Corrosion-resistant composition 1 and corrosion-resistant coating composition

Abstract

To provide a corrosion-resistant composition 1 which can yield a corrosion-resistant coating composition with a long pot life and can also form a corrosion-resistant coating layer with superior corrosion resistance.SOLUTION: A corrosion-resistant composition 1 contains an amine compound (A), a divalent or higher polyvalent carboxylic acid (B), and water (C).SELECTED DRAWING: None

Description

[Technical field]

[0001] One embodiment of the present invention relates to an anticorrosive composition 1, an anticorrosive coating composition, an anticorrosive coating film, a substrate with an anticorrosive coating film, or a method for producing the same. [Background technology]

[0002] 2. Description of the Related Art Solvent-based anticorrosive paints are applied to substrates such as ships, marine structures, plants, bridges, and land tanks in order to ensure their long-term use.

[0003] In recent years, with the strengthening of organic solvent emission regulations aimed at considering the natural environment and the painting work environment, etc., progress has been made in reducing the VOC (volatile organic compound) content of solvent-based paints such as those mentioned above. One method of reducing VOC content is the conversion of paints to water-based paints. For the purpose of making such paints water-based, for example, Patent Document 1 describes the use of a curing agent component containing a water-soluble amine resin and water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-221256 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a curing agent component used for the purpose of making a paint water-based, as described in Patent Document 1 and the like, is used, the anticorrosive coating composition obtained by mixing it with the main component has a short pot life, and the anticorrosive coating film obtained after reaction with the main component does not have sufficient anticorrosive properties, and there is room for improvement in these respects.

[0006] One embodiment of the present invention provides an anticorrosion composition 1 that can provide an anticorrosion coating composition having a long pot life and can form an anticorrosion coating film having excellent corrosion prevention properties. [Means for solving the problem]

[0007] As a result of extensive research into methods for solving the above problems, the present inventors have found that the above problems can be solved by the following configuration examples, and have thus completed the present invention. A configuration example of the present invention is as follows.

[0008] <1> An amine compound (A); A divalent or higher polyvalent carboxylic acid (B), Water (C) 1. A corrosion prevention composition comprising:

[0009] <2> The amine compound (A) comprises a water-dilutable amine compound; <1> The corrosion prevention composition 1 described in

[0010] <3> <1> or <2> The corrosion inhibitor composition 1 according to the present invention A corrosion prevention composition 2 containing a non-aqueous epoxy compound (D); 1. An anticorrosive coating composition comprising:

[0011] <4> The anticorrosive composition 2 further contains a polycarbodiimide compound. <3> The anticorrosive coating composition according to claim 1.

[0012] <5> The non-aqueous epoxy compound (D) is liquid at 23°C and has a bisphenol skeleton. <3> or <4> The anticorrosive coating composition according to claim 1.

[0013] <6> The anticorrosive composition 2 further contains a silane coupling agent. <3> ~ <5> 13. The anticorrosive coating composition according to claim 12,

[0014] <7> <3> ~ <6> 13. An anticorrosive coating film formed from the anticorrosive coating composition according to any one of claims 1 to 12.

[0015] <8> Substrate and <7> and a substrate having the anticorrosive coating film according to claim 1.

[0016] <9> A method for producing a substrate with a corrosion-resistant coating, comprising the following steps [1] and [2]: [1] The base material is <3> ~ <6> A step of applying the anticorrosive coating composition according to any one of the preceding claims. [2] A step of drying the anticorrosive coating composition applied to the substrate to form an anticorrosive coating film. Effect of the Invention

[0017] According to one embodiment of the present invention, it is possible to obtain an anticorrosive coating composition having a long pot life, and to provide an anticorrosive composition 1 capable of forming an anticorrosive coating film having excellent corrosion prevention properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] <Corrosion prevention composition 1> The anticorrosion composition 1 according to one embodiment of the present invention (hereinafter also referred to as "the composition 1") is not particularly limited as long as it contains an amine compound (A), a divalent or higher polyvalent carboxylic acid (B), and water (C), but may also contain other components described below. Since the present composition 1 is usually used when an amine compound reacts and hardens, it can also be called a hardener component of an anticorrosive coating composition containing a base component and a hardener component, and is preferably a hardener component of an epoxy compound, and more preferably a hardener component of a non-aqueous epoxy compound.

[0019] [Amine compound (A)] The amine compound (A) is not particularly limited, and any known amine compound that has been used as a curing agent for epoxy compounds and the like can be used. The amine compound (A) used in preparing the present composition 1 may be one type, or two or more types.

[0020] The amine compound (A) 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 an amine compound containing two or more amino groups in one molecule is preferred, and an aliphatic, alicyclic, aromatic, heterocyclic, or other amine compound is preferred.

[0021] Examples of the aliphatic amine compound include alkylene polyamines, polyalkylene polyamines, and alkylamino alkyl amines.

[0022] The alkylene polyamine may be, for example, a compound represented by the formula: 1 -NH2" (R 1 is a divalent hydrocarbon group having 1 to 12 carbon atoms. Specific examples thereof 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.

[0023] The polyalkylene polyamine may, for example, be a compound represented by the formula: "H2N-(C m H 2m N.H. n Specific examples of the compound include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0024] The alkylaminoalkylamine is, for example, a compound represented by the formula: 2 2N-(CH2) p -NH2" (R 2 are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (provided that at least one of R 2is an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 6. Specific examples thereof include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0025] Examples of aliphatic amine compounds other than these include tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylenepolyamines (particularly, diethylene glycol bis(3-aminopropyl)ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), menthenediamine (MDA), o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), and 1-[2'-(2''-aminoethylamino)ethyl]piperazine.

[0026] Specific examples of the alicyclic amine compound include cyclohexanediamine, diaminodicyclohexylmethane (particularly, 4,4'-methylenebiscyclohexylamine), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0027] Examples of the aromatic amine compound include aromatic polyamine compounds having two or more primary amino groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Specific examples of the aromatic amine compound include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and diethylmethylbenzenediamine.

[0028] Specific examples of the heterocyclic amine compound include 1,4-bis(3-aminopropyl)piperazine, 1,4-diazacycloheptane, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0029] The amine compound (A) may further include modified products of the above-mentioned amine compounds, such as fatty acid modified products such as polyamidoamines, amine adducts with epoxy compounds, Mannich modified products (e.g., Mannich modified amines having a phenol-derived skeleton (phenalkamine, phenalkamide, etc.)), Michael adducts, ketimines, and aldimines. Among these, polyamidoamines, amine adducts with epoxy compounds, and Mannich modified amines having a phenol-derived skeleton are preferred.

[0030] As the amine compound (A) used in preparing the present composition 1, a water-dilutable amine compound or a non-aqueous amine compound may be used. However, from the viewpoint of being able to easily form an anticorrosive coating film having excellent corrosion prevention properties and drying properties, it is preferable to use a water-dilutable amine compound, and it is more preferable to use a water-dilutable amine compound and a non-aqueous amine compound.

[0031] Here, whether the amine compound is a water-dilutable amine compound or a non-aqueous amine compound is determined based on the state of the raw material of the amine compound used when preparing the present composition 1 (if a commercially available product is used, the commercially available product). The water-dilutable amine compound refers to an epoxy-curable amine compound that is dissolved or emulsified and dispersed in a relatively large amount in a dispersion medium containing water (hereinafter also referred to as an "aqueous medium"). Specifically, first, the raw material of the amine compound used in preparing the present composition 1 is mixed with water, or the solvent and dispersion medium of the raw material of the amine compound are volatilized to prepare a mixed liquid so that the solid content is 50 mass% at 23°C. Then, the mixed liquid is thoroughly stirred, and even after leaving it at rest for 1 hour at 23°C, if 80 mass% or more of the solid content of the raw material is stably present in water, the raw material is regarded as a water-dilutable amine compound. Note that an amine compound with a solid content of less than 50 mass% is adjusted to 50 mass% using an evaporator or the like. The non-aqueous amine compound refers to an epoxy-curable amine compound that is not freely miscible with water, and is essentially insoluble in water. Specifically, when the raw material of the amine compound used in preparing the present composition 1 is mixed with water so that the solid content is 3 mass% at 23°C, the mixture is thoroughly stirred, and left to stand at 23°C for 1 hour, and the resulting mixture is not in a homogeneous state, and 90 mass% or more of the solid content of the raw material is separated, precipitated, or floated, the raw material is defined as a non-aqueous amine compound in this specification.

[0032] Specific examples of raw materials for amine compounds corresponding to water-dilutable amine compounds include water-soluble amine compounds, aqueous solutions of amine compounds, aqueous dispersions of amine compounds (e.g., amine emulsions), and self-emulsifying amine compounds. Among these, it is preferable to use amine emulsions and / or self-emulsifying amine compounds because they are easy to handle and make it easy to prepare the present composition 1. As the amine compound (A) used in preparing the present composition 1, from the viewpoint of being able to easily form an anticorrosive coating film having excellent corrosion prevention and moisture resistance, it is preferable to use at least one selected from an amine emulsion and a self-emulsifying amine compound, and a non-aqueous amine compound, and it is more preferable to use an amine emulsion, a self-emulsifying amine compound, and a non-aqueous amine compound.

[0033] Specific examples of the amine emulsion include hydrophilic amines obtained by reacting the amine compound with a glycidyl ether of a polyalkylene glycol, a polyoxyalkylene amine, an epoxy compound, or the like; amines having an amide structure obtained by using a fatty acid and the amine compound; and amines that have been given emulsifying ability by neutralizing the amine compound with an acid or mixing it with an emulsifier, and are (forcefully) dispersed in water.

[0034] The self-emulsifying amine compound is an amine compound that has the ability to emulsify by mixing with an aqueous medium described below without mixing with an acid or an emulsifier.Specific examples include hydrophilic amines obtained by reacting the amine compound with the glycidyl ether of polyalkylene glycol, polyoxyalkyleneamine, and epoxy compound, and amines having an amide structure obtained by using fatty acid and the amine compound.

[0035] The active hydrogen equivalent of the solid content of the amine emulsion and the self-emulsifying amine compound is preferably 50 or more, more preferably 60 or more, and is preferably 200 or less, more preferably 190 or less, from the viewpoint of being able to easily form an anticorrosive coating film having excellent curing properties and anticorrosive properties, etc.

[0036] The amine emulsion preferably contains at least one selected from polyamidoamine, an amine adduct with an epoxy compound, and a Mannich-modified amine having a phenol-derived skeleton, and it is more preferable to use a polyamidoamine in combination with an amine adduct with an epoxy compound and / or a Mannich-modified amine having a phenol-derived skeleton.

[0037] The self-emulsifying amine compound preferably contains a polyamidoamine.

[0038] The active hydrogen equivalent of the solid content of the amine adduct with the epoxy compound and the Mannich-modified amine having a phenol-derived skeleton is preferably 140 or more, more preferably 150 or more, and is preferably 200 or less, more preferably 190 or less, from the viewpoint of easily forming a corrosion-resistant coating film having excellent curing properties and corrosion resistance, etc.

[0039] The active hydrogen equivalent of the solid content of the polyamidoamine is preferably smaller than the active hydrogen equivalent of the solid content of the amine adduct with the epoxy compound and the Mannich-modified amine having a phenol-derived skeleton, from the viewpoint of easily obtaining a uniformly mixed composition 1, and is preferably 50 or more, more preferably 60 or more, and is preferably 130 or less, more preferably 120 or less.

[0040] The amine emulsion is a dispersion (emulsion) in which an amine compound is dispersed in an aqueous medium. The aqueous medium is not particularly limited as long as it contains water, but the water content in the aqueous medium is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass.

[0041] The aqueous medium may contain a medium other than water that has a boiling point of less than 180° C. under normal pressure, and examples of such a medium include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol monopropyl ether. These may be used alone or in combination.

[0042] The amine emulsion can be prepared by emulsifying the amine compound with one or more surfactants to form an emulsion.

[0043] As the amine emulsion and the self-emulsifying amine compound, those produced by a conventionally known method may be used, or commercially available products may be used. Commercially available amine emulsions include, for example, "Epilink 701" (manufactured by Evonik) and "Cardolite NX-8401" (manufactured by Cardolite). Furthermore, an example of a commercially available self-emulsifying amine compound is "Jointmide 3506" (manufactured by Yun Teh Industrial Co., Ltd.).

[0044] The nonaqueous amine compound is preferably an amine compound having a molecular weight of 3,000 or less, more preferably 2,500 or less, and having a cyclic structure, from the viewpoints of being able to easily form an anticorrosive coating film having excellent anticorrosive properties and being able to easily obtain an anticorrosive coating composition having a low viscosity.

[0045] The active hydrogen equivalent of the solid content of the nonaqueous amine compound is preferably 30 or more, more preferably 40 or more, and is preferably 200 or less, more preferably 150 or less, from the viewpoint of being able to easily form an anticorrosive coating film having excellent curability and anticorrosive properties.

[0046] As the non-aqueous amine compound, a compound obtained by a conventionally known method or a commercially available product may be used. Examples of commercially available products include "Ancamine 2280" (manufactured by Evonik) and "ETHACURE 100plus" (manufactured by Albemarle).

[0047] The solid content of the amine compound (A) is preferably 70 mass % or more, more preferably 80 mass % or more, relative to 100 mass % of the solid content of the present composition 1, from the viewpoint of being able to easily form an anticorrosive coating film having excellent corrosion prevention properties and drying properties, and is preferably 95 mass % or less, more preferably 90 mass % or less.

[0048] When a water-dilutable amine compound is used in preparing composition 1, the amount of the solid content of the water-dilutable amine compound used is preferably 45 mass % or more, more preferably 50 mass % or more, relative to 100 mass % of the solid content of composition 1, from the viewpoint of easily forming an anticorrosive coating film that is excellent in anticorrosive properties and drying properties, and is preferably 95 mass % or less, more preferably 90 mass % or less.

[0049] When preparing composition 1, an amine emulsion containing an amine adduct with the epoxy compound and / or a Mannich-modified amine having a phenol-derived skeleton is used, the amount of solids of the amine emulsion used is preferably 35 mass % or more, more preferably 40 mass % or more, and preferably 95 mass % or less, more preferably 90 mass % or less, relative to 100 mass % of the solids of composition 1, from the viewpoint of easily forming a corrosion-resistant coating film that is excellent in corrosion prevention and drying properties, etc.

[0050] When a self-emulsifying amine compound containing the polyamidoamine is used in preparing composition 1, the amount of the solid content of the self-emulsifying amine compound used is preferably 15 mass % or more, more preferably 20 mass % or more, and is preferably 40 mass % or less, more preferably 35 mass % or less, relative to 100 mass % of the solid content of composition 1, from the viewpoint of easily forming an anticorrosive coating film that is excellent in anticorrosive properties and drying properties.

[0051] When a non-aqueous amine compound is used in preparing composition 1, the amount of solids of the non-aqueous amine used is preferably 10 mass% or more, more preferably 15 mass% or more, relative to 100 mass% of the solids of composition 1, from the viewpoint of easily forming a corrosion-resistant coating film that is excellent in corrosion resistance and drying properties, and is preferably 40 mass% or less, more preferably 35 mass% or less.

[0052] [Divalent or higher polyvalent carboxylic acids (B)] The divalent or higher polyvalent carboxylic acid (B) is an organic acid having two or more carboxy groups in one molecule. Since the present composition 1 contains a divalent or higher polyvalent carboxylic acid (B) rather than an inorganic acid such as hydrochloric acid or a monovalent carboxylic acid such as acetic acid, it is possible to easily obtain an anticorrosive coating composition having a long pot life and to easily form an anticorrosive coating film with excellent corrosion resistance. The divalent or higher polyvalent carboxylic acid (B) used in preparing the present composition 1 may be one type or two or more types.

[0053] The polyvalent carboxylic acid (B) is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, maleic acid, and citric acid. Among these, malic acid, succinic acid, and tartaric acid are preferred because they can easily form an anticorrosive coating film with superior anticorrosive properties.

[0054] The molecular weight of the polyvalent carboxylic acid (B) is preferably 500 or less, more preferably 300 or less, and even more preferably 200 or less, from the viewpoint of easily obtaining an anticorrosive coating composition having a well-balanced pot life and drying properties.

[0055] The amount of polyvalent carboxylic acid (B) used in preparing the present composition 1 is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, per 100 parts by mass of the solid content of the amine compound (A), from the viewpoints that an anticorrosive coating composition having a long pot life can be easily obtained and an anticorrosive coating film having excellent corrosion resistance can be easily formed.

[0056] In addition, from the viewpoint of easily obtaining an anticorrosive coating composition having a long pot life, the ratio of the number of functional groups of the polyvalent carboxylic acid (B) to the active hydrogen equivalent of the solid content of the amine compound (A) used in preparing the present composition 1 can be calculated from the following formula (1): The ratio is preferably 0.1 or more, more preferably 0.2 or more, and is preferably 0.6 or less, more preferably 0.5 or less. Usage ratio=active hydrogen equivalent of solid content of amine compound (A) / usage amount (parts by mass) of solid content of amine compound (A) × (usage amount (parts by mass) of polycarboxylic acid (B) × valence of polycarboxylic acid (B)) / molecular weight of polycarboxylic acid (B) (g / mol) (1)

[0057] [Water(C)] Water may be contained in the raw materials such as the amine compound (A) used in preparing the present composition 1. For this reason, the water contained in the raw materials may be used as the water (C), but in order to facilitate the preparation of the present composition 1 and to easily obtain the present composition 1 having superior storage stability, it is preferable to further blend water (C) in the present composition 1 in addition to the water that may be contained in the raw materials such as the amine compound (A) used in preparing the present composition 1. The water (C) is not particularly limited, and tap water or the like may be used, but it is preferable to use ion-exchanged water, deionized water, or the like.

[0058] The water content in the present composition 1 (including water that may be contained in raw materials such as the amine compound (A) used in preparing the present composition 1) is not particularly limited, but is preferably 40 mass% or more, more preferably 45 mass% or more, and is preferably 80 mass% or less, more preferably 75 mass% or less. In addition, the content of water in the present composition 1 is preferably 50 mass % or more, more preferably 70 to 100 mass %, and particularly preferably 80 to 100 mass %, relative to 100 mass % of the total amount of the dispersion medium and the solvent in the present composition 1, in order to easily obtain the desired present composition 1, etc.

[0059] [Other ingredients] The composition 1 is not particularly limited as long as it contains the amine compound (A), the divalent or higher polyvalent carboxylic acid (B), and water (C). If desired, the composition may contain other components such as 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, a film-forming assistant, and an organic solvent, 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. The other components may be conventionally known components, and examples of the pigment, anti-sagging agent (anti-settling agent, thixotropic agent), flash rust inhibitor, plasticizer, defoamer, film-forming aid, and organic solvent include the same components as those described in the column for Composition 2 below.

[0060] <Anticorrosion coating composition> An anticorrosive coating composition according to one embodiment of the present invention (hereinafter also simply referred to as "Composition A") contains an anticorrosive composition 2 (hereinafter also simply referred to as "Composition 2") containing a non-aqueous epoxy compound (D), and the present composition 1.

[0061] The present composition A is a two-component or higher composition containing the above-mentioned composition 2 and the present composition 1. The present composition A may also be a three-component or higher composition containing an nth agent (n is 1 or more) other than the above-mentioned composition 2 and the present composition 1, but is preferably a two-component composition. The composition 2 and the present composition 1 are usually stored, preserved, transported, etc. in separate containers, and mixed together just before use of the present composition A. In other words, the present composition A is a composition obtained by mixing the composition 2, the present composition 1, and, if necessary, the nth agent. The composition 2, the present composition 1, and the nth agent can also be said to be components of a kit for preparing the present composition A, in other words, the present composition A can be said to be a kit for anticorrosive coating compositions containing the composition 2 and the present composition 1.

[0062] The non-volatile content of Composition A can be calculated in accordance with ISO3233:1998, and is preferably 65% ​​by volume or more, more preferably 70% by volume or more, and even more preferably 75% by volume or more. There is no particular upper limit, but it is, for example, 90% by volume. A composition having a non-volatile content in the above range can be said to be a high solid composition. When the non-volatile content of the composition A is in the above range, it is preferable because it has excellent drying properties, is less likely to sag when applied, can form a thick film in one application, and has excellent coating workability.

[0063] <Composition 2> The composition 2 is not particularly limited as long as it contains the non-aqueous epoxy compound (D), but may contain the following other components, and preferably contains the following other components. The composition 2 can also be called a main component since it is used as a constituent material of the present composition A together with the present composition 1, which can also be called a curing agent component.

[0064] Composition 2 may or may not contain water. When composition 2 contains water, the content of the water is preferably less than the amount that allows composition 2 to become an emulsion of the non-aqueous epoxy compound (D). Specifically, the water content is preferably 35 mass% or less, more preferably 25 mass% or less, relative to 100 mass% of the solid content of the non-aqueous epoxy compound (D) in composition 2.

[0065] [Non-aqueous epoxy compounds (D)] The term "non-aqueous" in the non-aqueous epoxy compound (D) refers to a state in which the compound is not freely miscible with water, and is substantially insoluble in water. Specifically, when an epoxy compound is mixed with water so that the concentration of the epoxy compound is 3% by mass at 23°C, the mixture is thoroughly stirred, and allowed to stand at 23°C for 1 hour. If the resulting mixture is not homogeneous and 90% by mass or more of the epoxy compound mixed with water is separated, precipitated, or suspended, the epoxy compound is considered to be a non-aqueous epoxy compound (D). The nonaqueous epoxy compound (D) used in preparing the composition 2 may be one type or two or more types.

[0066] In addition, when more than 10% by mass of the epoxy compound mixed with water is stably present in water in the mixed liquid and the mixed liquid is maintained in an emulsion state, the epoxy compound is considered to be a water-dilutable epoxy compound.In addition, when more than 10% by mass of the epoxy compound mixed with water is stably present in water in the mixed liquid and the epoxy compound exists in a state where the average particle size measured by a laser diffraction type particle size distribution measuring device (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)) is less than 10 nm, the epoxy compound is considered to be a water-soluble epoxy compound.

[0067] As the non-aqueous epoxy compound (D), it is preferable to use a liquid epoxy compound that is liquid at 23° C. Such a liquid epoxy compound is preferable because it makes composition 2 a composition with a relatively small amount of solvent, and even if the composition contains components other than the non-aqueous epoxy compound (D), it is easy to uniformly disperse the epoxy compound in said composition 2, and the reactivity with the amine compound (A) in the present composition 1 is also good.

[0068] Examples of non-aqueous epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, novolac type epoxy resins, cresol type epoxy resins, dimer acid modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, epoxidized oil-based epoxy resins, alkyl monoglycidyl ethers, alkyl monoglycidyl esters, alkyl diglycidyl ethers, alkyl diglycidyl esters, alkyl phenol monoglycidyl ethers, polyglycol monoglycidyl ethers, and polyglycol diglycidyl ethers. Suitable examples of the alkyl group include alkyl groups having 3 to 15 carbon atoms, and specific examples thereof include alkyl groups such as neopentyl and 2-ethylhexyl.

[0069] Among these, from the viewpoint of easily forming an anticorrosive coating film having excellent adhesion to the substrate, it is more preferable to use an epoxy compound, particularly an epoxy resin, which is liquid at 23°C and has a bisphenol skeleton, more preferably a bisphenol A-type or bisphenol F-type epoxy resin which is liquid at 23°C, and even more preferably a bisphenol A-type epoxy resin which is liquid at 23°C and a bisphenol F-type epoxy resin which is liquid at 23°C are used in combination.

[0070] The number average molecular weight of the non-aqueous epoxy compound (D) is preferably 500 or less, more preferably 400 or less, from the viewpoint that an anticorrosive coating composition which is high solid and has excellent coating workability can be easily obtained.

[0071] As the non-aqueous epoxy compound (D), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used. Examples of commercially available products that are liquid at 23°C include "E-028" (manufactured by Ohtake Meishin Chemical Co., Ltd.), "jER 828" (manufactured by Mitsubishi Chemical Corporation), "Cardura E10P" (manufactured by Hexion), and "ADEKA RESIN EP-4901" (manufactured by ADEKA Corporation).

[0072] The solid content of the non-aqueous epoxy compound (D) is preferably 15 mass% or more, more preferably 20 mass% or more, and preferably 35 mass% or less, more preferably 30 mass% or less, relative to 100 mass% of the non-volatile content of the composition A. In addition, the solid content of the non-aqueous epoxy compound (D) is preferably 15 mass% or more, more preferably 20 mass% or more, and preferably 40 mass% or less, more preferably 35 mass% or less, relative to 100 mass% of the solid content of composition 2. When the content of the non-aqueous epoxy compound (D) is within the above range, a corrosion-resistant coating film having excellent corrosion resistance and adhesion to the substrate can be easily formed.

[0073] The non-volatile content (mass %) of Composition A is the mass percentage calculated by measuring the heating residue (non-volatile content) and the mass of the wire when 1±0.1 g of Composition A (the composition immediately after mixing Composition 1, Composition 2, and (and Agent n, if Agent n is included)) is weighed out onto a flat-bottom dish, spread evenly using a wire of known mass, dried at 23°C for 24 hours, and then heated at 125°C for 1 hour (under normal pressure).

[0074] In this specification, among the components (e.g., amine compound (A)) that serve as raw materials constituting composition 2 or composition 1, components other than the solvent and dispersion medium (e.g., water) that have a boiling point of less than 180°C under normal pressure in composition 2 or composition 1 are referred to as "solid contents".

[0075] From the viewpoint of being able to easily form an anticorrosive coating film that is excellent in anticorrosive properties, coating strength, and drying properties, it is desirable to use the nonaqueous epoxy compound (D) in an amount such that the reaction ratio calculated by the following formula (2) is preferably 0.3 or more, more preferably 0.4 or more, and preferably 1.5 or less, more preferably 1.2 or less.

[0076] Reaction ratio={(amount of solid content of amine compound (A) / active hydrogen equivalent of solid content of amine compound (A))+(amount of solid content of component reactive to non-aqueous epoxy compound (D) / functional group equivalent of solid content of component reactive to non-aqueous epoxy compound (D))} / {(amount of solid content of non-aqueous epoxy compound (D) / epoxy equivalent of solid content of non-aqueous epoxy compound (D))+(amount of solid content of component reactive to amine compound (A) / functional group equivalent of solid content of component reactive to amine compound (A))} (2)

[0077] Here, examples of the "component reactive to the non-aqueous epoxy compound (D)" in the formula (2) include, for example, carboxylic acids and silane coupling agents described later, and examples of the "component reactive to the amine compound (A)" include, for example, polycarbodiimide compounds and silane coupling agents described later. 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 amine compound (A) or with the non-aqueous epoxy compound (D) and calculate the reactivity ratio.

[0078] The "functional group equivalent" of each component means the mass (g) per 1 mol of functional group obtained by dividing the mass of 1 mol of that component by the number of moles of the functional group contained therein.

[0079] [Other ingredients] The composition 2 is not particularly limited as long as it contains the non-aqueous epoxy compound (D), and may contain other components, such as a polycarbodiimide compound, a silane coupling agent, a pigment, a pigment dispersant, an anti-sagging agent (anti-settling agent, thixotropic agent), a flash rust inhibitor, a plasticizer, an antifoaming agent, a dehydrating agent, a film-forming assistant, and an organic solvent, if desired, 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.

[0080] [Polycarbodiimide compounds] The polycarbodiimide compound is not particularly limited as long as it is a compound having two or more carbodiimide groups in one molecule, and known compounds can be used. By using the composition 2 containing a polycarbodiimide compound together with the present composition 1 containing the polyvalent carboxylic acid (B), a corrosion-resistant coating film having superior corrosion prevention properties can be easily formed.

[0081] The polycarbodiimide compound can be obtained by a decarboxylation condensation reaction of a diisocyanate compound using a known synthesis method.

[0082] The diisocyanate compound is not particularly limited, and may be any of linear or alicyclic aliphatic isocyanate compounds, aromatic isocyanate compounds, and heterocyclic isocyanate compounds, and among these, one type may be used alone, or two or more types may be used. Specifically, linear aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as 1,4-bis(isocyanatomethyl)cyclohexane, 2,2-bis(4-isocyanatocyclohexyl)propane, isophorone diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate; Diisocyanates: aliphatic diisocyanates containing an aromatic ring, such as 1,3-bis(2-isocyanato-2-propyl)benzene; and aromatic isocyanates, such as toluene-2,4-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4,6-triisopropylbenzene-1,3-diyl diisocyanate.

[0083] The polycarbodiimide compound may be a polycarbodiimide compound having an isocyanate group at its terminal, but the polycarbodiimide compound having an isocyanate group at its terminal is preferably capped at the terminal isocyanate group by reacting the polycarbodiimide compound with a known end-capping agent having a substituent that reacts with an isocyanate group. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.

[0084] As the polycarbodiimide compound, commercially available products may be used, and examples of such commercially available products include the Carbodilite series (manufactured by Nisshinbo Chemical Inc.).

[0085] When the present composition A contains a polycarbodiimide compound, the solid content of the polycarbodiimide compound is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and preferably 8 mass % or less, more preferably 6 mass % or less, relative to 100 mass % of the non-volatile content of the present composition A. Furthermore, when composition 2 contains a polycarbodiimide compound, the solid content of the polycarbodiimide compound is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and preferably 10 mass% or less, more preferably 8 mass% or less, relative to 100 mass% of the solid content of composition 2. When the content of the polycarbodiimide compound is within the above range, a corrosion-resistant coating film excellent in corrosion resistance, moisture resistance and adhesion to a substrate can be easily formed.

[0086] [Silane coupling agents] By using a silane coupling agent, not only can the adhesion of the obtained anticorrosive coating film to the substrate be further improved, but also the corrosion resistance, such as moisture resistance and salt water resistance, and heat resistance, of the obtained anticorrosive coating film can be improved.

[0087] The silane coupling agent is not particularly limited, and any conventionally known compound can be used, but it is preferable that the silane coupling agent is a compound that has at least two functional groups in the same molecule and can contribute to improving adhesion to the substrate and reducing the viscosity of Composition A.

[0088] The silane coupling agent is, for example, a compound represented by the formula: "X-SiMe n Y 3-n " [n is 0 or 1, X is a functional group capable of reacting with an organic substance (e.g., an amino group, a vinyl group, an epoxy group, a mercapto group, a halogeno group, a group in which a hydrocarbon group is partially substituted with any of these groups, or a group in which a hydrocarbon group is partially substituted with an ether bond or the like and the group is partially substituted with any of these groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or an ethoxy group).] is preferable.

[0089] Among these, an epoxy group-containing silane coupling agent in which X is an epoxy group, a group in which a hydrocarbon group is partly substituted with an epoxy group, or a group in which a hydrocarbon group is partly substituted with an ether bond or the like and the part of the group is partly substituted with an epoxy group is preferred. When the composition A contains an epoxy group-containing silane coupling agent, the silane coupling agent is preferably blended in the composition 2.

[0090] As the silane coupling agent, commercially available products may be used, and examples of such commercially available products include 3-glycidoxypropyltrimethoxysilane "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.) and "Sila Ace S-510" (manufactured by JNC Corporation).

[0091] When the present composition A contains a silane coupling agent, the content of the silane coupling agent is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and preferably 10 mass% or less, more preferably 5 mass% or less, relative to 100 mass% of the non-volatile content of the present composition A. When the content of the silane coupling agent is within the above range, the viscosity of Composition A can be reduced, thereby improving not only the ease of painting but also the adhesion to the substrate, corrosion prevention, and heat resistance of the obtained anticorrosive coating film.

[0092] [Pigment] Composition A may contain a pigment, and preferably contains a pigment. Examples of the pigment include extender pigments, coloring pigments, and rust-preventive pigments, and they may be either organic or inorganic.

[0093] Examples of the extender pigment include talc, mica, (precipitated) barium sulfate, (potash) 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 (potash) feldspar are preferred.

[0094] When composition A contains an extender pigment, the content of the extender pigment is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, relative to 100% by mass of the non-volatile content of composition A.

[0095] Examples of the color pigment include inorganic pigments such as carbon black, titanium dioxide (titanium white), iron oxide (red oxide), yellow iron oxide, scaly iron oxide, and ultramarine, and organic pigments such as cyanine blue and cyanine green. Titanium white, carbon black, and red oxide are particularly preferred.

[0096] When Composition A contains a coloring pigment, the content of the coloring pigment is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, relative to 100% by mass of the non-volatile content of Composition A.

[0097] Examples of the anti-rust pigment include zinc powder, zinc alloy powder, zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, zinc cyanamide compounds, borate compounds, nitro compounds, and composite oxides.

[0098] When the present composition A contains an anti-rust pigment, the content of the anti-rust pigment is preferably 0.5 mass % or more, more preferably 1 mass % or more, and preferably 20 mass % or less, more preferably 10 mass % or less, relative to 100 mass % of the non-volatile content of the present composition A.

[0099] When composition A contains a pigment, the pigment volume concentration (PVC) in composition A is preferably 25% or more, more preferably 30% or more, and is preferably 45% or less, more preferably 40% or less, from the viewpoints that an anticorrosive coating composition having excellent coating workability can be easily obtained and an anticorrosive coating film having excellent adhesion to the substrate and corrosion resistance due to stress relaxation can be easily formed.

[0100] The PVC refers to the total volume concentration of pigments relative to the volume of the nonvolatile matter of Composition A. Specifically, the PVC can be calculated by the following formula. PVC [%] = Total volume of all pigments in Composition A × 100 / Volume of non-volatile matter in Composition A

[0101] The volume of the non-volatile content of the composition A can be calculated from the mass and true density of the non-volatile content of the composition A. 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, the volume of the pigment can be calculated by separating the pigment from other components from the non-volatile content of the composition A and measuring the mass and true density of the separated pigment.

[0102] [Anti-sagging agent] The anti-sagging agent is not particularly limited, but is preferably a material that can suppress sedimentation of pigments and the like in the present composition A and improve its storage stability, or a material that can improve the anti-sagging properties of the present composition A during or after coating. As the anti-sagging agent, there can be used conventionally known agents such as stearate salts, lecithin salts, alkylsulfonates and other organic clay-based waxes, polyethylene wax, amide wax, hydrogenated castor oil wax, mixtures of hydrogenated castor oil wax and amide wax, synthetic finely powdered silica, and oxidized polyethylene wax. Among these, amide wax, synthetic finely powdered silica, oxidized polyethylene wax, and organic clay-based wax are preferred.

[0103] As such a sagging prevention agent, commercially available products may be used. Examples of commercially available products include "Disparlon 305", "Disparlon 4200-20", "Disparlon 6650", and "Disparlon AQ600" manufactured by Kusumoto Chemical Industries, Ltd., "ASA T-250F" manufactured by Ito Oil Milling Co., Ltd., "Flonon RCM-300" manufactured by Kyoeisha Chemical Co., Ltd., "RHEOBYK 420" manufactured by BYK Japan K.K., "Benton SD-2" manufactured by Elementis Specialties, Inc., "Aerosil R972" manufactured by Nippon Aerosil Co., Ltd., and "Crayvallc Optima" manufactured by Arkema Coating Resins Co., Ltd.

[0104] When the present composition A contains an anti-sagging agent, the content of the solid content of the anti-sagging agent is preferably 0.1 to 10 mass % relative to 100 mass % of the non-volatile content of the present composition A.

[0105] [Flash rust inhibitor] The flash rust inhibitor is not particularly limited, but is preferably a material that can suppress rusting caused by the elution of iron ions from the steel surface or the like during the drying process immediately after painting of Composition A onto an active steel surface or the like, and suppresses flash rust, which is the appearance of such rust on the coating surface.

[0106] Examples of the flash rust inhibitor include nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite, and ammonium nitrite; benzoates such as sodium benzoate, potassium benzoate, calcium benzoate, and ammonium benzoate; phytates such as sodium phytate and potassium phytate; fatty acid salts such as sebacic acid and dodecanoic acid; phosphoric acid derivatives such as alkyl phosphoric acid and polyphosphoric acid; tannates; sulfonic acid metal salts; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), Examples of such chelating agents include amine-based chelating agents such as diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; addition reaction products of 4-methyl-γ-oxo-benzenebutanoic acid and N-ethylmorpholine; intercalation compounds obtained by intercalating monoalkylamines, polyamines, quaternary ammonium ions, etc., into layered phosphates such as aluminum dihydrogen tripolyphosphate; and hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds.

[0107] As the flash rust inhibitor, a commercially available product may be used. Examples of the commercially available product include "Killeslite W-410" and "Killeslite W-16B" (both manufactured by Chelest Co., Ltd. / organic acid salt type) and "HALOX FLASH-X 150" (manufactured by ICL Advanced Additives-Hammond / nitrite, benzoate type).

[0108] When composition A contains a flash rust inhibitor, the solids content of the flash rust inhibitor is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and preferably 5 mass % or less, more preferably 3 mass % or less, relative to 100 mass % of the non-volatile content of composition A.

[0109] [Plasticizer] Composition A may contain a plasticizer in order to improve the flexibility of the resulting anticorrosive coating film. As the plasticizer, a wide variety of conventionally known plasticizers can be used, including liquid hydrocarbon resins such as low-boiling fractions obtained by thermal decomposition of naphtha, petroleum resins that are solid at 23° C., xylene resins, coumarone-indene resins, etc. Specific examples include liquid hydrocarbon resins and flexibility-imparting resins described in JP-A-2006-342360.

[0110] Among these, liquid hydrocarbon resins are preferred, and phenol-modified hydrocarbon resins are more preferred, from the viewpoint of good compatibility with the non-aqueous epoxy compound (D). Examples of the phenol-modified hydrocarbon resin include resins obtained by copolymerizing diolefins, monoolefins, or α-methylstyrene contained in cracked oil fractions of petroleum or coal with phenols (phenolic compounds), as described in, for example, JP-A-9-268209 and JP-A-7-196793.

[0111] More specifically, the phenol-modified hydrocarbon resins include resins obtained by reacting phenols with C5 (aliphatic) petroleum resins made from C5 fractions, C9 (aromatic) petroleum resins made from C9 fractions, C5-C9 copolymerized petroleum resins, dicyclopentadiene resins made from dicyclopentadiene obtained by thermally dimerizing cyclopentadiene contained in C5 fractions, α-methylstyrene, etc. Among these, resins obtained by addition polymerization of styrene, vinyltoluene, coumarone, indene, α-methylstyrene, etc., contained in petroleum or coal cracked oil fractions, with phenols are preferred.

[0112] The phenol-modified hydrocarbon resin usually has an average molecular weight of 200 to 1000 and a viscosity of 30 to 10,000 mPa·s / 25°C.

[0113] As the liquid hydrocarbon resin, a commercially available product may be used. Examples of the commercially available product include "Nesiles EPX-L" and "Nesiles EPX-L2" (both manufactured by NEVCIN / phenol-modified hydrocarbon resin) and "Hirenol PL-1000S" (manufactured by Kolon Industries, Inc. / phenol-modified hydrocarbon resin).

[0114] When the present composition A contains a plasticizer, the solid content of the plasticizer is preferably 1 mass % or more, more preferably 3 mass % or more, relative to 100 mass % of the non-volatile content of the present composition A, in order to obtain a corrosion-resistant coating film having superior crack resistance, etc., and is preferably 15 mass % or less, more preferably 10 mass % or less.

[0115] [Antifoaming agent] It is preferable that the present composition A contains an antifoaming agent, since this can suppress the generation of bubbles during the production or application of the composition, or can break any bubbles that have generated in the present composition A, thereby making it possible to easily form a corrosion-protective coating film having the desired physical properties. The defoaming agent may be a commercially available product. Examples of the commercially available product include "BYK-392", "BYK-066N", and "BYK-1790" (all manufactured by BYK Japan K.K.), "TEGO Airex 902W" (manufactured by Evonik), and "Spectrasyn 40" (manufactured by Exxonmobil Chemical Company).

[0116] When the present composition A contains an antifoaming agent, the solid content of the antifoaming agent is preferably 0.005 mass % or more, more preferably 0.01 mass % or more, and preferably 1 mass % or less, more preferably 0.5 mass % or less, relative to 100 mass % of the nonvolatile content of the present composition A, from the viewpoints of being able to sufficiently suppress the generation of foam and to easily form a corrosion-protective coating film having the desired physical properties.

[0117] [Film-forming agent] Since composition A contains water, which may cause the composition to freeze in winter, and from the viewpoint of improving the film-forming properties at low temperatures and the finished appearance of the resulting coating film, it is preferable that composition A contains a film-forming auxiliary.

[0118] The film-forming aid may be an organic compound having a boiling point of 180°C or higher under normal pressure that is typically used in aqueous paint compositions, and examples of such an organic compound include linear or branched aliphatic alcohols having 5 to 15 carbon atoms; alcohols having an aromatic ring, such as benzyl alcohol; monoethers, such as (poly)ethylene glycol or (poly)propylene glycol; (poly)ethylene glycol ether esters; and (poly)propylene glycol ether esters.

[0119] When the present composition A contains a film-forming auxiliary, the content thereof is preferably 1 mass % or more, more preferably 2 mass % or more, and preferably 10 mass % or less, more preferably 8 mass % or less, relative to 100 mass % of the nonvolatile content of the present composition A, from the viewpoint of being able to easily form a corrosion-resistant coating film that has excellent film-forming properties and appearance at low temperatures.

[0120] [Organic solvents] The organic solvent is not particularly limited as long as it has a boiling point of less than 180° C. under normal pressure, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), ether solvents such as butyl cellosolve, ester solvents such as butyl acetate, alcohol solvents such as isopropanol, isobutyl alcohol, n-butanol, and methoxypropanol, and aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, and methylcyclohexane.

[0121] When composition 2 contains an organic solvent, the content of the organic solvent is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, relative to 100% by mass of composition 2.

[0122] <Method for preparing composition A> The present composition 1 and the composition 2 can be prepared by mixing (kneading) each component to be blended in these compositions. During this mixing (kneading), each component may be added and mixed at once, or may be added and mixed in several batches. The present composition A can be prepared by mixing (kneading) the present composition 1, the composition 2, and the nth agent which is used as needed. In the mixing (kneading), a conventionally known device such as a mixer, disperser, or stirrer can be used, and examples of such devices include a disperser, a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. In addition, the mixing (kneading) may be performed while heating or cooling depending on the season, environment, etc.

[0123] <Anti-corrosion coating, substrate with anti-corrosion coating> The anticorrosive coating film according to one embodiment of the present invention (hereinafter also referred to as "the present coating film") is formed using the present composition A, and the substrate with the anticorrosive coating film according to one embodiment of the present invention (hereinafter also referred to as "the substrate with the present coating film") is a laminate having the present coating film and a substrate.

[0124] The material of the substrate is not particularly limited, and examples thereof include steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, zinc plating, zinc spraying, etc.), and stainless steel (SUS304, SUS410, etc.). In addition, when using mild steel (SS400, etc.) as the substrate, it is desirable to adjust the surface of the substrate (e.g., adjust the arithmetic mean roughness (Ra) to about 30 to 75 μm) by polishing the surface of the substrate by grit blasting, etc., as necessary. The substrate may be a substrate that has been pretreated by a cleaning treatment or a blasting treatment for removing rust, dirt, paint (old coating), and the like adhering to the substrate.

[0125] The substrate is not particularly limited, and can be used without limitation on substrates that require corrosion resistance. However, in terms of the effect of using the present composition A being more pronounced, preferred substrates include (steel) structures such as ships, marine structures, plants, bridges, tanks, and containers.

[0126] The dry film thickness of the coating film is not particularly limited, but in order to obtain a coating film having sufficient corrosion protection, it is usually 10 μm or more, preferably 15 μm or more, and usually 400 μm or less, preferably 300 μm or less.

[0127] The substrate with the coating film of the present invention is a laminate including the coating film of the present invention and a substrate, and may be formed with an undercoat coating film (primer coating film) for the purpose of improving adhesion to the substrate and corrosion resistance, an intermediate coating film for the purpose of improving corrosion resistance, and a topcoat coating film that is excellent in weather resistance, appearance, etc. Specifically, when the present composition A is used as a substitute for a zinc primer, an undercoat coating film and a topcoat coating film may be formed on the present coating film. The undercoat coating film may be a coating film formed from various primer compositions such as an epoxy resin-based coating film. The intermediate coating film may be a coating film formed from various intermediate coating paint compositions such as a (meth)acrylic resin-based coating film, an epoxy resin-based coating film, and an urethane resin-based coating film. The topcoat coating film may be a coating film formed from various topcoat coating paint compositions such as a (meth)acrylic resin-based coating film, a (meth)acrylic silicone resin-based coating film, an urethane resin-based coating film, a silicone resin-based coating film, and a fluororesin-based coating film. The composition of the present composition A may be changed, and the present composition A may be used to form the undercoat coating film, intermediate coating film, and topcoat coating film.

[0128] <Manufacturing method for substrate with anticorrosive coating> A method for producing a substrate with a corrosion-resistant coating according to one embodiment of the present invention includes the following steps [1] and [2]. Step [1]: A step of applying the composition A to a substrate. Step [2]: A step of drying the composition A applied to the substrate to form a corrosion-resistant coating film.

[0129] <Process [1]> The coating method in the step [1] is not particularly limited, and examples thereof include conventionally known methods such as spray coating such as airless spray coating and air spray coating, brush coating, roller coating, etc. Among these, spray coating is preferred because it can easily coat a large-area substrate such as the structure. In such coating, it is preferable to coat the coating so that the dry film thickness of the resulting coating falls within the above range.

[0130] The spray coating conditions may be adjusted as appropriate depending on the desired dry film thickness. For example, in the case of airless spray coating, it is preferable that the primary (air) pressure is about 0.3 to 0.6 MPa, the secondary (paint) pressure is about 10 to 15 MPa, and the gun movement speed is about 50 to 120 cm / sec.

[0131] The coating is preferably performed so that the dry thickness of the main coating film formed in step [2] falls within the above range. In this case, the main coating film of the desired thickness may be formed by one coating (one coating), or may be formed by two or more coatings (two or more coatings). Note that two coats refers to performing steps [1] and [2], and then performing step [1] on the coating film obtained in step [2].

[0132] When applying the composition A to a substrate, it is preferable to treat the surface of the substrate as necessary (e.g., blasting (ISO8501-1 Sa2 1 / 2), degreasing to remove oil and dust) in order to remove rust, oil, moisture, dust, salt, etc. from the substrate and to improve the adhesion of the resulting coating film to the substrate. In addition, the substrate may be coated with a shop primer or the like for the purpose of primary rust prevention.

[0133] <Process [2]> The drying conditions in the step [2] are not particularly limited and may be appropriately set depending on the coating film formation method, the type of substrate, the application, the coating environment, etc., but the drying temperature is usually 5 to 35° C. in the case of drying at room temperature, and usually 30° C. or higher but lower than 100° C., more preferably 40 to 80° C. in the case of forced drying using a hot air dryer or the like. According to the present composition A, the composition can be dried and cured even by drying at room temperature. The drying time varies depending on the drying method used for the coating film; for example, it takes about 1 to 7 days when drying at room temperature, and for example, it takes about 5 to 60 minutes when drying by force. EXAMPLES

[0134] Hereinafter, one embodiment of the present invention will be further described with reference to examples, but the present invention is not limited thereto.

[0135] [Example 1] In a container, as shown in Table 1, 10 parts by mass of non-aqueous epoxy compound (Note 1), 16 parts by mass of non-aqueous epoxy compound (Note 2), 5.4 parts by mass of liquid hydrocarbon resin (Note 3), 4 parts by mass of methoxypropanol, 4 parts by mass of benzyl alcohol, 3 parts by mass of red iron oxide (Note 4), 36 parts by mass of potassium feldspar (Note 5), 15 parts by mass of talc (Note 6), 5 parts by mass of barium sulfate (Note 7), 1 part by mass of silane coupling agent (Note 8), 0.3 parts by mass of anti-sagging agent (Note 9), and 0.3 parts by mass of defoamer (Note 10) were placed, and the mixture was stirred at room temperature (23°C) using a high-speed disperser until it became uniform, and then dispersed at 55 to 60°C for 30 minutes. Then, the mixture was cooled to 30°C or less to prepare composition 2.

[0136] In addition, 50 parts by weight of a water-dilutable amine (Note 12), 25 parts by weight of deionized water, and 5 parts by weight of tartaric acid were placed in a separate container and stirred using a high-speed disperser until the mixture was homogenous, thereby preparing Composition 1.

[0137] The prepared Composition 2 and Composition 1 were mixed in the mixing ratio (mass ratio) shown in Table 1 before painting to prepare an anticorrosive coating composition.

[0138] [Examples 2 to 17 and Comparative Examples 1 to 17] An anticorrosive coating composition was prepared in the same manner as in Example 1, except that each component shown in Table 1, Table 2A or Table 2B was used in the amount (parts by mass) shown in Table 1, Table 2A or Table 2B. Table 3 provides a description of each component listed in Tables 1, 2A and 2B.

[0139] [Table 1]

[0140] [Table 2A]

[0141] [Table 2B]

[0142] [Table 3]

[0143] <Pot life test> In the Examples and Comparative Examples, 300 g of each anticorrosive coating composition immediately after preparation was weighed out into a container and the viscosity of each anticorrosive coating composition at 35°C (Rion viscometer: VT-04F, Rion Co., Ltd.) was adjusted with water to 2,000 mPa s. After holding the anticorrosive coating composition in a thermostatic chamber at 35°C for 3 hours, the presence or absence of precipitation and aggregation of each anticorrosive coating composition was observed, and the viscosity (35°C) was measured in the same manner as described above. The pot life was evaluated according to the evaluation criteria described below, and the results are shown in Tables 4 and 5. (Evaluation Criteria) ○: The anticorrosive coating composition after 3 hours of storage had no precipitation or aggregation, and the viscosity of the anticorrosive coating composition after 3 hours of storage was less than 2,500 mPa·s △: No precipitation or aggregation occurred in the anticorrosive coating composition after 3 hours of storage, and the viscosity of the anticorrosive coating composition after 3 hours of storage was 2,500 mPa·s or more and less than 4,000 mPa·s ×: Precipitation and / or aggregation occurred in the anticorrosive coating composition after 3 hours, the viscosity of the anticorrosive coating composition after 3 hours was 4,000 mPa·s or more, or the anticorrosive coating composition became putty-like or gelled.

[0144] [Preparation of substrate (test plate) with anticorrosive coating] A sandblasted steel plate of SS400 (arithmetic mean roughness (Ra): 30 to 75 μm) having dimensions of 150 mm × 70 mm × 2.3 mm (thickness) was prepared. The anticorrosive coating composition prepared as described above was applied to the surface of this steel plate using an air spray so that the dry film thickness was 70 μm. Next, the anticorrosive coating composition applied to the steel plate was dried at 60 ° C for 40 minutes, and then a water-based acrylic resin-based topcoat paint (EKOMATE FINISH, manufactured by Chugoku Toryo Co., Ltd.) was applied using an air spray so that the dry film thickness was 40 μm. Thereafter, the applied water-based acrylic resin-based topcoat paint was dried at 60 ° C for 30 minutes, and then dried at 23 ° C for 7 days to prepare a test plate 1.

[0145] The anticorrosive coating composition prepared as described above was applied to the surface of the same steel plate as that used for test plate 1 using an air spray so that the dry film thickness was 80 μm. The anticorrosive coating composition applied to the steel plate was then dried at 60° C. for 30 minutes, and then dried at 23° C. for 7 days to prepare test plate 2.

[0146] <Salt spray test> Based on JIS K 5600-7-1:1999, a salt spray test was performed by holding the test plates 1 and 2 in a salt spray tester under salt spray conditions of 5 mass% salt water concentration, 35°C temperature, and 98% relative humidity for 400 hours, and evaluating the corrosion resistance according to the evaluation criteria described below. The results are shown in Tables 4 and 5. Regarding corrosion resistance, if the salt spray test score is 3 or higher, it can be said that there are no problems in practical use. (Evaluation Criteria) 5: No rust or blisters 4: No blisters have occurred, but the area of ​​rust on the surface of the substrate beneath the coating is less than 0.03% of the entire surface of the substrate beneath the coating. 3: A very small amount of small blisters have occurred, and the area of ​​rust on the surface of the substrate under the coating is 0.03% or more but less than 0.1% of the entire surface of the substrate under the coating. 2: Blisters have occurred, and the area of ​​rust on the surface of the substrate beneath the coating is between 0.1% and 0.3% of the entire surface of the substrate beneath the coating. 1: Blisters have occurred and the area of ​​rust on the surface of the substrate beneath the coating is 0.3% or more of the entire surface of the substrate beneath the coating.

[0147] <Combined cycle test> According to ASTM D2803, a 25-cycle test was performed using the test plate 1 and the test plate 2. The appearance of the test plate after the test was evaluated according to the same evaluation criteria as in the salt spray test. The results are shown in Tables 4 and 5. In addition, if the corrosion resistance is rated 3 or higher in this combined cycle test, it can be said that there are no problems in practical use.

[0148] <Moisture resistance test> The test plate 2 was left to stand for 400 hours in a humidity tester maintained at a temperature of 50±1° C. and a relative humidity of 95%, and then the appearance of the test plate was evaluated according to the same evaluation criteria as in the salt spray test. The results are shown in Table 5. Regarding moisture resistance, if the evaluation in this moisture resistance test is 3 or higher, it can be said that there is no problem in practical use.

[0149] [Table 4]

[0150] [Table 5]

Claims

1. An amine compound (A), A divalent or higher polyvalent carboxylic acid (B), Water (C) 1. A corrosion prevention composition comprising:

2. The corrosion protection composition of claim 1 , wherein the amine compound (A) comprises a water-dilutable amine compound.

3. The anticorrosive composition 1 according to claim 1 or 2, A corrosion prevention composition 2 containing a non-aqueous epoxy compound (D); 1. An anticorrosive coating composition comprising:

4. The anticorrosive coating composition according to claim 3 , wherein the anticorrosive composition 2 further contains a polycarbodiimide compound.

5. 5. The anticorrosive coating composition according to claim 3, wherein the non-aqueous epoxy compound (D) is liquid at 23°C and has a bisphenol skeleton.

6. The anticorrosive coating composition according to any one of claims 3 to 5, wherein the anticorrosive composition 2 further contains a silane coupling agent.

7. An anticorrosive coating film formed from the anticorrosive coating composition according to any one of claims 3 to 6.

8. A substrate with an anticorrosive coating film, comprising a substrate and the anticorrosive coating film according to claim 7.

9. A method for producing a substrate with a corrosion-resistant coating, comprising the following steps [1] and [2]: [1] A step of coating a substrate with the anticorrosive coating composition according to any one of claims 3 to 6. [2] A step of drying the anticorrosive coating composition applied to the substrate to form an anticorrosive coating film.

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