Anticorrosion coating composition, anticorrosion coating film, substrate with anticorrosion coating film, and method for manufacturing the substrate with anticorrosion coating film.

Abstract

To provide an anticorrosive coating composition that can form an anticorrosive coating film with a well-balanced and excellent anticorrosive properties in combined environmental cycle tests, cathodic protection tests, and saltwater immersion tests. [Solution] A corrosion-resistant coating composition comprising a polyamidoamine (A), a polyetheramine-based polyamidoamine (B), a Mannich-modified amine (C), and an epoxy resin (D), wherein component (A) is a compound other than component (B), and is one or more compounds selected from the group consisting of TEPA polyamidoamine (a1) and DETA polyamidoamine (a2), and component (C) is a compound other than components (A) to (B), and is one or more compounds selected from the group consisting of phenalkamine (c1) and phenalkamide (c2), and the total content of components (A) to (C) is 7.0 to 25.0% by mass with respect to 100% by mass of the non-volatile content of the corrosion-resistant coating composition.

Description

[Technical Field]

[0001] The present invention relates to 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] Structures made of corrosive substrates such as steel are coated with an anti-corrosion coating film obtained from an epoxy resin-based anti-corrosion paint composition to suppress corrosion. The anticorrosion coating applied to each of the aforementioned structures may be required to have physical properties based on various standards, depending on the operating environment of the structure and the performance required of the structure. For example, anticorrosion coatings applied to offshore structures such as offshore wind power generation facilities may be required to have coating specifications and physical properties defined by standards such as ISO 20340 (2009), ISO 12944-9 (2018), and NORSOK 7th Edition (2022).

[0003] For example, Patent Document 1 describes a paint composition relating to an epoxy binder system as a paint composition that satisfies such standards. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2015-533870 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] For example, corrosion-resistant coatings used on substrates of marine structures and the like are exposed to much harsher operating environments than those on land, and are difficult to repair. Therefore, they are often required to have long lifespan and high durability in terms of corrosion resistance. They may also be required to exhibit corrosion resistance in long-term combined environmental cycle tests (UV irradiation + salt spray + low-temperature standing), cathodic protection tests (cathode peeling tests), and salt immersion tests. However, it was found that the anticorrosive coatings obtained from conventional epoxy resin-based anticorrosive coating compositions have room for improvement in at least one aspect of their corrosion resistance in these tests.

[0006] The present invention has been made in view of the above, and aims to provide a corrosion-resistant coating composition that can form a corrosion-resistant coating film that exhibits a good balance of corrosion resistance in the aforementioned combined environmental cycle test, cathodic protection test, and saltwater immersion test. [Means for solving the problem]

[0007] The inventors of the present invention have diligently studied to solve the above problems and have found that the above problems can be solved according to the following embodiments, and have completed the present invention. Embodiments of the present invention are shown below.

[0008] <1> A corrosion-preventive coating composition, The aforementioned anticorrosive coating composition contains a polyamidoamine (A), a polyetheramine-based polyamidoamine (B), a Mannich-modified amine (C), and an epoxy resin (D). The polyamidoamine (A) is a compound other than the polyamidoamine (B), and is one or more compounds selected from the group consisting of tetraethylenepentamine polyamidoamine (a1) and diethylenetriamine polyamidoamine (a2). The Mannich-modified amine (C) is a compound other than the polyamidoamine (A) and polyamidoamine (B), and is one or more compounds selected from the group consisting of phenalkamine (c1) and phenalkamide (c2). The total content of the polyamide amine (A), polyamide amine (B) and Mannich-modified amine (C) is 7.0 to 25.0% by mass based on 100% by mass of the nonvolatile components of the anticorrosive paint composition. Anticorrosive paint composition.

[0009] <2> The anticorrosive paint composition according to <1>, wherein the content of the nonvolatile components is 85 to 100% by mass.

[0010] <3> The anticorrosive paint composition according to <1> or <2>, further containing a reactive diluent (E). <4> The anticorrosive paint composition according to any one of <1> to <3>, further containing a silane coupling agent (F).

[0011] <5> Anticorrosive paint film formed from the anticorrosive paint composition according to any one of <1> to <4>.

[0012] <6> Substrate with an anticorrosive paint film, including the anticorrosive paint film according to <5> and a substrate. <7> Method for producing a substrate with an anticorrosive paint film, including the following steps [1] and [2]. [1] Step of coating a substrate with the anticorrosive paint composition according to any one of <1> to <4> [2] Step of drying the coated anticorrosive paint composition to form an anticorrosive paint film

Advantages of the Invention

[0013] According to the present invention, it is possible to provide an anticorrosive paint composition capable of forming an anticorrosive paint film that is excellently balanced in anticorrosion performance in a composite environment cycle (ultraviolet irradiation + salt water spray + low-temperature standing) test for a long time (e.g., 4200 hours), an electro-anticorrosion test (cathodic disbondment test), and a salt water immersion test. In the composite environmental cycle test, since the cold and heat processes are repeated, it is considered that a certain degree of flexibility is required for the anticorrosive coating film with excellent corrosion resistance in this test. However, in the cathodic disbondment test and the salt water immersion test, since immersion in water (salt water) is performed, such a flexible anticorrosive coating film tends to be inferior in corrosion resistance in the cathodic disbondment test and the salt water immersion test. That is, the composite environmental cycle test and the cathodic disbondment test and the salt water immersion test are in a trade-off relationship. According to the present invention, however, it is possible to form an anticorrosive coating film that is excellently balanced in corrosion resistance in such tests having a trade-off relationship. Therefore, such an anticorrosive coating composition can satisfy the coating specifications and physical properties defined by standards such as ISO 20340 (2009), ISO 12944-9 (2018), and NORSOK 7th Edition (2022), and thus is particularly suitably used for marine structures such as offshore wind power generation facilities.

Brief Description of the Drawings

[0014] [Figure 1] FIG. 1 is a schematic diagram of a scored test plate used in the cycle test and the salt water immersion test of the examples. [Figure 2] FIG. 2 is a schematic diagram showing nine locations where the length of rust was measured in the cycle test and the salt water immersion test of the examples. [Figure 3] FIG. 3 is a schematic diagram of a perforated test plate used in the cathodic disbondment test of the examples.

Modes for Carrying Out the Invention

[0015] In the following description, “(meth)acrylate” means “acrylate and / or methacrylate”, and “(meth)acryloyl” means “acryloyl and / or methacryloyl”. The numerical range A to B in the following description means A or more and B or less.

[0016] ≪Anticorrosive Coating Composition≫ The anticorrosion coating composition according to the present invention (hereinafter also referred to as "this composition") contains polyamidoamine (A) (hereinafter also referred to as "component (A)"; the same applies to other components), polyetheramine-based polyamidoamine (B), Mannich-modified amine (C), and epoxy resin (D). The aforementioned component (A) is a compound other than the aforementioned component (B), and is one or more selected from the group consisting of tetraethylenepentamine (TEPA) polyamidoamine (a1) and diethylenetriamine (DETA) polyamidoamine (a2). The aforementioned component (C) is a compound other than the aforementioned components (A) and (B), and is one or more selected from the group consisting of phenalkamine (c1) and phenalkamide (c2). The total content of components (A) to (C) is 7.0 to 25.0% by mass, relative to 100% by mass of the non-volatile content of this composition.

[0017] The total content of components (A) to (C) is 7.0% by mass or more, preferably 7.5% by mass or more, more preferably 8.0% by mass or more, 25.0% by mass or less, preferably 24.0% by mass or less, and more preferably 23.0% by mass or less, based on 100% by mass of the nonvolatile content of this composition, in order to provide a well-balanced and excellent corrosion protection in long-term combined environmental cycle tests, cathodic protection tests, and saltwater immersion tests, and to easily form a corrosion-resistant coating that is particularly excellent in long-term combined environmental cycle tests. When the upper limit of the total content of components (A) to (C) is within the above range, the present composition having a reaction ratio within the following range can be easily obtained, and a corrosion-resistant coating film with excellent adhesion to the topcoat film (especially polyurethane resin-based topcoat film) that can be formed can be easily created, with suppressed surface tackiness.

[0018] The total content of components (A) to (C) is preferably 20 to 120 parts by mass, more preferably 25 to 110 parts by mass, and even more preferably 30 to 100 parts by mass, per 100 parts by mass of the total of component (D), in order to easily form a corrosion-resistant coating that is well balanced and excellent in corrosion resistance in long-term combined environmental cycle tests, cathodic protection tests and saltwater immersion tests, and is particularly excellent in corrosion resistance in long-term combined environmental cycle tests.

[0019] In the present invention, the non-volatile content of the composition refers to the heat residue obtained when the composition is left at atmospheric pressure at 23°C for 24 hours, and then dried in a hot air dryer at 110°C for 1 hour to volatilize the solvent and the like. In this invention, the solid content refers to the residue remaining after heating when each raw material of the composition (e.g., component (A)) is dried at 135°C for 1 hour under normal pressure to volatilize the solvent, etc.

[0020] The non-volatile content in this composition is preferably 85% by mass or more, more preferably 88% by mass or more, and even more preferably 90% by mass or more. There is no particular upper limit, but for example it is 100% by mass, and preferably 99% by mass. Compositions with a non-volatile content within the aforementioned range can be described as high-solids compositions or solvent-free compositions, and can comply with painting specifications defined in standards such as ISO 20340 (2009), ISO 12944-9 (2018), and NORSOK 7th Edition (2022). Furthermore, if the non-volatile content in this composition is within the aforementioned range, it is possible to easily obtain a composition that has excellent drying properties, is less prone to dripping during painting, can form a thick film in a single coat, and has excellent painting workability. Furthermore, if the non-volatile content in this composition is less than 100% by mass, it is preferable that this composition is a so-called organic solvent type composition, different from an aqueous composition, and the water content in 100% by mass of this composition is preferably 0.5% by mass or less.

[0021] The reaction ratio calculated by the following formula (1) in this composition is preferably 0.3 to 1.5, more preferably 0.5 to 1.2, and even more preferably 0.7 to 1.0, from the viewpoint that it is possible to easily form an anticorrosive coating with excellent corrosion resistance, coating strength, and drying properties.

[0022] Reaction ratio = {(Amount of solid content of component (A) / Equivalent amount of active hydrogen in the solid content of component (A)) + (Amount of solid content of component (B) / Equivalent amount of active hydrogen in the solid content of component (B)) + (Amount of solid content of component (C) / Equivalent amount of active hydrogen in the solid content of component (C)) + (Amount of solid content of component reactive with component (D) / Equivalent amount of functional groups in the solid content of component reactive with component (D))} / {(Amount of solid content of component (D) / Equivalent amount of epoxy in the solid content of component (D)) + (Amount of solid content of component reactive with components (A) to (C) / Equivalent amount of functional groups in the solid content of component reactive with components (A) to (C))} ... (1)

[0023] Here, "components that are reactive with component (D)" include compounds having a primary or secondary amino group, and a specific example of this is the silane coupling agent (F) described below. Furthermore, the "component that is reactive with components (A) to (C)" in formula (1) above can be a compound having an epoxy group or a (meth)acryloyl group, and specific examples of such compounds include the reactive diluent (E), the silane coupling agent (F), and the polymerizable (meth)acrylate monomer. As the silane coupling agent (F), 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 (F) is reactive with component (D) or with components (A) to (C), and to calculate the reaction ratio.

[0024] 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.

[0025] The composition may be a one-component composition, but it is preferable to be a two-component or more composition from the viewpoint of excellent storage stability, and in this case it may be a three-component or more composition including a main agent, a curing agent and a third agent other than these, but it is more preferable to be a two-component composition consisting of a main agent and a curing agent. When the composition is a two-component or more composition, component (D) is usually blended into the main agent and components (A) to (C) are blended into the curing agent, and the composition can be prepared by mixing the main agent and the curing agent. The main component, hardener, and third component are usually stored, transported, and mixed immediately before use. Furthermore, the aforementioned two-component type composition can also be described as a kit containing each of the agents included in the composition (e.g., main agent, curing agent, or third agent).

[0026] <Ingredient (A)> This composition contains a polyamidoamine as component (A). Component (A) is a compound other than component (B) below, and is one or more compounds selected from the group consisting of tetraethylenepentamine (TEPA) polyamidoamine (a1) and diethylenetriamine (DETA) polyamidoamine (a2). Component (A) may consist of one type or two or more types.

[0027] The aforementioned component (a1) is not particularly limited, but examples include polyamidoamines obtained using TEPA and one or more acids. Specific examples include dehydration condensates of TEPA with carboxylic acids such as monobasic carboxylic acids or dimer acids, which have a reactive primary or secondary amino group in their molecule. The aforementioned component (a2) is not particularly limited, but examples include polyamidoamines obtained using DETA and one or more acids. Specific examples include dehydration condensates of DETA with carboxylic acids such as monobasic carboxylic acids or dimer acids, which have a reactive primary or secondary amino group in their molecule.

[0028] The monobasic carboxylic acid is not particularly limited, but examples include fatty acids of the C16, C18, and C19 types derived from oils and fats, especially soybean oil, tall oil, ricinoleic acid, or combinations thereof.

[0029] The aforementioned dimer acid is a dimer of an unsaturated fatty acid and usually contains small amounts of monomer or trimer. As unsaturated fatty acids, carboxylic acid compounds are preferred that have 12 to 24 carbon atoms, more preferably 16 to 18, including the carbon atoms of the carboxyl group, and that have one or more unsaturated bonds in one molecule. Examples of such unsaturated fatty acids include fatty acids with one unsaturated bond, such as oleic acid, elaidic acid, and cetoleic acid; fatty acids with two unsaturated bonds, such as linoleic acid; and fatty acids with three or more unsaturated bonds, such as linolenic acid and arachidonic acid. Furthermore, fatty acids obtained from plants and animals can also be used, and specific examples include soybean oil fatty acids, tall oil fatty acids, flaxseed oil fatty acids, and cottonseed fatty acids.

[0030] Component (A) may be a compound synthesized by conventionally known methods, or a commercially available product. Examples of such commercially available products include "ANCAMIDE 3419," "ANCAMIDE 506," and "SUNMIDE 75" (all manufactured by Evonik Specialty Chemicals (Nanjing) Co., Ltd.).

[0031] The amount of active hydrogen equivalent in the solid content of component (A) is preferably 30 to 300, more preferably 40 to 250, and even more preferably 50 to 200, from the standpoint that the reaction ratio calculated by formula (1) in this composition can be easily adjusted.

[0032] The content of component (A) is preferably 2.0 to 11.0% by mass, more preferably 2.5 to 10.5% by mass, and even more preferably 3.0 to 10.0% by mass, based on 100% by mass of the nonvolatile content of the composition, in order to easily form an anticorrosive coating that exhibits excellent corrosion resistance, particularly in long-term electrochemical corrosion protection tests and saltwater immersion tests.

[0033] <Ingredient (B)> This composition contains a polyetheramine-based polyamidoamine as component (B). Component (B) may consist of one type or two or more types.

[0034] The aforementioned component (B) is not particularly limited, but examples include polyamidoamines obtained using a polyoxyalkylene polyamine and one or more acids. Specific examples include dehydration condensates of a polyoxyalkylene polyamine with a carboxylic acid such as a monobasic carboxylic acid or a dimer acid, which have a reactive primary or secondary amino group in their molecule. Examples of the monobasic carboxylic acid and dimer acid include compounds similar to those described in the section for component (A) above.

[0035] Examples of the polyoxyalkylene polyamine include the polyoxyalkylene structure (-(RO) n Examples of amine compounds having -[R is an alkyl group, preferably an alkyl group having 2 to 6 carbon atoms, and n is a real number of 3 or more, preferably a real number of 3 to 70]) include polyoxyethylenediamine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxypropylene-polyoxyethylenediamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine.

[0036] Component (B) may be a compound synthesized by conventionally known methods, or a commercially available product. An example of such a commercially available product is "ANCAMIDE 910" (manufactured by Evonik Specialty Chemicals (Nanjing) Co., Ltd.).

[0037] The amount of active hydrogen equivalent in the solid content of component (B) is preferably 50 to 500, more preferably 100 to 400, and even more preferably 150 to 350, from the standpoint that the reaction ratio calculated by formula (1) in this composition can be easily adjusted.

[0038] The content of component (B) is preferably 0.5 to 9.0% by mass, more preferably 1.0 to 8.0% by mass, and even more preferably 2.0 to 7.0% by mass, based on 100% by mass of the nonvolatile content of the composition, in order to easily form a corrosion-resistant coating that exhibits excellent corrosion resistance, particularly in long-term combined environmental cycle tests.

[0039] <Ingredient (C)> This composition contains a Mannich-modified amine as component (C). Component (C) is a compound other than components (A) and (B), and is one or more compounds selected from the group consisting of phenalkamine (c1) and phenalkamide (c2). Component (C) may consist of one type or two or more types.

[0040] Phenalkamine (C1) is a compound obtained using alkylphenols such as cardanol, formaldehyde, and polyamines, and is a compound having a reactive primary or secondary amino group in its molecule. More specifically, it is a compound obtained by a Mannich reaction using 1 mole of alkylphenol, 2 moles of formaldehyde, and 2 moles of polyamine. Examples of the alkylphenols include compounds prepared from cashew nut shell liquid (CNSL). The polyamine is not particularly limited, and examples include compounds similar to those listed in the "Other Amine Compounds (K)" column below.

[0041] Phenalkamine (c1) may be a compound synthesized by conventionally known methods, or a commercially available product may be used. Examples of such commercially available products include "Cardolite NC-540" (manufactured by Cardolite Co.), "Cardolite NC-541" (manufactured by Cardolite Co.), "Ultra Lite 2009" (manufactured by Air Products), and "Cardolite NC-557" (manufactured by Cardolite Co.).

[0042] Examples of phenalkamides (C2) include compounds obtained using alkylphenols such as cardanol, formaldehyde, polyamines, and acids. Specific examples include dehydration condensates of phenalkamine with carboxylic acids such as monobasic carboxylic acids or dimer acids, and compounds having a reactive primary or secondary amino group in the molecule. Examples of the alkylphenol and polyamine include compounds of the alkylphenol and polyamine described in the column for phenalkamine (c1), and examples of the monobasic carboxylic acid and dimer acid include compounds similar to those described in the column for component (A).

[0043] The phenalcamide (c2) may be a compound synthesized by conventionally known methods, or a commercially available product may be used. Examples of such commercially available products include "Cardolite LITE 3040" (manufactured by Cardolite Co.) and "Cardolite LITE 3100" (manufactured by Cardolite Co.).

[0044] The amount of active hydrogen equivalent in the solid content of component (C) is preferably 30 to 300, more preferably 40 to 250, and even more preferably 50 to 200, from the standpoint that the reaction ratio calculated by formula (1) in this composition can be easily adjusted.

[0045] The content of component (C) is preferably 1.0 to 11.0% by mass, more preferably 1.5 to 10.5% by mass, and even more preferably 2.0 to 10.0% by mass, based on 100% by mass of the nonvolatile content of this composition, in order to easily form an anticorrosive coating that exhibits excellent corrosion resistance, particularly in long-term electrochemical corrosion protection tests and saltwater immersion tests.

[0046] <Ingredient (D)> This composition contains epoxy resin as component (D). Component (D) may consist of one type or two or more types.

[0047] Component (D) is not particularly limited, but examples include polymers or oligomers containing two or more epoxy groups, and polymers or oligomers produced by the ring-opening reaction of the epoxy groups.

[0048] Component (D) is preferably a non-aqueous epoxy resin. The term "non-aqueous" refers to a state in which the material does not freely mix with water, and is substantially insoluble in water; it can also be called a non-aqueous dispersion type. Specifically, if, at 23°C, epoxy resin and water are mixed so that the epoxy resin makes up 3% by mass, the mixture is thoroughly stirred, and the resulting 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 resin mixed with water is separated, settled, or suspended, then the epoxy resin is considered a non-aqueous epoxy resin.

[0049] Furthermore, if, in the aforementioned mixture, more than 10% by mass of the epoxy resin mixed with water is stably present in the water, and the mixture is maintained in an emulsion state, then the epoxy resin shall be a water-dilutable epoxy resin. Also, if, in the aforementioned mixture, more than 10% by mass of the epoxy resin mixed with water is stably present in the water, and the epoxy resin mixed with water is present in a state where the average particle diameter 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 resin shall be a water-soluble epoxy resin.

[0050] The epoxy equivalent of component (D) is preferably 200 or less, more preferably 100 to 200, and even more preferably 100 to 190, from the viewpoint of being able to easily form an anticorrosive coating film that is excellent in terms of paintability, adhesion to the substrate, water resistance, and corrosion resistance. In this specification, the epoxy equivalent is calculated based on JIS K 7236:2009.

[0051] The viscosity of component (D) at 25°C, measured with an E-type viscometer (TOKIMEC, FMD type, rotation speed: 60 rpm), is preferably 1,500 to 120,000 mPa·s, more preferably 3,000 to 30,000 mPa·s, from the viewpoint of easily forming an anticorrosive coating film with excellent paintability, adhesion to the substrate, water resistance, and corrosion resistance.

[0052] As component (D), a liquid epoxy resin that is liquid (fluid) at room temperature (e.g., 25°C) is preferred because it facilitates the uniform dispersion of other components other than component (D) used in the composition, has good reactivity with components (A) to (C), and allows for easy acquisition of the composition with a non-volatile content within the specified range.

[0053] Examples of component (D) include bisphenol-type epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, phenol novolac-type epoxy resins, cresol-type epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and epoxidized oil-based epoxy resins. Among these, bisphenol-type epoxy resins are preferred, and bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are more preferred, due to their ability to easily form an anticorrosive coating with excellent adhesion to the substrate and corrosion resistance.

[0054] Component (D) may be either a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, or both may be used. However, it is preferable to use a bisphenol A type epoxy resin and a bisphenol F type epoxy resin because they allow for the easy formation of a corrosion-resistant coating with excellent corrosion resistance. When bisphenol A type epoxy resin and bisphenol F type epoxy resin are used as component (D), the content of bisphenol F type epoxy resin relative to 100% by mass of the total of these is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 35% by mass, from the standpoint of easily obtaining a low viscosity composition.

[0055] Component (D) may be a compound synthesized by a conventionally known method, or a commercially available product. Examples of commercially available products include the bisphenol A type epoxy resin "E-028" (manufactured by Otake Akishin Chemical Co., Ltd., epoxy equivalent 180-190, solids content 100% by mass), the bisphenol F type epoxy resins "ADEKA Resin EP-4901" (manufactured by ADEKA Corporation, epoxy equivalent 170, solids content 100% by mass), "jER 807" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 160-175, solids content 100% by mass), and the novolac type epoxy resins "DEN 425" (manufactured by Olin Corporation, epoxy equivalent 169-175, solids content 100% by mass), "DEN 431" (manufactured by Olin Corporation, epoxy equivalent 172-179, solids content 100% by mass), and "DEN 438" (manufactured by Olin Corporation, epoxy equivalent 176-181, solids content 100% by mass).

[0056] The content of component (D) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on 100% by mass of the nonvolatile content of this composition, in order to easily form an anticorrosive coating film with excellent adhesion to the substrate, water resistance, and corrosion resistance.

[0057] <Other optional ingredients> This composition may, if necessary, contain other optional components besides components (A) to (D) mentioned above. Other optional components include, for example, reactive diluents (E), silane coupling agents (F), pigments (G), non-reactive diluents (H), anti-sagging / anti-settling agents (I), defoaming agents (J), other amine compounds (K), curing accelerators (L), organic solvents (M), (pigment) dispersants, and dehydrating agents. Each of the other optional components may be used individually or in combination of two or more types.

[0058] Furthermore, if the composition is of the type with two or more components, and if a component that is reactive with components (A) to (C) is used as the other optional component, it is preferable to incorporate that component into the main component, and if a component that is reactive with component (D) is used as the other optional component, it is preferable to incorporate that component into the curing agent. Furthermore, if the composition is of the type with two or more components, and if a component that does not react with components (A) to (C) or component (D) is used as the other optional component, the component may be incorporated into the main agent, into the curing agent, into both of these, or into the third agent.

[0059] [Reactive Diluent (E)] This composition may contain one or more reactive diluents (E) for purposes such as easily obtaining a low viscosity composition while keeping the non-volatile content within the aforementioned range. As the reactive diluent (E), an epoxy group-containing reactive diluent is preferred.

[0060] The epoxy group-containing reactive diluent is a compound other than component (D). Examples of the epoxy group-containing reactive diluent include epoxy compounds with a viscosity of 500 mPa·s or less at 25°C, as measured by an E-type viscometer (TOKIMEC, FMD type, rotation speed: 60 rpm). These diluents may be monofunctional or polyfunctional, but it is preferable to include a polyfunctional epoxy group-containing reactive diluent.

[0061] Examples of monofunctional epoxy group-containing reactive diluents include alkyl glycidyl ethers (preferred examples of alkyl groups: 1 to 13 carbon atoms), phenyl glycidyl ethers, o-cresyl glycidyl ethers, alkylphenyl glycidyl ethers (preferred examples of alkyl groups: 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms, e.g., methylphenyl glycidyl ether, ethylphenyl glycidyl ether, propylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether), phenol glycidyl ethers, alkylphenol glycidyl ethers, and phenol (EO). n Examples include glycidyl ethers (number of repeats n=3-20, EO:-C2H4O-), alkyl glycidyl esters (preferred examples of alkyl groups: 3-10 carbon atoms), and polyglycol glycidyl ethers.

[0062] Examples of polyfunctional epoxy group-containing reactive diluents include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, polyglycol diglycidyl ether, mono- or polyalkylene glycol diglycidyl ether (preferred examples of alkylene groups: 1 to 5 carbon atoms, e.g., ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether), trimethylolpropane triglycidyl ether, alkyl diglycidyl ether, and alkyl diglycidyl ester. Preferred examples of the alkyl group include alkyl groups having 3 to 10 carbon atoms, specifically, alkyl groups such as neopentyl group and 2-ethylhexyl group.

[0063] If the composition contains a reactive diluent (E), the amount of the reactive diluent (E) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the nonvolatile content of the composition, in order to easily form a corrosion-resistant coating that exhibits excellent corrosion resistance, particularly in long-term combined environmental cycle tests.

[0064] [Silane coupling agent (F)] This composition preferably contains one or more silane coupling agents (F). By using a silane coupling agent (F), it is possible to easily obtain this composition with low viscosity, and it is possible to easily form a corrosion-resistant coating with superior adhesion to the substrate, water resistance, saltwater resistance, and other corrosion-preventive properties.

[0065] The silane coupling agent (F) 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 composition.

[0066] The silane coupling agent (F) is, for example, formula: "X-SiMe n Y 3-n It is preferable that the compound is represented by "[n is 0 or 1, X represents 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 represents a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or ethoxy group)].

[0067] A commercially available product may be used as the silane coupling agent (F). 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).

[0068] When this composition contains a silane coupling agent (F), the content of the silane coupling agent (F) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the nonvolatile content of this composition, in order to easily form a corrosion-resistant coating that exhibits excellent corrosion resistance, particularly in long-term cathodic protection tests and salt immersion tests.

[0069] [Pigment (G)] This composition may contain one or more pigments (G). This composition may contain a coloring pigment (G1) to adjust the color tone of the formed anticorrosive coating film or to impart an arbitrary color tone, and it is preferable that it contains a coloring pigment (G1). Furthermore, to improve the properties of the formed anticorrosive coating film, such as water resistance and crack resistance, an extender pigment (G2) may be included, and it is preferable that the product contains an extender pigment (G2).

[0070] Examples of coloring pigments (G1) include various known organic or inorganic coloring pigments. Examples of organic coloring pigments include naphthol red and phthalocyanine blue. Examples of inorganic coloring pigments include carbon black, iron oxide (e.g., red iron oxide, yellow iron oxide), and titanium dioxide (titanium white). The coloring pigment (G1) may be one type or two or more types.

[0071] In this composition, a coloring agent other than the coloring pigment (G1), such as a dye, may be used together with the coloring pigment (G1) or in place of the coloring pigment (G1).

[0072] Examples of extender pigments (G2) include talc, silica, mica, clay, (settling) barium sulfate, (potassium) feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, condensed aluminum phosphate, aluminum phosphate, aluminum, magnesium carbonate, barium carbonate, and glass. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, (settling) barium sulfate, (potassium) feldspar, aluminum, and glass are preferred. Calcium carbonate and white carbon are also used as anti-sagging / anti-settling agents (I) and matting agents, respectively, as described later. As for the extender pigment (G2), it is preferable to include one or more flattened pigments, more preferably at least one selected from talc and mica, and even more preferably both talc and mica, because they tend to easily form corrosion-resistant coatings with excellent corrosion resistance. The extender pigment (G2) may be one type or two or more types. It is preferable to use three types of extender pigments (G2), such as (potassium) feldspar, talc, and mica, because they allow for the easy formation of a corrosion-resistant coating with excellent paintability and corrosion resistance.

[0073] If the composition contains pigment (G), the amount of pigment (G) is preferably 10 to 80% by mass, more preferably 15 to 65% by mass, and even more preferably 20 to 50% by mass, based on 100% by mass of the nonvolatile content of the composition, from the viewpoint of improving the aesthetics, opacity, corrosion resistance, water resistance, and mechanical properties of the formed anticorrosive coating film. If the composition contains a coloring pigment (G1), the amount of the coloring pigment (G1) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass, based on 100% by mass of the nonvolatile content of the composition, from the viewpoint of improving the aesthetics and opacity of the formed anticorrosive coating film. If the composition contains an extender pigment (G2), the amount of the extender pigment (G2) is preferably 5 to 80% by mass, more preferably 10 to 65% by mass, and even more preferably 15 to 50% by mass, based on 100% by mass of the nonvolatile content of the composition, from the viewpoint of improving the corrosion resistance, water resistance, and mechanical properties of the formed anticorrosive coating film.

[0074] [Non-reactive diluent (H)] This composition may contain one or more non-reactive diluents (H). A non-reactive diluent (H) is a compound that does not have functional groups that are reactive with epoxy groups and amino groups.

[0075] As the non-reactive diluent (H), a wide range of conventionally known materials can be used, including liquid hydrocarbon resins (including modified products of said liquid hydrocarbon resins) such as low boiling fractions obtained by thermal decomposition of naphtha, petroleum resins, xylene resins, and coumarone indene resins. Specific examples include the liquid hydrocarbon resins and flexibility-imparting resins described in Japanese Patent Publication No. 2006-342360, Japanese Patent Publication No. 9-268209, and Japanese Patent Publication No. 7-196793.

[0076] If the composition contains a non-reactive diluent (H), the content of the non-reactive diluent (H) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the composition.

[0077] [Anti-sagging agent / Anti-settling agent (I)] When applying this composition, the composition may contain one or more anti-sagging / anti-settling agents (I) to reduce the occurrence of dripping, suppress the occurrence of sediment during storage of the composition, and improve the agitability of the composition.

[0078] Examples of anti-sagging and anti-settling agents (I) include organic clay waxes (e.g., stearate salts, lecithin salts, alkyl sulfonates of Al, Ca, and Zn), organic waxes (e.g., polyethylene wax, oxidized polyethylene wax, amide wax, hydrogenated castor oil wax), mixtures of organic clay waxes and organic waxes, and synthetic fine silica. Among these, it is preferable that the composition contains at least one selected from polyethylene oxide wax and amide wax, as this composition has particularly excellent anti-sagging properties and can be easily obtained.

[0079] When this composition contains a drip-preventing agent / settling inhibitor (I), the amount of the drip-preventing agent / settling inhibitor (I) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of this composition, in order to easily obtain a composition that can reduce dripping and suppress the formation of sediment during storage.

[0080] [Antifoaming agent (J)] It is preferable that this composition contains one or more defoaming agents (J) because they can suppress the generation of foam during the manufacture or application of the composition, or can break the foam that has been generated in the composition, and can easily form a corrosion-resistant coating with desired physical properties.

[0081] Commercially available products may be used as the antifoaming agent (J), and examples of such commercial 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).

[0082] When the composition contains an antifoaming agent (J), the content of the antifoaming agent (J) 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 the composition, from the viewpoints that the generation of foam can be sufficiently suppressed and a corrosion-resistant coating film having desired physical properties can be easily formed.

[0083] [Other amine compound (K)] The composition may contain one or more other amine compounds (K). The other amine compound (K) is not particularly limited as long as it is an amine compound other than components (A) to (C) and a tertiary amine (an amine compound having only a tertiary amino group as an amino group), and examples include amine compounds used as curing agents for conventionally known epoxy compounds. An amine compound containing two or more amino groups in one molecule is preferred, and amine compounds such as aliphatic, alicyclic, aromatic, and heterocyclic amine compounds are preferred.

[0084] Examples of the aliphatic amine compound include alkylene polyamine, polyalkylene polyamine, and alkylaminoalkylamine.

[0085] 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 (EDA), 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.

[0086] Examples of the polyalkylene polyamine include compounds represented by the formula: "H2N-(C m H 2m NH) nCompounds represented by (H) (where m is an integer from 1 to 10, and n is an integer from 2 to 10, preferably an integer from 2 to 6) are examples, and specific examples include diethylenetriamine (DETA), dipropylenetriamine, triethylenetetramine (TETA), tripylenetetramine, tetraethylenepentamine (TEPA), tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0087] Examples of the alkylaminoalkylamine include those of the formula: "R 2 2N-(CH2)p-NH2" 2 These are independently hydrogen atoms or C1-C8 alkyl groups (where at least one R) 2 A is an alkyl group having 1 to 8 carbon atoms, and p is an integer from 1 to 6. Examples of compounds represented by ) include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0088] Other aliphatic amine compounds 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.

[0089] Specific examples of the aforementioned alicyclic amine compounds include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0090] Examples of the aromatic amine compounds 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 compounds 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.

[0091] Specific examples of the heterocyclic amine compounds include 1,4-diazacycloheptane, 1,4-bis(3-aminopropyl)piperazine, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0092] Other amine compounds (K) include modified products of the aforementioned amine compounds, such as fatty acid modified products of polyamidoamines (excluding components (A) and (B)), amine adducts with epoxy compounds, Mannich-modified amines (excluding component (C)), Michael adducts, ketimines, and aldimines.

[0093] If this composition contains another amine compound (K), the content of the other amine compound (K) is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, relative to 100% by mass of the nonvolatile content of this composition, in order to easily form a corrosion-resistant coating with excellent corrosion resistance.

[0094] [Curing accelerator (L)] This composition may contain one or more curing accelerators (L). Examples of the curing accelerator (L) include tertiary amines and polymerizable (meth)acrylate monomers. Specific examples of tertiary amines include triethanolamine, dialkylaminoethanol, triethylenediamine (1,4-diazabicyclo[2.2.2]octane), and 2,4,6-tris(dimethylaminomethyl)phenol. A commercially available example is "ANCAMINE K54" (manufactured by Evonik Specialty Chemicals (Nanjing) Co., Ltd., 2,4,6-tri(dimethylaminomethyl)phenol).

[0095] Examples of commercially available polymerizable (meth)acrylate monomers include "M-CURE 100," "M-CURE 200," "M-CURE 201," "M-CURE 300," and "M-CURE 400" (all manufactured by SARTOMER COMPANY, INC.).

[0096] When this composition contains a curing accelerator (L), the amount of the curing accelerator (L) is preferably 0.01 to 3% by mass relative to 100% by mass of the non-volatile content of this composition, in order to easily form a corrosion-resistant coating film with excellent curability and adhesion to the substrate.

[0097] [Organic solvent (M)] This composition may use one or more organic solvents (M). Examples of the organic solvent (M) 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 (poly)ethylene glycol or (poly)propylene glycol and butyl cellosolve, ester solvents such as butyl acetate, alcohol solvents such as isopropanol, isobutyl alcohol, n-butanol, methoxypropanol, and benzyl alcohol, and aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, and methylcyclohexane.

[0098] If the composition contains an organic solvent (M), the content of the organic solvent (M) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the composition.

[0099] <Method for producing this composition> This composition can be prepared using the same apparatus and means as known general anticorrosive paints. For example, it can be produced by adding components (A) to (D), and any other optional components as needed, all at once or sequentially, and mixing them. During the mixing process, heating or cooling may be performed depending on the season, environment, etc.

[0100] <<Corrosion-resistant coating, substrate with corrosion-resistant coating, and method for manufacturing the substrate with corrosion-resistant coating>> The anticorrosion coating film according to the present invention (hereinafter also referred to as "the coating film") is formed from the composition and can usually be obtained by drying the composition. The coating film is usually formed on a substrate and used as a substrate with the coating film, having the substrate and the coating film. A preferred method for manufacturing a substrate coated with this coating includes a step of applying the composition to at least a portion of the substrate and then drying it, and preferably a step of coating the substrate with the composition [1] and a step of drying the coated composition to form a corrosion-resistant coating [2]. This method can also be called a method for corrosion protection of a substrate.

[0101] The aforementioned base material is not particularly limited, but since this composition is preferably used in a wide range of industrial fields such as ships, fishing materials, marine structures, and underwater structures to prevent corrosion of the base material over a long period of time, the base material may be, for example, ships (e.g., large steel ships such as container ships and tankers, fishing boats, FRP ships, wooden ships, yachts, etc., especially the hull plating from the waterline to the bottom. This includes both newly built and repaired ships), fishing materials (e.g., ropes, fishing nets, fishing gear, floats, buoys), and sea Examples include offshore structures (e.g., offshore (wind) power generation facilities, port facilities), underwater structures (e.g., oil pipelines, water intake pipes, circulating water pipes, water supply and drainage pipes for factories and thermal / nuclear power plants, submarine cables, seawater utilization equipment (seawater pumps, etc.), mega-floats, port roads, underwater tunnels, port facilities, and various underwater civil engineering structures in canals and waterways), and items used underwater or on the water (e.g., diving suits, goggles, swimwear, underwater lights, underwater sensors, oxygen tanks, torpedoes). Among these, offshore structures are more preferred, and offshore (wind) power generation facilities are even more preferred.

[0102] 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.).

[0103] The substrate may be one which has been treated as necessary to remove rust, oil, moisture, dust, slime, salt, etc., and to improve the adhesion of the formed rust-preventive coating film (for example, blasting (ISO8501-1 Sa2 1 / 2), power tool treatment (ISO8501-1 St3, St2), friction method, degreasing to remove oil and dust). Furthermore, when using, for example, mild steel (SS400, etc.) as the substrate, it is desirable to prepare the substrate surface by polishing it with grit blasting or the like (e.g., adjusting it so that the arithmetic mean roughness (Ra) is approximately 30 to 75 μm) as necessary.

[0104] Furthermore, the substrate may be a substrate having a conventionally known anticorrosion coating or rust-preventive coating (e.g., an organic zinc-rich coating), or a primer coating, or it may be a substrate on which the coating is formed. The object that the coating comes into direct contact with is not particularly limited.

[0105] The method for providing the composition on at least a portion of the substrate is not particularly limited, but examples include painting the composition onto the substrate or immersing the substrate in the composition (impregnating the substrate with the composition). Examples of painting methods include known methods such as using brushes, rollers, and sprayers.

[0106] Methods of painting using spray include, for example, air spray painting, airless spray painting, and electrostatic spray painting. The aforementioned electrostatic spray coating, also simply called electrostatic painting, generally involves applying a high voltage (usually around tens of thousands of volts) to atomize the paint using a spray gun or other spraying device, thereby imparting a positive or negative charge to the paint particles. In this process, the object to be painted (workpiece) is grounded, and the charged paint particles are attracted to and adhere to the workpiece surface by electrostatic force. Electrostatic spray painting can offer several advantages, including improved coating efficiency, reduced paint loss, suppression of paint dust scattering, and better adaptation to complex shapes (allowing paint to easily penetrate uneven surfaces and the back surface). When applying electrostatic spray painting, it is important to consider the conductivity of the paint, humidity control, safety measures (handling high voltages), and the grounding design of the object being painted.

[0107] The drying method mentioned above includes, for example, leaving the product at room temperature (e.g., 25°C) for about 0.5 to 14 days, more preferably for about 1 to 7 days. The drying may be carried out under heating or while blowing air.

[0108] The thickness of the coating film after drying can be arbitrarily selected depending on the application and duration of use, but for example, a thickness of approximately 30 to 1,000 μm is preferred. A method for producing a coating film of this thickness is to apply the composition in one to multiple coats, preferably 10 to 800 μm, more preferably 30 to 600 μm, per coating application.

[0109] Depending on the intended use and specifications of this coating, a conventionally known topcoat (e.g., a polyurethane resin-based topcoat) may be formed on top of this coating, or a further topcoat may be formed from this composition on top of this coating. These topcoats may be one layer or two or more layers. When a topcoat is formed on the coating film using the composition, the composition used to form the topcoat may be the same composition used to form the coating film, or it may be a different composition (e.g., a composition with a different color tone) from the composition used to form the coating film. [Examples]

[0110] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0111] [Examples 1-11, Comparative Examples 1-6] The main ingredient was prepared by using the ingredients listed in the "Main Ingredient" column of Table 1 below in the amounts (numerical value, parts by mass) shown in Table 1 below, dispersing them uniformly at room temperature (23°C) using a high-speed disperser, then heating to 60-65°C, and finally cooling to below 30°C. Furthermore, a hardening agent was prepared by mixing the raw materials shown in the hardening agent column of Table 1 below with the proportions (numerical values, parts by mass) shown in Table 1 below, using a high-speed disperser at room temperature and atmospheric pressure. The prepared main component and hardener were mixed before painting to create the anticorrosive paint composition. Table 2 shows the details of the raw materials used in the examples and comparative examples.

[0112] <Method for measuring the solid content of each raw material> One g of each raw material was weighed into a flat-bottomed dish, spread evenly using a wire of known mass (x g), and dried at 135°C for one hour under atmospheric pressure. The mass of the heat residue and the wire (y g) was then measured. The solid content (mass %) of each raw material was calculated using the following formula. Solid content of raw material = (yx) × 100

[0113] <Method for measuring the non-volatile content of anticorrosive paint compositions> One g of the prepared anticorrosive coating composition (the composition immediately after mixing the main component and the hardener component) was weighed into a flat-bottomed dish, spread evenly using a wire of known mass (x g), left at 23°C for 24 hours under normal pressure, and then dried at 110°C for 1 hour. After that, the mass of the heat residue and the wire (y g) was weighed. The non-volatile content (mass %) of the anticorrosive coating composition was calculated using the following formula. Non-volatile content of anticorrosive coating composition = (yx) × 100

[0114] <Preparation of test panels with corrosion-resistant coating> A test plate with an anticorrosive coating was prepared by applying each anticorrosive coating composition prepared in the examples and comparative examples to a sandblasted steel plate (150 mm long x 70 mm wide x 2.3 mm thick) using an airless sprayer to a dry film thickness of 300 μm, drying it at 23°C for 1 day, and then applying the same anticorrosive coating composition to the dried surface to a dry film thickness of 300 μm, drying it at 23°C for 7 days to form an anticorrosive coating film.

[0115] <Cycle Testing> The cyclic aging test was conducted in accordance with ISO 12944-9(2018). Specifically, it was performed as follows: A 2mm wide cut was made in the fabricated test plate with a corrosion-resistant coating, reaching a depth from the corrosion-resistant coating to the sandblasted steel plate, as shown in Figure 1. Note that the width (thickness) of cut 11 in Figure 1 is 2mm. Using a Q-lab Co. ultraviolet fluorescent lamp type accelerated weathering tester (QUV), the aforementioned incised test plate with a corrosion-resistant coating was subjected to the following procedure: irradiation with ultraviolet light (UVA-340) for 4 hours at 60±3℃, as per ISO 16474-3(2021) method A cycle 1, followed by standing at 50±3℃ in a humid environment for 4 hours. This constituted one cycle, and this cycle was repeated for 72 hours (9 cycles) (Stage 1). Using a salt spray tester (STP-120) manufactured by Suga Test Instruments Co., Ltd., the corrosion-resistant coated test plate that underwent the first stage of testing was sprayed with 50 g / L of salt solution for 72 hours at 35 ± 2°C in accordance with ISO 9227 (2012) (second stage). The test plates with the corrosion-resistant coating that underwent the second stage of testing were washed with deionized water and left to stand in a constant temperature chamber at -20±2℃ for one day while still wet (third stage). The process described above, from the first to the third stage, was considered one cycle, and this was repeated 25 times (4,200 hours).

[0116] After repeating the process 25 times, the paint film around the cut was removed. As shown in Figure 2, the length of the rust perpendicular to the cut 11 was measured at a total of nine locations (indicated by the dotted lines in Figure 2): the center 20 of the cut 11 and four locations 5 mm to the left and right of the center 20. The length of the measured rust was divided by the width of the initial cut (2 mm), and the arithmetic mean of the lengths at nine points was calculated and evaluated according to the evaluation criteria below. The results are shown in Table 1. A pass / fail rating in the cycle test is determined by a score of 3 or 2.

[0117] (Evaluation Criteria) 3: Arithmetic mean is less than 6.5 mm 2: Arithmetic mean is 6.5 mm or more, but less than 8 mm. 1: Arithmetic mean is 8mm or more

[0118] <Cathode peeling test> The cathode peeling test was performed in accordance with ISO 15711 (2003). Specifically, it was carried out as follows: As shown in Figure 3, a 6 mm diameter hole 30 was drilled in the corrosion-resistant coating of the fabricated test plate, reaching a depth that reached the sandblasted steel plate. Artificial seawater was prepared using aquamarine manufactured by Yashu Pharmaceutical Co., Ltd. and deionized water. A potentiometer / galvanostat (HA-151B), platinum electrode (HX-C1), and silver / silver chloride electrode (HX-RAg) manufactured by Meiden Hokuto Co., Ltd. were used, and current was applied for 4200 hours under conditions of 23±2℃ and -1050mV.

[0119] The peel length of the anticorrosive coating from the center of the hole was measured at two locations on the upper and lower sides of the test plate, parallel to the vertical direction of the hole, and at two locations on the right and left sides of the test plate, parallel to the horizontal direction of the hole, and the arithmetic mean A (mm) of the peel lengths at these four locations was calculated. Using this value A, the total area B (mm) was calculated from the following formula. 2 ) is calculated, and using the value of B, the peeling area C (mm²) is calculated from the following formula. 2 The value of C was calculated, and then the peeling length D (mm) was calculated using the following formula. The calculated peeling width and peeling length D (mm) were evaluated according to the following evaluation criteria. The results are shown in Table 1. A pass in the cathode peeling test is defined as a score of 3 or 2.

[0120] Total area B (mm²) 2 ) = 3.14 × A × A / 4 Peeling area C (mm²) 2 )=B-28.3 Peel length D (mm) = 2 × √(C / 3.14)

[0121] (Evaluation Criteria) 3: Peel length D is less than 15 mm 2: Peeling length D is 15 mm or more and less than 20 mm. 1: Peel length D is 20 mm or more

[0122] <Saltwater immersion test> The saltwater immersion test was conducted in accordance with JIS K 5600-6-1:2016. Specifically, it was carried out as follows: A 2mm wide cut was made in a test plate with an anti-corrosion coating, reaching the depth of the sandblasted steel plate, as shown in Figure 1. Note that the width (thickness) of cut 11 in Figure 1 is 2mm. A 3% saline solution was prepared using deionized water. The test plate with the anti-corrosion coating and the aforementioned cuts was immersed in a 3% saline solution prepared in a 40°C constant temperature oven for 4200 hours. Except for using a test plate that had been immersed for 4200 hours, the length of rust at nine locations was measured, the arithmetic mean was calculated, and the results were evaluated according to the evaluation criteria below, as in the cycle test described above. The results are shown in Table 1. A pass / fail rating was given if the evaluation criteria for the cycle test was 3 or 2.

[0123] (Evaluation Criteria) 3: Arithmetic mean is less than 3 mm 2: The arithmetic mean is 3 mm or more, but less than 6 mm. 1: Arithmetic mean is 6 mm or more

[0124] [Table 1]

[0125] [Table 2] [Explanation of Symbols]

[0126] 10: Test plate 11: Cut 20: Center of the cut 30: Hole

Claims

1. A corrosion-preventive coating composition, The aforementioned anticorrosive coating composition contains a polyamidoamine (A), a polyetheramine-based polyamidoamine (B), a Mannich-modified amine (C), and an epoxy resin (D). The polyamidoamine (A) is a compound other than the polyamidoamine (B), and is one or more compounds selected from the group consisting of tetraethylenepentamine polyamidoamine (a1) and diethylenetriamine polyamidoamine (a2). The Mannich-modified amine (C) is a compound other than the polyamidoamine (A) and polyamidoamine (B), and is one or more compounds selected from the group consisting of phenalkamine (c1) and phenalkamide (c2). The total content of the polyamidoamine (A), polyamidoamine (B), and Mannich-modified amine (C) is 7.0 to 25.0% by mass, relative to 100% by mass of the non-volatile content of the anticorrosive coating composition. Anticorrosion coating composition.

2. The anticorrosion coating composition according to claim 1, wherein the non-volatile content is 85 to 100% by mass.

3. The anticorrosion coating composition according to claim 1, further comprising a reactive diluent (E).

4. The anticorrosion coating composition according to claim 1, further containing a silane coupling agent (F).

5. A corrosion-resistant coating film formed from the corrosion-resistant coating composition according to any one of claims 1 to 4.

6. A substrate with a corrosion-resistant coating, comprising the corrosion-resistant coating and the substrate according to claim 5.

7. A method for manufacturing a substrate with a corrosion-resistant coating, comprising the following steps [1] and [2]. [1] A step of applying the anticorrosive coating composition according to any one of claims 1 to 4 to the substrate. [2] A step of drying the painted anticorrosive coating composition to form an anticorrosive coating film.

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