive paints for the purpose of using them over a long period of time.

[0003] In recent years, with the strengthening of regulations on the emission of organic solvents for the purpose of considering the natural environment, painting work environment, etc., the reduction of VOC (volatile organic compounds) in the above-mentioned solvent-based paints has been progressing. One of the methods for reducing VOC is the water-based conversion of paints. Since water-based anticorrosive paints mainly use water as a solvent and a dispersion medium, it is possible to significantly reduce VOC compared to conventional solvent-based paints while maintaining an appropriate paint viscosity.

[0004] As such water-based anticorrosive paints, for example, 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 a water-based epoxy resin paint composition containing a water-soluble amine resin and a hydrophobic liquid epoxy resin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the anticorrosive coating film formed from the conventional anticorrosive paints described in Patent Documents 1 and 2, etc. has insufficient anticorrosive performance, and there is room for improvement in this regard.

[0007] Also, as a method for improving the efficiency of the painting operation, such as reducing the number of painting times for forming an anticorrosive coating film with a predetermined film thickness, high-solidification of the paint is effective. However, in the conventional anticorrosive paints, due to the increase in viscosity accompanying high-solidification, the workability of the painting operation has deteriorated. That is, in the conventional anticorrosive paints, there is a trade-off relationship between high-solidification and painting workability, and it has been difficult to achieve both.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing an anticorrosive paint composition that can form an anticorrosive coating film excellent in anticorrosive properties and is high-solid while having excellent painting workability, and a kit for the anticorrosive paint composition.

Means for Solving the Problems

[0009] As a result of the present inventors' intensive studies on a method for solving the above problems, it has been found that the above problems can be solved according to the following configuration examples, and the present invention has been completed. The configuration examples of the present invention are as follows.

[0010] <1> Step 1 of preparing a first agent using a non-aqueous epoxy compound (A), Step 2 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 3 of mixing the first agent and the second agent A method for manufacturing an anticorrosive paint composition having a non-volatile content of 70% by volume or more, including

[0011] <2> Step 1 of preparing a first agent using a non-aqueous epoxy compound (A), Step 2a of preparing a second a-agent using a water-dilutable component (B) containing an amine compound, Step 2b of preparing a second b-agent using a non-aqueous component (C) containing an amine compound, Step 3' of mixing the first agent, the second a-agent, and the second b-agent, and A method for producing an anticorrosive paint composition having a non-volatile content of 70% by volume or more, the method comprising:

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

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

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

[0015] <6> The method for producing an anticorrosive 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 An anticorrosive paint composition kit having a non-volatile content of 70% by volume or more.

[0017] <8> A first agent containing a non-aqueous epoxy compound (A), A second a-agent containing a water-dilutable component (B) containing an amine compound, and A second b-agent containing a non-aqueous component (C) containing an amine compound, and An anticorrosive paint composition kit having a non-volatile content of 70% by volume or more.

[0018] <9> An anticorrosive paint film formed from the anticorrosive paint composition kit according to <7> or <8>. <10> A substrate with a corrosion - resistant coating film, which comprises a substrate and the corrosion - resistant coating film described in <9>.

[0019] <11> A method for manufacturing a substrate with a corrosion - resistant coating film, which comprises the following steps [1] and [2]. [1] A step of coating a substrate with a corrosion - resistant coating composition manufactured by the manufacturing method described in any one of <1> to <6>, or a corrosion - resistant coating composition obtained from the kit for a corrosion - resistant coating composition described in <7> or <8>. [2] A step of drying the corrosion - resistant coating composition coated on the substrate to form a corrosion - resistant coating film.

Advantages of the Invention

[0020] According to the present invention, it is possible to obtain a corrosion - resistant coating composition that can form a corrosion - resistant coating film with excellent corrosion resistance, 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 likely to sag during coating, can form a thick film in one coating, has little adverse impact on the natural environment and painters, and can form a corrosion - resistant coating film with excellent corrosion resistance.

Embodiments for Carrying out the Invention

[0021] ≪Kit for Corrosion - Resistant Coating Composition≫ The kit for a corrosion - resistant coating composition according to the present invention (hereinafter also referred to as "this kit") is a kit for a corrosion - resistant coating composition (hereinafter also referred to as "this composition") having a non - volatile content of 70% by volume or more, 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 is a kit (hereinafter also referred to as "this kit 1") containing, or a first agent containing a non - aqueous epoxy compound (A), a second agent a (2a) containing a water - dilutable component (B) containing an amine compound, a second agent b (2b) containing a non - aqueous component (C) containing an amine compound A kit containing the same (hereinafter also referred to as "this kit 2").

[0022] This kit 1 can obtain this composition by mixing a first agent and a second agent, and this kit 2 can obtain this composition by mixing a first agent, a second a agent, and a second b agent. In the case of this kit 1, when obtaining this composition, if necessary, a nth agent (n is 3 or more) other than the first agent and the second agent may be used. In the case of this kit 2, when obtaining this composition, if necessary, a nth agent (n is 3 or more) other than the first agent, the second a agent, and the second b agent may be used, but it is preferable not to use the nth agent. That is, this kit 1 is preferably a kit for a two-component type of this composition, and this kit 2 is preferably a kit for a three-component type of this composition.

[0023] The first agent, the second agent, the second a agent, the second b agent, etc. that constitute this kit are usually stored, stored, transported, etc. in separate containers, and are mixed and used immediately before using this composition.

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

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

[0026] Further, this method may include a step of preparing an nth agent (n is 3 or more). In this case, the step 3 may be a step of mixing the first agent, the second agent, and the nth agent, and the step 3' may be a step of mixing the first agent, the second agent a, the second agent b, and the nth agent.

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

[0028] Specifically, the step 1 is a step of mixing (kneading) each component to be blended in the first agent. At the time of this mixing (kneading), each component may be added and mixed at once, or may be added and mixed in multiple times. At the time of the mixing (kneading), devices such as conventionally known mixers, dispersers, and stirrers can be used. Examples of such devices include a disper, a mixing and dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. Note that at the time of the mixing (kneading), it may be carried out while heating, cooling, etc. according to the season, environment, etc.

[0029] In Project 1, water may or may not be used. That is, the first agent may or may not contain water. When the first agent contains water, the water content is preferably less than an amount at which the first agent can become an emulsion of the non-aqueous epoxy compound (A). Specifically, based on 100% by mass of the non-aqueous epoxy compound (A) in the first agent, it is preferably 35% by mass or less, more preferably 25% by mass or less.

[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 kind or two or more kinds.

[0031] "Non-aqueous" in the non-aqueous epoxy compound (A) means a state that is not freely miscible with water and substantially insoluble in water. Specifically, at 23°C, the epoxy compound and water are mixed so that the epoxy compound becomes 3% by mass, stirred well, and left standing at 23°C for 1 hour. If the resulting mixture is not in a uniform state and 90% by mass or more of the epoxy compound mixed with water is separated, precipitated, or floating, the epoxy compound is defined as the non-aqueous epoxy compound (A).

[0032] In the above mixture, when more than 10% by mass of the epoxy compound mixed with water is stably present in water and the mixture is maintained in an emulsion state, the epoxy compound is defined as a water-dilutable epoxy compound. Also, in the above mixture, when more than 10% by mass of the epoxy compound mixed with water is stably present in water and there is an epoxy compound mixed with water in a state where the average particle size measured by a laser diffraction particle size distribution measuring device (e.g., Mastersizer 3000 manufactured by Spectris Co., Ltd.) is less than 10 nm, the epoxy compound is defined as a water-soluble epoxy compound.

[0033] The non-aqueous epoxy compound (A) is preferably a liquid epoxy compound that is liquid at normal temperature (e.g., 15 to 25 °C). Such a liquid epoxy compound is preferred because it can be easily dispersed uniformly in the first agent even when the first agent is an agent with a relatively small amount of solvent and an agent containing 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 the non-aqueous epoxy compound (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine 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. Preferable examples of the alkyl group include alkyl groups having 3 to 15 carbon atoms, and specifically include 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 from the viewpoints such as being able to easily form a corrosion-resistant coating film excellent in corrosion resistance and adhesion to the base material.

[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 viewpoints such as being able to easily obtain a corrosion-resistant coating composition that is high-solid and excellent in coating workability.

[0037] As the non-aqueous epoxy compound (A), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used. As commercially available products, those in a liquid state at normal temperature (e.g., 15 to 25 °C) include, for example, "E-028" (manufactured by Akitake 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 such that the solid content thereof is 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 present composition. Also, the solid content of the non-aqueous epoxy compound (A) is preferably 20 to 40% by mass, more preferably 25 to 30% by mass, based on 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 film excellent in corrosion resistance and adhesion to the substrate can be easily formed.

[0039] [Other Components] In Step 1, if desired, other components such as silane coupling agents, pigments, pigment dispersants, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, defoaming agents, dehydrating agents, film-forming aids, and organic solvents 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 above other components, commercially available products may be used. In this case, there may be commercially available products for solvent-based and water-based systems. When using a commercially available product for solvent-based systems, it is preferably blended into the first agent or the second agent b. When using a commercially available product for water-based systems, it is preferably blended into the second agent or the second agent a.

[0041] 〈Silane Coupling Agent〉 By using a silane coupling agent, not only can the adhesion of the resulting anticorrosive coating film to the substrate be further improved, but also the anticorrosive properties such as water resistance and salt water resistance, and the heat resistance of the resulting anticorrosive coating film can be improved.

[0042] The silane coupling agent is not particularly limited, and conventionally known compounds can be used. However, it is preferably a compound having at least two functional groups in the same molecule, which can contribute to improving the adhesion to the substrate and reducing the viscosity of the anticorrosive 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 represents 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 part of a hydrocarbon group is substituted with these groups, or a group in which a part of a group in which a part of a hydrocarbon group is substituted with an ether bond or the like is substituted with these groups), Me is a methyl group, and Y represents a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or an ethoxy group).]

[0044] Among these, it is preferably an epoxy group-containing silane coupling agent in which the above X is an epoxy group, a group in which a part of a hydrocarbon group is substituted with an epoxy group, or a group in which a part of a group in which a part of a hydrocarbon group is substituted with an ether bond or the like is substituted with an epoxy group. 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 products may be used as the silane coupling agent. Examples of such commercially available products include "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.), which is 3-glycidoxypropyltrimethoxysilane, and "Silane 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 such that the content thereof is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, based on 100% by 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 present composition can be reduced, so that not only the coating workability is improved, but also the adhesion, corrosion resistance and heat resistance of the obtained anticorrosive coating film to the substrate are improved.

[0047] 〈Pigment〉 The present composition may contain a pigment, and it is preferable that the present composition contains a pigment. Examples of the pigment include extender pigments, coloring pigments, and rust preventive pigments, and they 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. In particular, talc, mica, silica, (precipitated) barium sulfate, and (potassium) feldspar are preferable.

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

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

[0051] When producing the present composition containing a coloring pigment, it is preferable to use the coloring pigment such that the content of the coloring pigment 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 the present composition.

[0052] Examples of the rust preventive pigment include zinc powder, zinc alloy powder, zinc phosphate-based compound, calcium phosphate-based compound, aluminum phosphate-based compound, magnesium phosphate-based compound, zinc phosphite-based compound, calcium phosphite-based compound, aluminum phosphite-based compound, strontium phosphite-based compound, aluminum tripolyphosphate-based compound, molybdate-based compound, zinc cyanamide-based compound, borate compound, nitro compound, and composite oxide.

[0053] When producing the present composition containing a rust preventive pigment, it is preferable to use the rust preventive pigment such that the content of the rust preventive pigment 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 present composition.

[0054] When producing the present composition containing a pigment, it is preferable to use the pigment such 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, a corrosion preventive paint composition excellent in coating workability can be easily obtained, and a corrosion preventive coating film excellent in adhesion to the substrate and corrosion prevention due to stress relaxation can be easily formed.

[0055] The PVC refers to the total volume concentration of the pigments with respect to the volume of the non-volatile content of the present composition. Specifically, the PVC can be obtained from the following formula. PVC [%] = total volume of all pigments in the present composition × 100 / volume of the non-volatile content of the present composition

[0056] The volume of the non-volatile content of the present composition can be calculated from the mass and true density of the non-volatile content of the present composition. The mass and true density of the non-volatile 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 and other components from the non-volatile matter of the present 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 it is preferably a material that can suppress the sedimentation of pigments and the like in the present composition and improve its storage stability, or a material that can improve the anti-sagging property of the present composition during or after painting.

[0058] Examples of the anti-sagging agent include stearate salts of Al, Ca, and Zn, lecithin salts, organic clay-based waxes such as alkyl sulfonates, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, mixtures of hydrogenated castor oil waxes and amide waxes, synthetic fine silica, polyethylene oxide-based waxes, etc. Among them, amide waxes, synthetic fine silica, polyethylene oxide-based waxes, and organic clay-based waxes 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", "Disparlon AQ600" manufactured by Nanben Kasei Co., Ltd., "A-S-A T-250F" manufactured by Ito Seiyu Co., Ltd., "Flowron RCM-300" manufactured by Kyoeisha Chemical Co., Ltd., "RHEOBYK 420" manufactured by BYK-Chemie Japan Co., Ltd., "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 such that the solid content of the anti-sagging agent is preferably 0.1 to 10% by mass based on 100% by mass of the non-volatile content of the present composition.

[0061] 〈Flash rust inhibitor〉 The flash rust inhibitor is not particularly limited, but when the present composition is applied to an active steel surface or the like, during the drying process immediately after application, it is preferable that the flash rust inhibitor is a material that can suppress rusting caused by elution of iron ions from the steel surface or the like, and flash rust in which such rust floats to 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, ammonium nitrite; benzoates such as sodium benzoate, potassium benzoate, calcium benzoate, ammonium benzoate; phytates such as sodium phytate, potassium phytate; fatty acid salts such as sebacic acid, dodecanoic acid; phosphate derivatives such as alkyl phosphoric acid, polyphosphoric acid; tannates; sulfonic acid metal salts; amine-based chelating agents such as N-(2-hydroxyethyl)ethylenediamine triacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; an addition reaction product of 4-methyl-γ-oxo-benzenebutanoic acid and N-ethylmorpholine; an intercalation compound obtained by intercalating a monoalkylamine, polyamine, quaternary ammonium ion, etc. into a layered phosphate such as aluminum dihydrogen tripolyphosphate; hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, hydrazone compounds.

[0063] As the flash rust inhibitor, a commercially available product may be used. Examples of such commercially available products include "Kireslite W-410", "Kireslite W-16B" (both manufactured by Kest 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 such that the content of the solid component of the flash rust inhibitor 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> The present composition may contain a plasticizer from the viewpoint of improving the flexibility of the resulting anticorrosive coating film and the like. As the plasticizer, conventionally known ones can be widely used, and examples include liquid hydrocarbon resins such as low-boiling point fractions obtained by thermally decomposing naphtha, petroleum resins that are solid at normal temperature, xylene resins, coumarone-indene resins, and the like. Specifically, liquid hydrocarbon resins and flexibility-imparting resins described in JP-A-2006-342360 are included.

[0066] Among these, liquid hydrocarbon resins are preferable, and phenol-modified hydrocarbon resins are more preferable 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, and α-methylstyrene contained in cracked oil fractions of petroleum or coal with phenols (phenol compounds), as also described in JP-A-9-268209, JP-A-7-196793, and the like.

[0067] As the phenolic modified hydrocarbon resin, more specifically, C5-based (aliphatic) petroleum resins made from C5 fractions; C9-based (aromatic) petroleum resins made from C9 fractions; C5·C9 copolymerized petroleum resins; dicyclopentadiene resins made from dicyclopentadiene obtained by thermally dimerizing cyclopentadiene contained in C5 fractions; α-methylstyrene; and resins obtained by reacting these with phenols can be mentioned. Among these, resins obtained by addition polymerization of styrene, vinyltoluene, coumarone, indene, α-methylstyrene, etc. contained in cracked oil fractions of petroleum or coal with phenols are preferred.

[0068] The average molecular weight of the phenolic modified hydrocarbon resin is usually 200 to 1000, and the viscosity is usually 30 to 10,000 mPa·s / 25°C.

[0069] Commercially available products may be used as the liquid hydrocarbon resin. Examples of such commercially available products include "NESILESS EPX-L", "NESILESS EPX-L2" (both manufactured by NEVCIN / phenolic modified hydrocarbon resins), "Hirenol PL-1000S" (manufactured by Kolon Industries, Inc. / phenolic modified hydrocarbon resin), etc.

[0070] When producing the 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 non-volatile content of the composition. When the content of the plasticizer is within the above range, a corrosion-resistant coating film excellent in crack resistance and the like can be easily formed.

[0071] <Defoaming agent> This composition preferably contains a defoaming agent because it can suppress the generation of bubbles during the production or painting of the composition, or can break the bubbles generated in the composition, and can easily form a corrosion-resistant coating film with desired physical properties.

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

[0073] When producing the present composition containing a defoaming agent, it is preferable to use the defoaming agent such that the solid content of the defoaming 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 non-volatile content of the present composition. When the content of the defoaming agent is within the above range, the generation of bubbles can be sufficiently suppressed, and a corrosion-resistant coating film with desired physical properties can be easily formed.

[0074] <Film-forming aid> Since the present composition contains water, it may freeze in winter. Also, from the viewpoints of improving the film-forming property at low temperatures and the finished appearance of the resulting corrosion-resistant coating film, it is preferable to include a film-forming aid.

[0075] As the film-forming aid, those commonly used in aqueous paint compositions, such as organic compounds having a boiling point of 180°C or higher under normal pressure, can be used. For example, 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; (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 such that the content of the film-forming aid is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the present composition. When the content of the film-forming aid is within the above range, a corrosion-resistant coating film excellent in film-forming property and appearance at low temperatures can be easily formed.

[0077] <Organic solvent> The organic solvent is not particularly limited as long as it is an organic solvent having a boiling point of less than 180°C under normal pressure. For example, 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 can be mentioned.

[0078] When producing the present composition containing an organic solvent, it is preferable to use an organic solvent so that the content of VOC in the present composition falls within the following range. When preparing the first agent containing an organic solvent, it is preferable to use an organic solvent so that the content of the organic solvent is preferably 12% by mass or less, more preferably 10% by mass or less, based on 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 a 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 a 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 a second b agent 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 the second b agent. 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, further, the following other components may be used.

[0080] Specifically, Step 2, Step 2a, and Step 2b are steps of mixing (kneading) each component to be blended in each agent. At the time of this mixing (kneading), each component may be added and mixed at once, or may be added and mixed in multiple times. At the time of the above mixing (kneading), devices such as conventionally known mixers, dispersers, and stirrers can be used. Examples of such devices include a disper, a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. Note that at the time of the above mixing (kneading), it may be carried out while heating, cooling, etc. according to the season, environment, etc.

[0081] The water-dilutable component (B) containing the amine compound in the present invention 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, at 23°C, the component containing the amine compound and water are mixed so that the solid content becomes 50% by mass, or after the solvent / dispersion medium is volatilized, it is sufficiently stirred and left standing at 23°C for 1 hour. In the resulting mixed solution, 80% by mass or more of the solid content of the component mixed with water is stably present in water, and when the mixed solution is maintained in an emulsion state, the component is defined as the water-dilutable component (B). Note that a component containing an amine compound with a solid content of less than 50% by mass is adjusted to have a solid content of 50% by mass using an evaporator or the like.

[0082] Further, the non-aqueous component (C) containing the amine compound refers to a component containing an epoxy-curable amine compound that is not freely miscible with water, and refers to a component containing an epoxy-curable amine compound that is substantially insoluble in water. Specifically, at 23°C, the component containing the amine compound and water are mixed so that the solid content becomes 3% by mass, sufficiently stirred, and when the resulting mixed solution obtained by leaving it standing at 23°C for 1 hour is not in a uniform state and 50% by mass or more of the solid content of the component mixed with water is separated, precipitated, or floating, the component is defined as the non-aqueous component (C). In the mixture, when 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 in a state where the average particle size measured by a laser diffraction particle size distribution measuring device (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)) is less than 10 nm, in this specification, the component is defined as a water-soluble component. In addition, in this specification, the water-dilutable component (B), the non-aqueous component (C), and the component containing an amine compound other than the water-soluble component are defined as other amine components.

[0083] From the viewpoints such as being able to easily form a corrosion-resistant coating film excellent in corrosion resistance, coating film strength, and drying property, etc., 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 = { (blending amount of solid content of water-dilutable component (B) / active hydrogen equivalent of solid content of water-dilutable component (B)) + (blending amount of solid content of non-aqueous component (C) / active hydrogen equivalent of solid content of non-aqueous component (C)) + (blending 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))} / { (blending amount of solid content of non-aqueous epoxy compound (A) / epoxy equivalent of solid content of non-aqueous epoxy compound (A)) + (blending 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 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 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 reactive with the non-aqueous epoxy compound (A), and calculate the reaction ratio.

[0086] The "functional group equivalent weight" of each of the above components means the mass (g) per 1 mol of functional groups obtained by dividing the mass of 1 mol of these components by the number of moles of functional groups contained therein.

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

[0088] The active hydrogen equivalent weight of the solid content of the water-dilutable component (B) is preferably 50 to 200, more preferably 60 to 190, from the viewpoints such as being able to easily form a corrosion protection coating film excellent in curability and corrosion protection.

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

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

[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 amine compounds such as aliphatic, alicyclic, aromatic, and heterocyclic amine compounds are preferred.

[0092] Examples of the aliphatic amine compound include alkylene polyamines, polyalkylene polyamines, and alkylaminoalkylamines.

[0093] Examples of the alkylene polyamine include compounds 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 compounds represented by the formula: “H2N-(C m H 2m NH) n H” (where m is an integer from 1 to 10, n is an integer from 2 to 10, preferably an integer from 2 to 6). Specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0095] Examples of the alkylaminoalkylamine include compounds represented by the formula: “R 2 2N-(CH2) p -NH2” (where each R 2 is 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 from 1 to 6). Specific examples include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0096] Examples of aliphatic amine curing agents other than these include, for example, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylene polyamine (particularly, diethylene glycol bis(3-aminopropyl)ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), m-xylenediamine (MXDA), p-xylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), 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, 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 this 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, diethylmethylbenzenediamine.

[0099] Specific examples of the complex ring 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] Furthermore, as the amine compound used as the curing agent for the epoxy compound, modified products of the above-described amine compounds, for example, fatty acid modified products such as polyamideamine, 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 can be mentioned. Among these, polyamideamine, amine adducts with epoxy compounds, and Mannich modified amines having a phenol-derived skeleton are preferable.

[0101] As the water-dilutable component (B), it is preferable to use in combination a component (B1) containing polyamideamine b1 and at least one amine b2 selected from an amine adduct with an epoxy compound and a Mannich modified amine having a phenol-derived skeleton in terms of easily forming a corrosion-resistant coating film with excellent corrosion resistance. However, in this case, from the viewpoint of further exerting the effect, it is not preferable to use two or more components (B3) containing polyamideamine b1 and amine b2. That is, it is preferable that at least one of the components (B1) and (B2) is not the component (B3), and it is more preferable that both are not the component (B3).

[0102] As the water-dilutable component (B), those obtained by manufacturing by a conventionally known method may be used, or commercially available products may be used.

[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 easily forming a corrosion-resistant coating film excellent in curability and corrosion resistance.

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

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

[0106] As the component (B2), those obtained by manufacturing using a conventionally known method may be used, or commercially available products may be used. Examples of such 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) from the viewpoint of improving the miscibility of the water-dilutable component (B) and the non-aqueous component (C), preferably 50 to 130, more preferably 60 to 120.

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

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

[0110] As the component (B1), those obtained by manufacturing by a conventionally known method may be used, or commercially available products may be used. Examples of the commercially available product include "Jointmide 3506" (manufactured by Yun Teh Industral 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 the amine compound itself (100% amine compound).

[0112] The aqueous medium only needs to contain water, and may also contain a medium having a boiling point of less than 180°C under normal pressure other than water. Examples of the medium having a boiling point of less than 180°C under normal pressure other than water 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 can be used alone or in combination of two or more.

[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 contains an amine compound, and is not particularly limited as long as it contains an amine compound. Specifically, among the amine compounds used as a curing agent for the epoxy compound, amine compounds that satisfy the above definition can be mentioned. The non-aqueous component (C) used in Step 2 may be one kind or two or more kinds.

[0115] From the viewpoints of being able to easily form a corrosion-resistant coating film with excellent corrosion resistance and being able to easily obtain a corrosion-resistant coating composition with low viscosity, 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 such an amine compound.

[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, in terms of easily forming a corrosion-resistant coating film excellent in curability and corrosion resistance.

[0117] The amount of the non-aqueous component (C) used in Step 2 is preferably such that the content of its solid content satisfies the above formula (2), and more preferably such that it falls within the following range. The content of 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 present composition. Also, the content of the solid content of the non-aqueous component (C) is preferably 15 to 55% by mass, more preferably 20 to 50% by mass, based on 100% by mass of the solid content of the second agent. Also, the content of the solid content of the non-aqueous component (C) is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, based on 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 film excellent in corrosion resistance and drying properties can be easily formed.

[0118] As the non-aqueous component (C), those obtained by manufacturing by a conventionally known method may be used, or commercially available products may be used. Examples of such commercially available products include "Ancamine 2280" (manufactured by Evonik) and "ETHACURE 100plus" (manufactured by Albemarle).

[0119] [Other components] The second agent is not particularly limited as long as it contains the water-dilutable component (B) and the non-aqueous component (C). The second a-agent is not particularly limited as long as it contains the water-dilutable component (B). The second b-agent is not particularly limited as long as it contains the non-aqueous component (C). Optionally, within a range that does not impair the effects of the present invention, it may contain other components such as water (D), a water-soluble component containing an amine compound, other amine components, a pigment, a pigment dispersant, an anti-sagging agent (anti-settling agent, thixotropic agent), a flash rust inhibitor, a plasticizer, an antifoaming agent, a curing accelerator, a curing catalyst, and an organic solvent. These other components may each be used alone or in combination of two or more. As the other components, conventionally known components can be used, and examples of pigments, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, defoamers, and organic solvents include the same components as those described in the section of the first agent.

[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 from the viewpoints of facilitating the preparation of the present composition and easily obtaining a corrosion preventive coating composition having more excellent storage stability and coating workability, etc., it is preferable to further incorporate water (D) in addition to the water that can be contained in the water-dilutable component (B) in the second agent and the second a agent. Water (D) is not particularly limited, and tap water or the like may be used, but ion-exchanged water or the like is preferably used.

[0121] The content of water in the second agent (including the water that can 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 content of water in the second a agent (including the water that can 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 preferably water-free. When the second b agent contains water, the content of the water is not particularly limited, but is preferably 0 to 5% by mass, more preferably 0 to 2% by mass. Also, from the viewpoints of easily obtaining a desired corrosion preventive coating composition, etc., the content of water in the second agent and the second a agent is preferably 50% by mass or more, more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, based on 100% by mass of the total amount of the dispersion medium and the solvent in the second agent and the second a agent.

[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 2a agent and the 2b agent prepared in Steps 1, 2a and 2b respectively. By mixing (kneading) these first agent, second agent and, if necessary, the nth agent, and also by mixing (kneading) these first agent, 2a agent, 2b agent and, if necessary, the nth agent, the present composition can be produced. When performing the mixing (kneading), devices such as conventionally known mixers, dispersers, stirrers, etc. can be used. Examples of such devices include a disper, a mixing and dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. Note that when performing the mixing (kneading), it may be carried out while heating, cooling, etc. according to seasons, environment, etc.

[0123] <The present composition> The non-volatile content of the present composition is 70% by volume or more, preferably 72% by volume or more, more preferably 74% by volume or more. The upper limit is not particularly limited, for example, it is 85% by volume. Note that the non-volatile content (% by volume) of the present composition can be calculated in accordance with ISO3233:1998. It can be said that a composition with a non-volatile content within the above range is a high-solid composition. When the non-volatile content of the present composition is within the above range, it has excellent drying properties, is less likely to sag during painting, can form a thick film with a single coating, and an anticorrosive paint composition with excellent painting workability can be easily obtained.

[0124] The viscosity of the present composition measured at 23°C is preferably 7000 mPa·s or less, more preferably 5500 mPa·s or less, still 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, still more preferably 2500 mPa·s or more. According to the present method, an anticorrosive paint composition having a viscosity within these ranges and a nonvolatile content within the above ranges can be easily obtained. When the viscosity is within the above ranges, an anticorrosive paint composition excellent in handleability and sag resistance, not limited in coating methods, and capable of being coated by various desired coating methods with excellent coating workability can be easily obtained. In addition, although this composition may be diluted with a solvent or a dispersion medium (e.g., water) according to coating methods or the like, according to the present invention, since the viscosity is within the above ranges even without dilution with a solvent or a dispersion medium, it is possible to coat without dilution with a solvent or a dispersion medium. Each description in this specification is an explanation before dilution with a solvent or a dispersion medium.

[0125] The content of VOC in 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 from the viewpoints such as being an anticorrosive paint composition having little influence on the natural environment and the coating work environment.

[0126] The VOC content in this composition can be calculated from the following formula (1) using the values of the composition specific gravity, the heating residue ratio (mass ratio of nonvolatile matter), and the moisture ratio. Note that the composition specific gravity, the heating residue ratio, and the moisture ratio may be measured values as follows or values calculated from the raw materials used. VOC content (g / L) = composition specific gravity × 1000 × (100 - heating residue ratio - moisture ratio) / 100 ···(1)

[0127] Paint specific gravity (g / cm 3 ): The value calculated by filling the composition (the first agent and the second agent (and the nth agent if the nth agent is included), or the composition immediately after mixing the first agent, the 2a agent, the 2b agent (and the nth agent if the nth agent is included)) into a specific gravity cup with an internal volume of 100 ml and weighing the mass of the composition under the temperature condition of 23°C

[0128] Heating residue ratio (mass%): The value of the mass percentage calculated by measuring the heating residue (non-volatile matter) and the mass of the wire when 1 ± 0.1 g of this composition (the composition immediately after mixing the first agent and the second agent (and the nth agent if the nth agent is included), or the first agent, the second a agent, the second b agent, and the nth agent if the nth agent is included)) is weighed into 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). In addition, among the respective components (e.g., non-aqueous epoxy compound (A)) that are raw materials constituting the first agent, the second agent, etc., the components other than the solvents and dispersion media (e.g., water) with a boiling point of less than 180°C under normal pressure in the first agent, the second agent, the second a agent, and the second b agent are referred to as "solid content".

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

[0130] ≪Anticorrosive coating, substrate with anticorrosive coating≫ The anticorrosive coating according to the present invention (hereinafter also referred to as "this coating") is formed from this kit, specifically, it is formed from this composition obtained from this kit or this composition produced by this method. This coating is preferably used as a substrate with an anticorrosive coating (hereinafter also referred to as "substrate with this coating") including the substrate and this coating. The substrate with this coating is a laminate having this coating and the substrate.

[0131] The material of the substrate is not particularly limited, and examples include steel (iron, steel, alloy iron, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, zinc plating, zinc spraying, etc.), and stainless steel (SUS304, SUS410, etc.). Also, when using, for example, mild steel (such as SS400) as the substrate, if necessary, it is desirable to perform substrate conditioning (e.g., adjusting so that the arithmetic mean roughness (Ra) is about 30 to 75 μm), such as polishing the surface of the substrate with grit blasting or the like. As the base material, a base material that has been subjected to pretreatment such as a cleaning treatment or a blasting treatment to remove rust, dirt, paint (old coating film), etc. adhered to the base material may also be used.

[0132] The base material is not particularly limited and can be used without limitation for base materials that require corrosion resistance. However, from the viewpoint of more effectively exerting the effects of using this composition, preferably, (steel) structures such as ships, offshore structures, plants, bridges, tanks, containers, etc. are exemplified.

[0133] The dry film thickness of this coating film is not particularly limited, but usually it is 10 to 400 μm, preferably 15 to 300 μm, from the viewpoint of obtaining a coating film having sufficient corrosion resistance.

[0134] The base material with this coating film is a laminate including this coating film and the base material, and an undercoat film (primer coating film) for the purpose of improving the adhesion to the base material and corrosion resistance, an intermediate coating film for the purpose of improving corrosion resistance, and a topcoat film excellent in weather resistance, aesthetics, etc. may be formed. Specifically, when using this composition as an alternative to a zinc primer, an intermediate coating film or a topcoat film may be formed on this coating film. Examples of the undercoat 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 paint compositions such as (meth)acrylic resin-based, epoxy resin-based, and urethane resin-based ones. Further, examples of the topcoat film include coating films formed from various topcoat paint compositions such as (meth)acrylic resin-based, (meth)acrylic silicone resin-based, urethane resin-based, silicone resin-based, and fluororesin-based ones. Also, by changing the composition, etc. of this composition, an undercoat film, an intermediate coating film, and a topcoat film may be formed with this composition.

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

[0136] <Step [1]> The coating method in the above Step [1] is not particularly limited, and examples thereof include spray coating such as airless spray coating and air spray coating, brushing, roller coating, and other conventionally known methods. Among these, spray coating is preferred in terms of being able to easily coat a large-area substrate such as the above-mentioned structure. During such coating, it is preferable to coat so that the dry film thickness of the obtained coating film falls within the above range.

[0137] The conditions for the spray coating may be appropriately adjusted according to the dry film thickness to be formed. For example, in the case of airless spray coating, the primary (air) pressure is preferably about 0.3 to 0.6 MPa, the secondary (paint) pressure is preferably about 10 to 15 MPa, and the gun moving speed is preferably about 50 to 120 cm / second.

[0138] The above coating is preferably carried out so that the dry film thickness of the present coating film formed in Step [2] falls within the above range. In this case, the present coating film with the desired film thickness may be formed by a single coating (one-coat), or the present coating film with the desired film thickness may be formed by two or more coatings (two or more coats). Note that two-coat means performing Step [1] on the present coating film obtained in Step [2] after performing Steps [1] and [2].

[0139] When coating the present composition on the substrate, in order to remove rust, grease, moisture, dust, salt, etc. on the substrate, and also to improve the adhesion of the obtained coating film to the substrate, if necessary, the surface of the substrate is preferably treated (for example, blast treatment (ISO8501-1 Sa2 1 / 2), treatment for removing oil and dust by degreasing, etc.). In addition, for the purpose of primary rust prevention, a shop primer or the like may be coated on the substrate.

[0140] <Step [2]> The drying conditions in the above-mentioned step [2] are not particularly limited and may be appropriately set according to the coating film formation method, the type of substrate, the use, the painting environment, etc. However, when drying at room temperature, the drying temperature is usually 5 to 35°C, and when forced drying is performed with a hot air dryer or the like, it is usually 30°C or higher and lower than 100°C, more preferably 40 to 80°C. According to this composition, the composition can be dried and cured even by such room temperature drying. The drying time varies depending on the drying method of the coating film. In the case of room temperature drying, it is, for example, about 1 day to 7 days, and in the case of forced drying, it is, for example, about 5 minutes to 60 minutes.

Examples

[0141] Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto.

[0142] [Example 1] As shown in Table 1, into a container, 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 a silane coupling agent (Note 8), 0.9 part by mass of an anti-sagging agent (Note 9), and 0.3 part by mass of an antifoaming agent (Note 10) were put, and stirred using a high-speed disper until uniform at room temperature (23°C), and then dispersed at 55 to 60°C for 30 minutes. Then, the first agent was prepared by cooling to 30°C or lower.

[0143] Also, into another container, 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 put, and stirred using a high-speed disper until uniform to prepare the second agent.

[0144] The prepared first agent and second agent were mixed at the mixing ratio (mass ratio) described in Table 1 before painting to prepare an anticorrosive paint composition. The explanations of each component described in Table 1 are shown in Table 2.

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

[0146] The viscosity at 23°C of each corrosion - resistant paint composition immediately after preparation in the Examples and Comparative Examples was measured using a Rheon viscometer (VT - 04F, manufactured by Rheon Co., Ltd.). The results are shown in Table 1.

[0147] [Table 1]

[0148] [Table 2]

[0149] [Preparation of Substrate (Test Plate) with Corrosion - Resistant Coating] A sand - blasted steel plate of SS400 with dimensions of 150 mm×70 mm×2.3 mm (thickness) (arithmetic mean roughness (Ra): 30 - 75 μm) was prepared. On the surface of this steel plate, the corrosion - resistant paint composition prepared as described above was applied using an air spray so that the dry film thickness was 70 μm. Next, the corrosion - resistant paint composition coated on the steel plate was dried at 60°C for 40 minutes, and then an aqueous acrylic resin top - coat paint (EKOMATE FINISH, manufactured by Nippon Paint Co., Ltd.) was applied using an air spray so that the dry film thickness was 40 μm. Thereafter, the coated aqueous acrylic resin top - coat paint was dried at 60°C for 30 minutes and then at 23°C for 7 days to prepare Test Plate 1.

[0150] Also, on the surface of a steel plate similar to the one used for Test Plate 1, the corrosion - resistant paint composition prepared as described above was applied using an air spray so that the dry film thickness was 80 μm. Next, the corrosion - resistant paint composition coated on the steel plate was dried at 60°C for 30 minutes and then at 23°C for 7 days to prepare Test Plate 2.

[0151] [Salt Spray Test] Based on JIS K 5600-7-1:1999, the salt spray test was carried out by holding the test plates 1 and 2 in a salt spray tester under the conditions of 5% by mass of salt water concentration, 35 °C of temperature, and 98% of relative humidity for 400 hours, and the corrosion resistance was evaluated according to the evaluation criteria described below. The results are shown in Table 3. Note that if the evaluation in this salt spray test is 3 or more, it can be said that there is no practical problem with the corrosion resistance. (Evaluation Criteria) 5: Neither rust nor swelling occurred. 4: No swelling occurred, but the area of rust on the substrate surface under the coating film is less than 0.03% of the entire substrate surface under the coating film. 3: A very small amount of small swelling occurred, and the area of rust on the substrate surface under the coating film is 0.03% or more and less than 0.1% of the entire substrate surface under the coating film. 2: Swelling occurred, and the area of rust on the substrate surface under the coating film is 0.1% or more and less than 0.3% of the entire substrate surface under the coating film. 1: Swelling occurred, and the area of rust on the substrate surface under the coating film is 0.3% or more of the entire substrate surface under the coating film.

[0152] <Composite Cycle Test> In accordance with ASTM D2803, a 25-cycle test was carried out using the test plates 1 and 2. The appearance of the test plates after the test was evaluated according to the same evaluation criteria as in the salt spray test. The results are shown in Table 3. Note that if the evaluation in this composite cycle test is 3 or more, it can be said that there is no practical problem with the corrosion resistance.

[0153]

Table 3

Claims

1. Step 1 of preparing the first agent using a non-aqueous epoxy compound (A); Step 2 of preparing the 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 and comprising wherein 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; wherein the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A method for producing a corrosion protection paint composition having a non-volatile content of 70% by volume or more.

2. Step 1 of preparing the first agent using a non-aqueous epoxy compound (A); Step 2a of preparing the second agent a using a water-dilutable component (B) containing an amine compound; Step 2b of preparing the second agent b using a non-aqueous component (C) containing an amine compound; Step 3' of mixing the first agent, the second agent a and the second agent b and comprising wherein 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; wherein the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A method for producing a corrosion protection paint composition having a non-volatile content of 70% by volume or more.

3. The method for producing a corrosion protection paint composition according to claim 1 or 2, wherein the viscosity of the corrosion protection paint composition measured at 23 °C is 7,000 mPa·s or less.

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

5. The method for producing a corrosion protection paint 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. The method for producing a corrosion protection paint 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 and containing wherein 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; wherein the non-aqueous component (C) containing the amine compound is a non-aqueous amine compound, A kit for a corrosion - resistant paint composition having a non - volatile content of 70% by volume or more.

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, wherein 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, A kit for a corrosion - resistant paint composition having a non - volatile content of 70% by volume or more.

9. A corrosion - resistant paint film formed from the kit for a corrosion - resistant paint composition according to Claim 7 or 8.

10. A substrate with a corrosion - resistant paint film, comprising a substrate and the corrosion - resistant paint film according to Claim 9.

11. A method for manufacturing a substrate with a corrosion - resistant paint film, comprising the following steps [1] and [2]. [1] A step of coating a substrate with a corrosion - resistant paint composition produced by the production method according to any one of Claims 1 to 6, or a corrosion - resistant paint composition obtained from the kit for a corrosion - resistant paint composition according to Claim 7 or 8 [2] A step of drying the corrosion - resistant paint composition coated on the substrate to form a corrosion - resistant paint film

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