Anticorrosion composition 1 and anticorrosion coating composition

Abstract

One embodiment of the present invention relates to an anticorrosion composition 1, an anticorrosion coating composition, an anticorrosion coating film, a substrate with an anticorrosion coating film, and a method for producing the same. The anticorrosion composition 1 contains an amine compound (A), a divalent or higher polycarboxylic acid (B), and water (C).

Description

Technical Field

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

[0002] Solvent-based anti-corrosion coatings are applied to substrates such as ships, marine components, large equipment, bridges, and surface storage tanks to ensure long-term use.

[0003] In recent years, with the strengthening of organic solvent emission regulations to take into account the natural environment and the coating work environment, the reduction of VOC (volatile organic compounds) in solvent-based paints has been promoted. One of the methods for reducing VOC is to make paints water-based.

[0004] For the purpose of making such a coating material water-based, Patent Document 1, for example, describes the use of a curing agent component containing a water-soluble amine resin and water.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-221256 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, in the case of using a curing agent component for the purpose of making the coating water-based as described in the above-mentioned Patent Document 1, the usable period of the anti-corrosion coating composition obtained by mixing with the main agent component is short, and the anti-corrosion performance of the anti-corrosion coating film obtained after the reaction with the main agent component is insufficient. There is still room for improvement in these aspects.

[0010] One embodiment of the present invention provides an anti-corrosion composition 1 that can provide an anti-corrosion coating composition having a long usable life and can also form an anti-corrosion coating film having excellent anti-corrosion performance.

[0011] Technical means to solve problems

[0012] The present inventors have conducted intensive research on a method for solving the above-mentioned problems and have found that the above-mentioned problems can be solved by the following configuration examples, thereby completing the present invention.

[0013] The composition examples of the present invention are shown below.

[0014] <1> An anticorrosion composition 1 comprises an amine compound (A); a divalent or higher polyvalent carboxylic acid (B); and water (C).

[0015] <2> like <1> In the anticorrosion composition 1, the amine compound (A) contains a water-dilutable amine compound.

[0016] <3> An anti-corrosion coating composition, comprising <1> or <2> The anti-corrosion composition 1 and the anti-corrosion composition 2 containing a non-aqueous epoxy compound (D).

[0017] <4> like <3> The anti-corrosion coating composition, wherein the anti-corrosion composition 2 further contains a polycarbodiimide compound.

[0018] <5> like <3> or <4> In the anti-corrosion coating composition, the non-aqueous epoxy compound (D) is liquid at a temperature of 23° C. and has a bisphenol skeleton.

[0019] <6> like <3> ~ <5> The anticorrosion coating composition according to any one of the preceding claims, wherein the anticorrosion composition 2 further contains a silane coupling agent.

[0020] <7> An anti-corrosion coating film comprising <3> ~ <6> The anti-corrosion coating composition described in any one of the preceding claims is formed.

[0021] <8> A substrate with an anti-corrosion coating, comprising a substrate and <7> The anti-corrosion coating.

[0022] <9> A method for producing a substrate with an anti-corrosion coating, comprising the following steps [1] and [2].

[0023] [1] Coating on substrate <3> ~ <6> The process of producing an anti-corrosion coating composition according to any one of the preceding claims;

[0024] [2] A process of drying the anticorrosion coating composition applied on a substrate to form an anticorrosion coating film.

[0025] Effects of the Invention

[0026] According to one embodiment of the present invention, there is provided an anticorrosion composition 1 that can provide an anticorrosion coating composition having a long usable life and can also form an anticorrosion coating film having excellent anticorrosion performance. DETAILED DESCRIPTION

[0027] Anticorrosion Composition 1

[0028] The anticorrosion composition 1 according to one embodiment of the present invention (hereinafter also referred to as "composition 1 of the present invention") is not particularly limited as long as it contains an amine compound (A), a divalent or higher polycarboxylic acid (B) and water (C), and may also contain the following other components.

[0029] Since the composition 1 of the present invention is usually used when the amine compound reacts and cures, it can also be said to be a curing agent component of the anti-corrosion coating composition containing a main agent component and a curing agent component, preferably a curing agent component of an epoxy compound, and more preferably a curing agent component of a non-aqueous epoxy compound.

[0030] [Amine compound (A)]

[0031] The amine compound (A) is not particularly limited, and conventionally known amine compounds that have been used as curing agents for epoxy compounds and the like can be used.

[0032] The amine compound (A) used in preparing the composition 1 of the present invention may be one kind or two or more kinds.

[0033] 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). Preferably, it is an amine compound containing two or more amino groups in one molecule, and preferably an aliphatic, alicyclic, aromatic, or heterocyclic amine compound.

[0034] Examples of the aliphatic amine compound include alkylene polyamines, polyalkylene polyamines, and alkylaminoalkylamines.

[0035] Examples of the alkylene polyamines include those of the formula: "H2N-R 1 -NH2" represented by the compound, wherein R 1 It is a divalent hydrocarbon group having 1 to 12 carbon atoms. Specific examples include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and trimethylhexanediamine.

[0036] Examples of the polyalkylene polyamines include those of the formula: “H2N-(C m H 2m NH) n A compound represented by H", wherein m is an integer of 1 to 10, and n is an integer of 2 to 10, preferably an integer of 2 to 6. Specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecaamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0037] Examples of the alkylaminoalkylamine include: 2 2N-(CH2) p -NH2" represented by the compound, wherein R2 are independently hydrogen atoms or alkyl groups with 1 to 8 carbon atoms, but at least one R 2 is an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 6. Specific examples include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0038] Examples of aliphatic amine compounds other than these compounds include tetrakis(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylene polyamines (particularly diethylene glycol bis(3-aminopropyl) ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), menthanediamine (MDA), o-xylenediamine, m-xylenediamine (MXDA), p-xylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2′-aminoethylpiperazine), and 1-[2′-(2″-aminoethylamino)ethyl]piperazine.

[0039] Specific examples of the alicyclic amine compound include cyclohexanediamine, diaminodicyclohexylmethane (particularly 4,4′-methylenebiscyclohexylamine), 4,4′-isopropylidenedicyclohexylamine, norbornanediamine, and 2,4-bis(4-aminocyclohexylmethyl)aniline.

[0040] 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.

[0041] 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 diethylmethylphenylenediamine.

[0042] 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.

[0043] Examples of the amine compound (A) include modified forms of the above-mentioned amine compounds, such as fatty acid-modified forms such as polyamidoamine, amine adducts with epoxy compounds, Mannich-modified forms (e.g., Mannich-modified amines having a phenolic skeleton (phenalkamine, phenalkamide, etc.)), Michael adducts, ketimines, and aldimines. Among these, polyamidoamine, amine adducts with epoxy compounds, and Mannich-modified amines having a phenolic skeleton are preferred.

[0044] As the amine compound (A) used in preparing the composition 1 of the present invention, a water-dilutable amine compound or a non-aqueous amine compound can be used. From the viewpoint of being able to easily form an anti-corrosion coating film having excellent anti-corrosion performance and drying performance, it is preferred to use a water-dilutable amine compound, and it is more preferred to use a water-dilutable amine compound and a non-aqueous amine compound.

[0045] In the present invention, whether it is a water-dilutable amine compound or a non-aqueous amine compound is determined by the state of the raw material of the amine compound used in preparing the composition 1 of the present invention (a commercial product when used).

[0046] A 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 referred to as an "aqueous medium"). Specifically, first, the raw material of the amine compound used in the preparation of the composition 1 of the present invention is mixed with water, or the solvent / dispersion medium of the raw material of the amine compound is volatilized to prepare a mixed solution having a solid component of 50% by mass at a temperature of 23°C. Subsequently, the mixed solution is thoroughly stirred, and the raw material is considered to be a water-dilutable amine compound if more than 80% by mass of the solid component of the raw material is still stably present in water even after being allowed to stand for 1 hour at a temperature of 23°C. It should be noted that for amine compounds having a solid component of less than 50% by mass, the solid component is adjusted to 50% by mass using an evaporator or the like.

[0047] A non-aqueous amine compound refers to an epoxy-curable amine compound that is not freely miscible with water and is substantially insoluble in water. Specifically, a raw material for the amine compound used to prepare Composition 1 of the present invention is mixed with water at 23°C until the solids content reaches 3% by mass, stirred thoroughly, and allowed to stand at 23°C for 1 hour. If the resulting mixture does not become homogeneous, and if at least 90% by mass of the solids content of the raw material is separated, precipitated, or floating, the raw material is considered a non-aqueous amine compound in this specification.

[0048] Specific examples of the raw material of the amine compound corresponding to the water-dilutable amine compound 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 them, amine emulsions and / or self-emulsifying amine compounds are preferably used from the viewpoints of ease of reference and ease of preparation of the composition 1 of the present invention.

[0049] As the amine compound (A) used in preparing the composition 1 of the present invention, from the viewpoint of being able to easily form an anticorrosive coating film having excellent anticorrosive performance and moisture resistance, it is preferred 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 preferred to use an amine emulsion, a self-emulsifying amine compound and a non-aqueous amine compound.

[0050] Specific examples of the above-mentioned amine emulsions include hydrophilic amines obtained by reacting the above-mentioned amine compounds with glycidyl ethers of polyalkylene glycols, polyoxyalkyleneamines, epoxy compounds, etc., amines having an amide structure obtained by using fatty acids and the above-mentioned amine compounds, or products in which the above-mentioned amine compounds are neutralized with an acid or mixed with an emulsifier to impart emulsifying ability and are (forcibly) dispersed in water.

[0051] The self-emulsifying amine compound is an amine compound that acquires emulsification ability by mixing with an aqueous medium described below, rather than by mixing with an acid or emulsifier. Specific examples include hydrophilic amines obtained by reacting the above amine compound with a glycidyl ether of a polyalkylene glycol, a polyoxyalkyleneamine, an epoxy compound, and the like, and amines having an amide structure obtained by using a fatty acid and the above amine compound.

[0052] The active hydrogen equivalent of the solid components of the amine emulsion and the self-emulsifying amine compound is preferably 50 or more, more preferably 60 or more, and 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.

[0053] 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 phenolic skeleton. More preferably, polyamidoamine is used in combination with an amine adduct with an epoxy compound and / or a Mannich-modified amine having a phenolic skeleton.

[0054] The self-emulsifying amine compound preferably contains polyamidoamine.

[0055] From the viewpoint of being able to easily form an anticorrosive coating film having excellent curing properties and anticorrosive properties, the active hydrogen equivalent of the solid component of the above-mentioned 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 preferably 200 or less, more preferably 190 or less.

[0056] From the viewpoint of being able to easily obtain the uniformly mixed composition 1 of the present invention, the active hydrogen equivalent of the solid component of the polyamide amine is preferably smaller than the active hydrogen equivalent of the solid component of the adduct with the epoxy compound and the Mannich-modified amine having a phenol-derived skeleton, and is preferably 50 or more, more preferably 60 or more, and preferably 130 or less, more preferably 120 or less.

[0057] The amine emulsion is a dispersion (emulsion) in which an amine compound is dispersed in an aqueous medium.

[0058] The aqueous medium is not particularly limited as long as it contains water. The water content in the aqueous medium is preferably 50 to 100% by mass, more preferably 60 to 100% by mass.

[0059] The aqueous medium may contain a medium other than water having a boiling point of less than 180° C. under normal pressure. Examples of such a medium include acetone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol monopropyl ether. One or more of these may be used.

[0060] The amine emulsion can be prepared by emulsifying the above-mentioned amine compound using one or two or more surfactants to form an emulsion.

[0061] As the amine emulsion and the self-emulsifying amine compound, those produced by conventional methods may be used, or commercially available products may be used.

[0062] Examples of commercially available amine emulsions include "Epilink 701" (manufactured by Evonik) and "Cardolite NX-8401" (manufactured by Cardolite).

[0063] Moreover, as a commercial item of a self-emulsifying amine compound, "Jointmide3506" (made by YunTeh Industrial Co., Ltd.) is mentioned, for example.

[0064] From the viewpoint of being able to easily form an anticorrosive coating film with excellent anticorrosive performance and being able to easily obtain a low-viscosity anticorrosive coating composition, the above-mentioned non-aqueous amine compound is preferably an amine compound having a molecular weight of preferably 3000 or less, more preferably 2500 or less and having a cyclic structure.

[0065] From the viewpoint of easily forming an anticorrosive coating film having excellent curability and anticorrosive performance, the active hydrogen equivalent of the solid component of the non-aqueous amine compound is preferably 30 or more, more preferably 40 or more, and preferably 200 or less, more preferably 150 or less.

[0066] As the non-aqueous amine compound, a product produced by a known method may be used, or a commercially available product may be used.

[0067] Examples of the commercially available products include "Ancamine 2280" (manufactured by Evonik) and "ETHACURE 100 plus" (manufactured by Albemarle).

[0068] From the viewpoint of being able to easily form an anti-corrosion coating film with excellent anti-corrosion performance and drying performance, the solid component content of the amine compound (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, relative to 100% by mass of the solid component of the composition 1 of the present invention.

[0069] When a water-dilutable amine compound is used when preparing the composition 1 of the present invention, from the viewpoint of being able to easily form an anti-corrosion coating film with excellent anti-corrosion and drying properties, the amount of the solid component of the water-dilutable amine compound used is preferably 45% by mass or more, more preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, relative to 100% by mass of the solid component of the composition 1 of the present invention.

[0070] When an amine emulsion containing an adduct with the above-mentioned epoxy compound and / or a Mannich-modified amine having a skeleton derived from phenol is used to prepare the composition 1 of the present invention, from the viewpoint of being able to easily form an anti-corrosion coating film having excellent anti-corrosion performance and drying performance, the amount of the solid component of the amine emulsion used is preferably 35% by mass or more, more preferably 40% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, relative to 100% by mass of the solid component of the composition 1 of the present invention.

[0071] When a self-emulsifying amine compound containing the above-mentioned polyamide amine is used when preparing the composition 1 of the present invention, from the viewpoint of being able to easily form an anti-corrosion coating film with excellent anti-corrosion performance and drying performance, the amount of the solid component of the self-emulsifying amine compound used is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, relative to 100% by mass of the solid component of the composition 1 of the present invention.

[0072] When a non-aqueous amine compound is used when preparing the composition 1 of the present invention, from the viewpoint of being able to easily form an anti-corrosion coating with excellent anti-corrosion and drying properties, the amount of the solid component of the non-aqueous amine used is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, relative to 100% by mass of the solid component of the composition 1 of the present invention.

[0073] [Divalent or higher polycarboxylic acid (B)]

[0074] The divalent or higher polyvalent carboxylic acid (B) is an organic acid having two or more carboxyl groups in one molecule.

[0075] Since the composition 1 of the present invention does not contain inorganic acids such as hydrochloric acid or monocarboxylic acids such as acetic acid, but contains a polycarboxylic acid (B) having a valence of two or more, it is easy to obtain an anti-corrosion coating composition with a long usable period and to easily form an anti-corrosion coating film with excellent anti-corrosion performance.

[0076] The divalent or higher polycarboxylic acid (B) used in preparing the composition 1 of the present invention may be one type or two or more types.

[0077] The polycarboxylic 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. Of these, malic acid, succinic acid, and tartaric acid are preferred from the viewpoint of being able to easily form an anticorrosive coating with better anticorrosive properties.

[0078] From the viewpoint of easily obtaining an anticorrosive coating composition having a good balance between pot life and drying performance, the molecular weight of the polycarboxylic acid (B) is preferably 500 or less, more preferably 300 or less, and even more preferably 200 or less.

[0079] From the viewpoint of being able to easily obtain an anticorrosive coating composition with a long usable life and being able to easily form an anticorrosive coating film with excellent anticorrosive performance, the amount of the polycarboxylic acid (B) used in preparing the composition 1 of the present invention 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, relative to 100 parts by mass of the solid component of the amine compound (A).

[0080] Furthermore, from the viewpoint of being able to easily obtain an anticorrosive coating composition having a long usable life, the usage ratio of the number of functional groups of the polycarboxylic acid (B) relative to the active hydrogen equivalent of the solid component of the amine compound (A) when preparing the present invention composition 1 can be calculated by the following formula (1). This usage ratio is preferably 0.1 or more, more preferably 0.2 or more, and preferably 0.6 or less, more preferably 0.5 or less.

[0081] Usage ratio = active hydrogen equivalent of the solid component of the amine compound (A) / amount of the solid component of the amine compound (A) used (parts by mass) × (amount of the polycarboxylic acid (B) used (parts by mass) × number of valences of the polycarboxylic acid (B)) / molecular weight of the polycarboxylic acid (B) (g / mol) (1)

[0082] [Water (C)]

[0083] Raw materials such as the amine compound (A) used in preparing the composition 1 of the present invention may contain water. Therefore, the water contained in the raw materials may be referred to as water (C). However, from the viewpoint of facilitating the preparation of the composition 1 of the present invention and obtaining a composition 1 of the present invention having excellent storage stability, it is preferred that water (C) be added to the composition 1 of the present invention in addition to the water contained in the raw materials such as the amine compound (A) used in preparing the composition 1 of the present invention.

[0084] The water (C) is not particularly limited, and tap water or the like can be used. However, ion-exchanged water, deionized water or the like is preferably used.

[0085] The water content in the composition 1 of the present invention (including water contained in raw materials such as the amine compound (A) used when preparing the composition 1 of the present invention) is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less.

[0086] Furthermore, from the viewpoint of being able to easily obtain the desired composition 1 of the present invention, the content of water in the composition 1 of the present invention is preferably 50% by mass or more, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to 100% by mass of the total amount of the dispersion medium and the solvent in the composition 1 of the present invention.

[0087] [Other components]

[0088] The composition 1 of the present invention is not particularly limited, as long as it contains an amine compound (A), a divalent or higher polycarboxylic acid (B) and water (C). As needed, within the scope that does not impair the effects of the present invention, it may also contain other components such as pigments, pigment dispersants, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, defoaming agents, curing accelerators, curing catalysts, film-forming aids, organic solvents, etc.

[0089] Each of these other components may be used alone or in combination of two or more.

[0090] The above-mentioned other components can use conventionally known components, such as pigments, anti-sagging agents (anti-settling agents, thixotropic agents), flash rust inhibitors, plasticizers, defoaming agents, film-forming aids, and organic solvents, and the same components as those described in the following composition 2 column can be mentioned.

[0091] Anti-corrosion coating composition

[0092] An anticorrosive coating composition according to one embodiment of the present invention (hereinafter also referred to as "present invention composition A") comprises an anticorrosive composition 2 (hereinafter also referred to as "composition 2") containing a non-aqueous epoxy compound (D) and the present invention composition 1 described above.

[0093] The composition A of the present invention is a two-component or higher composition comprising the above-mentioned composition 2 and the present invention composition 1. Furthermore, the composition A of the present invention may be a three-component or higher composition comprising an nth component (n is 1 or greater) other than the above-mentioned composition 2 and the present invention composition 1, and is preferably a two-component composition.

[0094] The above-mentioned composition 2 and the present invention composition 1 are typically stored, transported, and other components in separate containers and then mixed together immediately before use of the present invention composition A. Specifically, the present invention composition A is a composition obtained by mixing the above-mentioned composition 2, the present invention composition 1, and, if necessary, the nth component. Furthermore, the above-mentioned composition 2, the present invention composition 1, and the nth component can also be considered as components of a kit for preparing the present invention composition A. In other words, the present invention composition A can be considered as a kit for an anticorrosion coating composition containing the above-mentioned composition 2 and the present invention composition 1.

[0095] The content of the non-volatile component in the composition A of the present invention can be calculated according to ISO 3233:1998 and is preferably 65% ​​by volume or more, more preferably 70% by volume or more, and even more preferably 75% by volume or more. The upper limit is not particularly limited, for example, 90% by volume.

[0096] Compositions having a non-volatile component content within the above range can be considered high-solids compositions. Composition A of the present invention having a non-volatile component content within the above range is preferred because it exhibits excellent drying properties, is less prone to sagging during application, can form a thick coating film in a single application, and exhibits excellent coating processability.

[0097] <Composition 2>

[0098] The composition 2 is not particularly limited as long as it contains the non-aqueous epoxy compound (D), and may contain the following other components, and preferably contains the following other components.

[0099] Since the above-mentioned composition 2 is used as a constituent material of the composition A of the present invention together with the composition 1 of the present invention which can be said to be a curing agent component, it can also be said to be a main agent component.

[0100] Composition 2 may or may not contain water.

[0101] When composition 2 contains water, the water content is preferably less than the amount required for composition 2 to form an emulsion of the non-aqueous epoxy compound (D). Specifically, it is preferably 35% by mass or less, more preferably 25% by mass or less, relative to 100% by mass of the solid component of the non-aqueous epoxy compound (D) in composition 2.

[0102] [Non-aqueous epoxy compound (D)]

[0103] The "non-aqueous" in the non-aqueous epoxy compound (D) means a state in which the compound is not freely miscible with water and is substantially insoluble in water.

[0104] Specifically, an epoxy compound is mixed with water at a temperature of 23°C to a concentration of 3% by mass of the epoxy compound, stirred thoroughly, and left to stand at a temperature of 23°C for 1 hour. If the resulting mixed solution does not become uniform, and more than 90% by mass of the epoxy compound mixed with water separates, precipitates, or floats, the epoxy compound is considered to be a non-aqueous epoxy compound (D).

[0105] The non-aqueous epoxy compound (D) used in preparing the composition 2 may be one kind or two or more kinds.

[0106] It should be noted that when more than 10% by mass of the epoxy compound mixed with water in the mixed solution is stably present in water and the mixed solution remains in an emulsion state, the epoxy compound is a water-dilutable epoxy compound. Furthermore, when more than 10% by mass of the epoxy compound mixed with water in the mixed solution is stably present in water and the epoxy compound has an average particle size of less than 10 nm as measured using a laser diffraction particle size distribution analyzer (e.g., Master Sizer 3000, manufactured by Spectris Co., Ltd.), the epoxy compound is a water-soluble epoxy compound.

[0107] As the non-aqueous epoxy compound (D), a liquid epoxy compound that is liquid at a temperature of 23° C. is preferably used. This liquid epoxy compound is preferred because it is easy to uniformly disperse the epoxy compound in the composition 2 even when the composition 2 has a relatively small amount of solvent and contains components other than the non-aqueous epoxy compound (D). It also has good reactivity with the amine compound (A) in the composition 1 of the present invention.

[0108] Examples of the non-aqueous epoxy compound include bisphenol A epoxy resins, bisphenol F epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, novolac epoxy resins, cresol epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, epoxidized oil-based epoxy resins, alkyl monoglycidyl ethers, alkyl monoglycidyl esters, alkyl diglycidyl ethers, alkyl diglycidyl esters, alkylphenol monoglycidyl ethers, polyethylene glycol monoglycidyl ethers, and polyethylene glycol diglycidyl ethers. Preferred examples of the alkyl group include those having 3 to 15 carbon atoms, specifically, neopentyl and 2-ethylhexyl groups.

[0109] Among them, from the viewpoint of being able to easily form an anti-corrosion coating with excellent adhesion to the substrate, it is more preferred to use an epoxy compound that is liquid at a temperature of 23°C and has a bisphenol skeleton, especially an epoxy resin; it is further preferred to use an epoxy resin that is liquid at a temperature of 23°C and is of the bisphenol A type or bisphenol F type; and it is further preferred to use a bisphenol A type epoxy resin that is liquid at a temperature of 23°C and a bisphenol F type epoxy resin that is liquid at a temperature of 23°C in combination.

[0110] 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 of easily obtaining an anticorrosive coating composition having a high solid content and excellent coating processability.

[0111] 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.

[0112] 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 Corporation), and "Adeka Resin EP-4901" (manufactured by Adeka Corporation).

[0113] The solid content of the non-aqueous epoxy compound (D) is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the non-volatile components of the composition A of the present invention.

[0114] The solid content of the non-aqueous epoxy compound (D) is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, relative to 100% by mass of the solid content of the composition 2.

[0115] When the content of the non-aqueous epoxy compound (D) is within the above range, an anticorrosion coating film having excellent anticorrosion performance and adhesion to a substrate can be easily formed.

[0116] The non-volatile component (mass %) of the composition A of the present invention is calculated by weighing 1±0.1 g of the composition A of the present invention (the composition immediately after mixing the composition 1 and the composition 2 of the present invention (including the nth component when the nth component is contained)) into a flat dish, spreading it evenly with a metal wire of known mass, and measuring the mass of the heating residue (non-volatile component) and the metal wire after drying at a temperature of 23°C for 24 hours and then heating at a heating temperature of 125°C for 1 hour (under normal pressure), and calculating the mass percentage.

[0117] It should be noted that in this specification, the components (such as amine compound (A)) that constitute the raw materials of the above-mentioned composition 2 and the composition 1 of the present invention, other than the solvent and dispersion medium (such as water) having a boiling point lower than 180°C at normal pressure in the above-mentioned composition 2 and the composition 1 of the present invention, are referred to as "solid components".

[0118] From the viewpoint of being able to easily form an anticorrosive coating film having excellent anticorrosive performance, coating film strength and drying performance, the non-aqueous epoxy compound (D) is preferably used 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.

[0119] Reaction ratio = {(amount of the solid component of the amine compound (A) blended / active hydrogen equivalent of the solid component of the amine compound (A)) + (amount of the solid component of the component reactive with the non-aqueous epoxy compound (D) blended / functional group equivalent of the solid component of the component reactive with the non-aqueous epoxy compound (D)) / {(amount of the solid component of the non-aqueous epoxy compound (D) blended / epoxy equivalent of the solid component of the non-aqueous epoxy compound (D)) + (amount of the solid component of the component reactive with the amine compound (A) blended / functional group equivalent of the solid component of the component reactive with the amine compound (A)) ... (2)

[0120] In the present invention, examples of the “component reactive with the non-aqueous epoxy compound (D)” in the above formula (2) include carboxylic acids, silane coupling agents described below, and the like, and examples of the “component reactive with the amine compound (A)” include polycarbodiimide compounds, silane coupling agents, and the like described below.

[0121] 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, it is necessary to determine whether the silane coupling agent is reactive with the amine compound (A) and whether the silane coupling agent is reactive with the non-aqueous epoxy compound (D) based on the type of the reactive group, and calculate the reaction ratio.

[0122] The "functional group equivalent" of each of the above components means the mass (g) per 1 mol of functional groups obtained by dividing the mass of 1 mol of these components by the number of moles (mol) of functional groups contained therein.

[0123] [Other components]

[0124] There are no particular limitations on composition 2, as long as it contains a non-aqueous epoxy compound (D). As needed, and within the scope that does not impair the effects of the present invention, it may further 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, a defoaming agent, a dehydrating agent, a film-forming aid, and an organic solvent.

[0125] Each of these other components may be used alone or in combination of two or more.

[0126] [Polycarbodiimide compound]

[0127] The polycarbodiimide compound is not particularly limited as long as it is a compound having two or more carbodiimide groups in one molecule, and a known compound can be used.

[0128] By using the composition 2 containing a polycarbodiimide compound together with the composition 1 of the present invention containing the polycarbolic acid (B), an anticorrosive coating film having a more excellent anticorrosive performance can be easily formed.

[0129] The polycarbodiimide compound can be obtained by a decarbonation condensation reaction of a diisocyanate compound using a known synthesis method.

[0130] The diisocyanate compound is not particularly limited, and any of chain or alicyclic aliphatic isocyanate compounds, aromatic isocyanate compounds, and heterocyclic isocyanate compounds can be used. One of these compounds may be used alone, or two or more thereof may be used in combination. Specific examples include chain 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; 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-diacyl diisocyanate.

[0131] The polycarbodiimide compound may be one having an isocyanate group at the end of the molecular chain. The polycarbodiimide compound having an isocyanate group at the end is preferably blocked by reacting with a known blocking agent having a substituent reactive with the isocyanate group. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.

[0132] As the polycarbodiimide compound, a commercially available product can be used, and examples of the commercially available product include the CARBODILITE series (manufactured by Nisshinbo Chemical Co., Ltd.).

[0133] When the composition A of the present invention contains a polycarbodiimide compound, the solid content of the polycarbodiimide compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 8% by mass or less, more preferably 6% by mass or less, relative to 100% by mass of the non-volatile component of the composition A of the present invention.

[0134] When composition 2 contains a polycarbodiimide compound, the solid content of the polycarbodiimide compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, relative to 100% by mass of the solid content of composition 2.

[0135] When the content of the polycarbodiimide compound is within the above range, an anticorrosion coating film having excellent corrosion resistance, moisture resistance, and adhesion to a substrate can be easily formed.

[0136] [Silane coupling agent]

[0137] By using a silane coupling agent, not only can the adhesion of the obtained anti-corrosion coating to the substrate be further improved, but also the anti-corrosion properties and heat resistance of the obtained anti-corrosion coating, such as moisture resistance and salt water corrosion resistance, can be improved.

[0138] The silane coupling agent is not particularly limited, and conventionally known compounds can be used. Preferably, the silane coupling agent has at least two functional groups in the same molecule and can contribute to improving adhesion to a substrate and reducing the viscosity of the composition A of the present invention.

[0139] The silane coupling agent is preferably a silane coupling agent such as the formula "X-SiMe n Y 3-n " wherein 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 halo group, a group in which a portion of a hydrocarbon group is substituted with the above groups, or a group in which a portion of a hydrocarbon group is substituted with an ether bond or the like, is substituted with the above groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., an alkoxy group such as a methoxy group and an ethoxy group).

[0140] Among them, preferred are epoxy group-containing silane coupling agents in which X is an epoxy group, a group in which a portion of a hydrocarbon group is substituted with an epoxy group, or a group in which a portion of a hydrocarbon group is substituted with an ether bond or the like and a portion of a hydrocarbon group is substituted with an epoxy group.

[0141] When the composition A of the present invention contains a silane coupling agent containing an epoxy group, the silane coupling agent is preferably compounded into the composition 2.

[0142] As the silane coupling agent, a commercially available product can be used. Examples of the commercially available product include "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.), which is 3-glycidyloxypropyltrimethoxysilane, and "Sila-Ace S-510" (manufactured by JNC Corporation).

[0143] When the composition A of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the non-volatile components of the composition A of the present invention.

[0144] When the content of the silane coupling agent is within the above range, the viscosity of the composition A of the present invention can be reduced, which not only improves the coating processability but also improves the adhesion to the substrate, corrosion resistance and heat resistance of the resulting anti-corrosion coating.

[0145] [pigment]

[0146] The composition A of the present invention may contain a pigment, and preferably contains a pigment.

[0147] Examples of the pigment include extender pigments, coloring pigments, and rust-proof pigments, and the pigments may be either organic or inorganic.

[0148] Examples of the extender pigment include talc, mica, (precipitated) barium sulfate, (potassium) feldspar, kaolin, alumina white, bentonite, wollastonite, clay, glass flakes, aluminum flakes, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silica. Talc, mica, silica, (precipitated) barium sulfate, and (potassium) feldspar are particularly preferred.

[0149] When the composition A of the present invention 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 components of the composition A of the present invention.

[0150] Examples of the coloring pigments include inorganic pigments such as carbon black, titanium oxide (titanium white), iron oxide (iron red), iron oxide yellow, flaky iron oxide, and ultramarine, and organic pigments such as cyanine blue and cyanine green. Titanium white, carbon black, and iron red are particularly preferred.

[0151] When the composition A of the present invention 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 components of the composition A of the present invention.

[0152] Examples of the rust-proof 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 complex oxides.

[0153] When the composition A of the present invention contains a rust-preventive pigment, the content of the rust-preventive pigment relative to 100 mass% of the non-volatile components of the composition A of the present invention 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.

[0154] When the composition A of the present invention contains a pigment, the pigment volume concentration (PVC) in the composition A of the present invention is preferably 25% or more, more preferably 30% or more, and preferably 45% or less, more preferably 40% or less, from the viewpoint of being able to easily obtain an anti-corrosion coating composition with excellent coating processability, and being able to easily form an anti-corrosion coating film with excellent adhesion to the substrate and anti-corrosion performance affected by stress relaxation.

[0155] The above-mentioned PVC refers to the volume concentration of the total amount of pigments relative to the volume of the non-volatile components in the present invention composition A. Specifically, PVC can be calculated by the following formula.

[0156] PVC [%] = the total volume of all pigments in the composition A of the present invention × 100 / the volume of non-volatile components in the composition A of the present invention

[0157] The volume of the non-volatile component in the composition A of the present invention can be calculated based on the mass and true density of the non-volatile component of the composition A of the present invention. The mass and true density of the non-volatile component can be measured values ​​or values ​​calculated based on the raw materials used.

[0158] 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 can be measured values ​​or calculated based on the raw materials used. For example, the volume can be calculated by separating the pigment from other components in the non-volatile component of Composition A of the present invention and measuring the mass and true density of the separated pigment.

[0159] [Anti-sagging agent]

[0160] The anti-sagging agent is not particularly limited, as long as it is a material that can inhibit the sedimentation of pigments and the like in the composition A of the present invention and improve its storage stability, or a material that can improve the anti-sagging performance of the composition A of the present invention during and after coating.

[0161] As the above-mentioned anti-sagging agent, organic clay waxes such as stearates, lecithin salts, alkyl sulfonates of Al, Ca, and Zn, polyethylene wax, amide wax, hydrogenated castor oil wax, a mixture of hydrogenated castor oil wax and amide wax, synthetic micropowder silica, oxidized polyethylene wax and other existing known products can be used. Among them, amide wax, synthetic micropowder silica, oxidized polyethylene wax and organic clay wax are preferred.

[0162] As such an anti-sagging agent, a commercially available product can be used. Examples of the commercially available product include "Disparlon 305", "Disparlon 4200-20", "Disparlon 6650", and "Disparlon AQ600" manufactured by Kusumoto Chemicals Co., Ltd., "ASA T-250F" manufactured by Ito Seiyu Co., Ltd., "FLOWNON RCM-300" manufactured by Kyoeisha Chemical Co., Ltd., "RHEOBYK 420" manufactured by BYK Chemie Japan, "Bentone SD-2" manufactured by Elementis Specialties, Inc., "Aerosil R972" manufactured by Nippon Aerosil Co., Ltd., and "Crayvalc Optima" manufactured by Arkema Coating Resins Co., Ltd.

[0163] When the composition A of the present invention contains an anti-sagging agent, the solid content of the anti-sagging agent is preferably 0.1 to 10% by mass relative to 100% by mass of the non-volatile components of the composition A of the present invention.

[0164] [Flash Rust Inhibitor]

[0165] The flash rust inhibitor is not particularly limited, but is preferably a material that can inhibit rust formation caused by the dissolution of iron ions from the surface of an active steel material, etc., during the period from immediately after application to drying when the composition A of the present invention is applied to the surface of the steel material, etc., and flash rust that arises on the surface of the coating film due to the generated rust.

[0166] 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 alkylphosphoric acid and polyphosphoric acid; tannates; sulfonic acid metal salts; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminetetraacetic acid (EDTA), and the like. Amine chelating agents such as tert-butyltriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts of these acids; addition reaction products of 4-methyl-γ-oxophenylbutyric acid and N-ethylmorpholine; intercalation compounds formed by the insertion of monoalkylamines, polyamines, quaternary ammonium ions, etc. into layered phosphates such as dihydrogen aluminum tripolyphosphate; hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds.

[0167] As the flash rust inhibitor, commercially available products can be used. Examples of such commercial products include "CHELESLITE W-410" and "CHELESLITE W-16B" (each an organic acid salt-based product manufactured by Chelest Co., Ltd.) and "HALOX FLASH-X 150" (a nitrite and benzoate-based product manufactured by ICL Advanced Additives-Hammond Co., Ltd.).

[0168] When the composition A of the present invention contains a flash rust inhibitor, the content of the solid component of the flash rust inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the non-volatile components of the composition A of the present invention.

[0169] [Plasticizer]

[0170] The composition A of the present invention may contain a plasticizer from the viewpoint of improving the flexibility of the anticorrosion coating film obtained.

[0171] As the plasticizer, a wide range of conventionally known products can be used, including liquid hydrocarbon resins such as low-boiling fractions obtained by thermal cracking of naphtha, petroleum resins that are solid at 23°C, xylene resins, and coumarone indene resins. Specific examples include liquid hydrocarbon resins and flexibility-enhancing resins described in Japanese Patent Application Laid-Open No. 2006-342360.

[0172] Among them, 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).

[0173] Examples of the phenol-modified hydrocarbon resin include resins obtained by copolymerizing phenolic compounds (phenol compounds) with dienes, monoolefins, α-methylstyrene, and the like contained in cracked oil fractions of petroleum or coal, as described in Japanese Patent Application Laid-Open Nos. 9-268209 and 7-196793.

[0174] More specifically, the phenol-modified hydrocarbon resins include C5-based (aliphatic) petroleum resins derived from C5 fractions, C9-based (aromatic) petroleum resins derived from C9 fractions, C5-C9 copolymerized petroleum resins, dicyclopentadiene resins derived from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in the C5 fraction, and resins obtained by reacting phenols with α-methylstyrene or the like. Among these, resins obtained by addition polymerization of phenols with styrene, vinyltoluene, coumarone, indene, α-methylstyrene, or the like contained in cracked oil fractions of petroleum or coal are preferred.

[0175] The phenol-modified hydrocarbon resin generally has an average molecular weight of 200 to 1,000 and a viscosity of 30 to 10,000 mPa·s / 25°C.

[0176] As the liquid hydrocarbon resin, a commercially available product can be used. Examples of the commercially available product include "NECIRES EPX-L" and "NECIRES EPX-L2" (each manufactured by NEVCIN Corporation / phenol-modified hydrocarbon resin) and "Hirenol PL-1000S" (manufactured by Kolon Industries, Inc. / phenol-modified hydrocarbon resin).

[0177] When the composition A of the present invention contains a plasticizer, from the viewpoint of being able to obtain an anticorrosive coating film with better crack resistance, etc., the solid content of the plasticizer is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, relative to 100% by mass of the non-volatile component of the composition A of the present invention.

[0178] [Defoaming agent]

[0179] The composition A of the present invention preferably contains a defoaming agent from the viewpoint of suppressing the generation of bubbles during the production or coating process of the composition or bursting bubbles generated in the composition A of the present invention to facilitate formation of an anticorrosive coating film having desired physical properties.

[0180] As the defoaming agent, a commercially available product can be used. Examples of the commercially available product include "BYK-392," "BYK-066N," and "BYK-1790" (all manufactured by BYK Chemie Japan Co., Ltd.), "TEGO Airex 902W" (manufactured by Evonik), and "Spectrasyn 40" (manufactured by ExxonMobil Chemical Company).

[0181] When the composition A of the present invention contains a defoaming agent, the content of the solid component of the defoaming agent is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to 100% by mass of the non-volatile component of the composition A of the present invention, from the viewpoint of being able to fully suppress the generation of bubbles and easily form an anti-corrosion coating film with desired physical properties.

[0182] [Film-forming aid]

[0183] Since the composition A of the present invention contains water, the composition may freeze in winter. In order to improve the film-forming performance at low temperatures and improve the product appearance of the resulting coating film, it preferably contains a film-forming aid.

[0184] As the above-mentioned film-forming aid, substances commonly used in aqueous coating compositions such as organic compounds having a boiling point of 180°C or above at normal pressure can be used, and examples thereof 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.

[0185] When the composition A of the present invention contains a film-forming aid, its content is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, relative to 100% by mass of the non-volatile components of the composition A of the present invention, from the viewpoint of being able to easily form an anti-corrosion coating with excellent film-forming properties at low temperatures and beautiful appearance.

[0186] [Organic solvents]

[0187] The organic solvent is not particularly limited as long as it is an organic solvent having a boiling point of less than 180° C. at normal pressure. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as butanone (MEK) and methyl isobutyl ketone (MIBK), ether solvents such as butyl cellosolve, ester solvents such as butyl acetate, alcohol solvents such as isopropyl alcohol, 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.

[0188] When the composition 2 contains an organic solvent, the content of the organic solvent is preferably 1 mass % or more, more preferably 2 mass % or more, and preferably 10 mass % or less, more preferably 5 mass % or less, based on 100 mass % of the composition 2.

[0189] <Preparation Method of Composition A of the Present Invention>

[0190] The composition 1 of the present invention and the above-mentioned composition 2 can be prepared by mixing (kneading) the components to be formulated into these compositions. During the mixing (kneading), the components can be added and mixed at once or in multiple times.

[0191] The composition A of the present invention can be prepared by mixing (kneading) the composition 1 and composition 2 of the present invention and the nth component used as needed.

[0192] When performing the above-mentioned mixing (kneading), conventionally known mixing equipment, dispersing equipment, stirring equipment, etc. can be used. Examples of such equipment include dispersers, mixing / dispersing mills, mortar mixers, roll mills, paint stirrers, and homogenizers. It should be noted that when performing the above-mentioned mixing (kneading), the mixing (kneading) can be performed while heating or cooling, etc., depending on the season, environment, etc.

[0193] Anti-corrosion coatings and substrates with anti-corrosion coatings

[0194] An anti-corrosion coating according to one embodiment of the present invention (hereinafter referred to as "the coating according to the present invention") is formed using the above-mentioned composition A of the present invention, and a substrate with an anti-corrosion coating according to one embodiment of the present invention (hereinafter also referred to as "the substrate with the coating according to the present invention") is a laminate having the coating according to the present invention and a substrate.

[0195] The material of the substrate is not particularly limited, and examples thereof include steel (iron, steel, iron alloy, carbon steel, low carbon steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, galvanized, zinc sprayed, etc.), and stainless steel (SUS304, SUS410, etc.).

[0196] When low carbon steel (SS400, etc.) is used as the substrate, it is preferable to perform texture adjustment (for example, adjusting the arithmetic mean roughness (Ra) to about 30 to 75 μm) by polishing the substrate surface by sandblasting, etc., as needed.

[0197] The substrate may be one that has been pre-treated by cleaning, sandblasting, or the like to remove rust, dirt, paint (old coating), or the like adhering to the substrate.

[0198] The above-mentioned substrate is not particularly limited and can be used for any substrate requiring anti-corrosion performance. However, from the perspective of better exerting the effects of using the composition A of the present invention, preferred examples include (steel) structures such as ships, marine structures, factories, bridges, storage tanks, and containers.

[0199] The dry film thickness of the coating film of the present invention is not particularly limited, but is usually 10 μm or more, preferably 15 μm or more, and usually 400 μm or less, preferably 300 μm or less, from the viewpoint of obtaining a coating film having sufficient anticorrosive properties.

[0200] The substrate with the coating film of the present invention is a laminate comprising the coating film of the present invention and a substrate, which can be formed into a primer film (primer coating film) for the purpose of improving adhesion to the substrate and anti-corrosion performance, a mid-coat film for the purpose of improving anti-corrosion performance, and a topcoat film with excellent weather resistance, aesthetics, etc.

[0201] Specifically, when the composition A of the present invention is used as a substitute for zinc primer, a mid-coat film or a top-coat film can be formed on the coating film of the present invention.

[0202] As above-mentioned primer film, can enumerate the film etc. that various primer compositions such as epoxy resin system form.As above-mentioned middle paint film, can enumerate the film etc. that various middle coating compositions such as (methyl) acryloyl resin system, epoxy resin system, polyurethane resin system form.In addition, as above-mentioned topcoat film, can enumerate the film etc. that various topcoat compositions such as (methyl) acryloyl resin system, (methyl) acryloyl silicone resin system, polyurethane resin system, organosilicon resin system, fluororesin system form.In addition, also can change the composition etc. of present invention composition A, form primer film, middle paint film and topcoat film by present invention composition A.

[0203] Method for producing a substrate with an anti-corrosion coating

[0204] A method for producing a substrate with an anticorrosive coating according to one embodiment of the present invention includes the following steps [1] and [2].

[0205] Step [1]: a step of applying the composition A of the present invention to a substrate;

[0206] Step [2]: A step of drying the composition A of the present invention applied on the substrate to form an anti-corrosion coating film.

[0207] <Process[1]>

[0208] The coating method in the above step [1] is not particularly limited, and examples thereof include spray coating such as airless spraying and air spraying, brush coating, roller coating, and other conventionally known methods. Among them, spray coating is preferred from the viewpoint of being able to easily coat a large-area substrate such as the above-mentioned component.

[0209] When applying the coating, it is preferred to apply the coating so that the dry film thickness of the resulting coating film falls within the above-mentioned range.

[0210] The above-mentioned spraying conditions can be appropriately adjusted according to the dry film thickness to be formed. For example, in the case of airless spraying, it is preferred 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 spray gun movement speed is about 50 to 120 cm / second.

[0211] The above-mentioned coating is preferably applied so that the dry film thickness of the coating film of the present invention formed in step [2] is within the above-mentioned range. In this case, the coating film of the present invention of the desired film thickness can be formed by a single coating (one coating layer) or by two or more coating layers (two or more coating layers).

[0212] It should be noted that the two-layer coating is performed after steps [1] and [2], and then step [1] is performed again on the coating film obtained in step [2].

[0213] When applying the composition A of the present invention to a substrate, the substrate surface is preferably treated as needed (e.g., sandblasting (ISO8501-1 Sa2 1 / 2), degreasing to remove oil and dust) to remove rust, grease, moisture, dust, salt, etc. from the substrate, or to improve the adhesion of the resulting coating film to the substrate. Furthermore, for the purpose of primary rust prevention, the substrate may be coated with a maintenance primer or the like.

[0214] <Process [2]>

[0215] The drying conditions in step [2] are not particularly limited and can be appropriately set depending on the coating film formation method, substrate type, application, coating environment, etc. The drying temperature is generally 5 to 35°C when drying at room temperature; and is generally 30°C or higher and lower than 100°C, more preferably 40 to 80°C, when forced drying is performed using a hot air dryer or the like. According to the composition A of the present invention, the composition can be dried and cured even under such room temperature drying conditions.

[0216] The drying time varies depending on the method of drying the coating film. In the case of drying at room temperature, it is, for example, about 1 to 7 days; and in the case of forced drying, it is, for example, about 5 to 60 minutes.

[0217] Example

[0218] An embodiment of the present invention is further described below by way of examples, but the present invention is not limited thereto.

[0219] [Example 1]

[0220] In a container, as shown in Table 1, 10 parts by mass of a non-aqueous epoxy compound (Note 1), 16 parts by mass of a non-aqueous epoxy compound (Note 2), 5.4 parts by mass of a 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 a silane coupling agent (Note 8), 0.3 parts by mass of an anti-sagging agent (Note 9), and 0.3 parts by mass of a defoaming agent (Note 10) were added. The mixture was stirred at room temperature (23°C) using a high-speed disperser until uniform, and then dispersed at 55-60°C for 30 minutes. The mixture was then cooled to below 30°C to prepare Composition 2.

[0221] Separately, in another container, 50 parts by mass of a water-dilutable amine (Note 12), 25 parts by mass of deionized water, and 5 parts by mass of tartaric acid were added to the container and stirred using a high-speed disperser until uniform, to prepare Composition 1.

[0222] The prepared composition 2 and composition 1 were mixed according to the mixing ratio (mass ratio) described in Table 1 before coating to prepare an anti-corrosion coating composition.

[0223] [Examples 2 to 17 and Comparative Examples 1 to 17]

[0224] An anticorrosion coating composition was prepared in the same manner as in Example 1, except that the components described in Tables 1, 2A, and 2B were used in the amounts (parts by mass) described in Tables 1, 2A, and 2B.

[0225] Table 3 shows the description of each component described in Table 1, Table 2A, and Table 2B.

[0226] [Table 1]

[0227]

[0228] [Table 2A]

[0229]

[0230] [Table 2B]

[0231]

[0232] [Table 3]

[0233]

[0234] <Availability Test>

[0235] According to the examples and comparative examples, 300 g of each freshly prepared anti-corrosion coating composition was weighed into a container, and the viscosity of each anti-corrosion coating composition at 35°C was adjusted to 2,000 mPa·s with water (LION viscometer: VT-04F, manufactured by LION Corporation). After keeping the anti-corrosion coating composition in a constant temperature bath at 35°C for 3 hours, the presence of precipitation and coagulation was observed, and the viscosity (35°C) was measured in the same manner as above.

[0236] The usable period was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.

[0237] (Evaluation Criteria)

[0238] ◯: The anticorrosion coating composition after 3 hours of heat preservation has no precipitation and aggregation, and the viscosity of the anticorrosion coating composition after 3 hours of heat preservation is less than 2,500 mPa·s.

[0239] Δ: There is no precipitation or aggregation in the anticorrosion coating composition after heat preservation for 3 hours, and the viscosity of the anticorrosion coating composition after heat preservation for 3 hours is 2,500 mPa·s or more and less than 4,000 mPa·s.

[0240] ×: The anticorrosion coating composition showed precipitation and / or aggregation after 3 hours. The viscosity of the anticorrosion coating composition after 3 hours of heat preservation became 4,000 mPa·s or more, or the composition became putty-like or gel-like.

[0241] [Preparation of a base material (test plate) with an anti-corrosion coating]

[0242] A sandblasted steel plate of SS400 (arithmetic mean roughness (Ra): 30-75 μm) with a size 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 the steel plate by air spraying so that the dry film thickness was 70 μm. Subsequently, the anticorrosive coating composition applied to the steel plate was dried at a temperature of 60° C. for 40 minutes, and then an aqueous acrylic resin topcoat (EKOMATE FINISH, manufactured by Japan China Paint Co., Ltd.) was applied by air spraying so that the dry film thickness was 40 μm. The applied aqueous acrylic resin topcoat was then dried at a temperature of 60° C. for 30 minutes and then dried at a temperature of 23° C. for 7 days to prepare a test plate 1.

[0243] Separately, the anticorrosion coating composition prepared as described above was applied by air spray to the surface of the same steel plate used in Test Plate 1 to a dry film thickness of 80 μm. The anticorrosion coating composition applied to the steel plate was then dried at 60°C for 30 minutes and then at 23°C for 7 days to produce Test Plate 2.

[0244] <Salt spray test>

[0245] In accordance with JIS K 5600-7-1:1999, the above-mentioned test panels 1 and 2 were subjected to a salt spray tester for 400 hours under salt spray conditions of 5% by mass, 35°C, and 98% relative humidity. The anticorrosion performance was evaluated according to the evaluation criteria described below. The results are shown in Tables 4 and 5.

[0246] In addition, when the evaluation in this salt spray test was 3 or more, it was considered that there was no problem in practical use in terms of anticorrosion performance.

[0247] (Evaluation Criteria)

[0248] 5: No rust, no bubbling

[0249] 4: There is no blistering, but the area of ​​rust on the substrate surface under the coating is less than 0.03% with respect to the entire substrate surface under the coating.

[0250] 3: Very small amounts of small bubbles are generated, and the area of ​​rust on the substrate surface under the coating is 0.03% or more and less than 0.1% of the entire substrate surface under the coating.

[0251] 2: Blisters are present, and the area of ​​rust on the substrate surface under the coating is 0.1% or more and less than 0.3% of the entire substrate surface under the coating.

[0252] 1: Blisters are present, and the area of ​​rust on the substrate surface under the coating is 0.3% or more relative to the entire substrate surface under the coating.

[0253] <Combined cycle test>

[0254] According to ASTM D2803, 25 cycles of testing were performed using the above-mentioned test panels 1 and 2. The appearance of the test panels after the test was evaluated according to the same evaluation criteria as the above-mentioned salt spray test. The results are shown in Tables 4 and 5.

[0255] In addition, when the evaluation in this combined cycle test was 3 or more, it was considered that there was no problem in practical use in terms of anticorrosion performance.

[0256] <Humidity resistance test>

[0257] After the test plate 2 was allowed to stand for 400 hours in a humidity test chamber maintained at a temperature of 50±1°C and a relative humidity of 95%, its appearance was evaluated using the same evaluation criteria as the salt spray test. The results are shown in Table 5.

[0258] In addition, when the evaluation in this moisture resistance test was 3 or more, it was considered that there was no problem in practical use of the moisture resistance performance.

[0259] [Table 4]

[0260]

[0261] [Table 5]

[0262]

Claims

1. An anti-corrosion coating composition, characterized in that contain, Anticorrosion composition 1 and anticorrosion composition 2, The anticorrosion composition 1 contains an amine compound (A); a divalent or higher polyvalent carboxylic acid (B); and water (C). The anticorrosion composition 2 contains a non-aqueous epoxy compound (D), The amine compound (A) includes a water-dilutable amine compound and a non-aqueous amine compound.

2. An anti-corrosion coating composition, characterized in that contain, Anticorrosion composition 1 and anticorrosion composition 2, The anticorrosion composition 1 contains an amine compound (A); a divalent or higher polyvalent carboxylic acid (B); and water (C). The anticorrosion composition 2 contains a non-aqueous epoxy compound (D), The amine compound (A) contains a water-dilutable amine compound and a non-aqueous amine compound, The ratio of the number of functional groups of the polycarboxylic acid (B) calculated by the following formula (1) to the active hydrogen equivalent of the solid component of the amine compound (A) when preparing the composition 1 of the present invention is 0.1 or more and 0.6 or less: Usage ratio = active hydrogen equivalent of the solid component of the amine compound (A) / usage amount of the solid component of the amine compound (A) (parts by mass) × (usage amount of the polycarboxylic acid (B) (parts by mass) × number of valences of the polycarboxylic acid (B)) / molecular weight of the polycarboxylic acid (B) (g / mol)···(1).

3. The anticorrosion coating composition according to claim 1 or 2, wherein The anti-corrosion composition 2 further contains a polycarbodiimide compound.

4. The anticorrosion coating composition according to claim 1 or 2, wherein The non-aqueous epoxy compound (D) is liquid at 23° C. and has a bisphenol skeleton.

5. The anti-corrosion coating composition according to claim 1 or 2, wherein The anti-corrosion composition 2 further contains a silane coupling agent.

6. An anti-corrosion coating, characterized in that: The anticorrosion coating composition is formed from the anticorrosion coating composition according to any one of claims 1 to 5.

7. A substrate with an anti-corrosion coating, characterized in that: The invention comprises a substrate and the anti-corrosion coating film according to claim 6.

8. A method for producing a substrate with an anti-corrosion coating, characterized in that: The process includes the following steps [1] and [2]: [1] A step of applying the anti-corrosion coating composition according to any one of claims 1 to 5 to a substrate; [2] A process of drying the anticorrosion coating composition applied on a substrate to form an anticorrosion coating film.

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