Water-based paint composition kit, water-based paint composition, coating film, painted product, and method for manufacturing the painted product.

Abstract

To provide a water-based paint composition kit that exhibits excellent curing properties even under high humidity or low temperatures, is less prone to tack formation, and can form a coating film with excellent walkability. [Solution] A water-based paint composition kit comprising a first agent containing a non-aqueous epoxy compound (A1) and a silicate compound (B), and a second agent containing an amine compound (C) and water.

Description

[Technical Field]

[0001] This disclosure relates to a water-based paint composition kit, a water-based paint composition, a coating film, a coated product, and a method for manufacturing a coated product. [Background technology]

[0002] Various industrial structures, such as bridges, tanks, plants, and (transport) containers, are typically coated with paint to prevent corrosion. In recent years, there has been a growing demand for a shift from solvent-based paints to water-based paints (water-based paint compositions) as the composition of these paint films, from the perspectives of environmental protection and workplace safety.

[0003] As the above-mentioned water-based paint composition, paint compositions such as epoxy-amine curing systems, which react epoxy resin with an amine-based curing agent, are known. For example, as a paint composition such as an epoxy-amine curing system, Patent Document 1 discloses a paint composition containing an epoxy resin, an amine curing agent, a silane coupling agent, water, and a pigment. Patent Document 2 also discloses a kit for a corrosion-preventive paint composition containing a first agent containing a non-aqueous epoxy compound, and a second agent containing a water-diluting component containing an amine compound and a non-aqueous component containing an amine compound. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2017 / 159740 [Patent Document 2] Japanese Patent Publication No. 2022-154829 [Overview of the project] [Problems that the invention aims to solve]

[0005] Conventional water-based paint compositions, such as epoxy-amine curing systems, contain a certain amount of water to ensure workability. However, the evaporation rate of water is affected by the curing environment, which in turn affects the drying properties of the paint film. In particular, it has been found that under high humidity or low temperature conditions (e.g., ambient humidity of 70% and ambient temperature of 5°C), the paint film becomes sticky (tack occurs). This is because, under these curing conditions, the evaporation rate of water from the paint film decreases drastically, making it easier for non-aqueous components such as non-aqueous epoxy resins and non-aqueous amine compounds to rise to the surface of the paint film. Once tack occurs, it can remain for several days, delaying the process on site. In addition to tack, as mentioned above, the non-aqueous components rise to the surface of the paint film, resulting in an uneven state of the film. This can lead to delayed curing, and when walking on the dried paint film, it can cause damage to the surface, such as shoe prints or twist marks, or even peeling of the paint film. The condition of the paint film surface after drying affects walkability, indicating that there is room for improvement from the perspective of walkability.

[0006] This disclosure aims to provide a water-based paint composition kit that exhibits excellent curing properties even under high humidity or low temperatures (e.g., 70% humidity or 5°C), is less prone to tack formation, and can form a coating film with excellent walkability. [Means for solving the problem]

[0007] One embodiment of the aqueous coating composition kit of the present disclosure comprises a first agent containing a non-aqueous epoxy compound (A1) and a silicate compound (B), and a second agent containing an amine compound (C) and water. [Effects of the Invention]

[0008] According to this disclosure, it is possible to obtain a water-based paint composition kit that exhibits excellent curing properties even under high humidity or low temperature conditions (e.g., 70% humidity or 5°C), is less prone to tack formation, and can form a coating film with excellent walkability. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a diagram illustrating the method for evaluating drying and curing properties in the examples. [Modes for carrying out the invention]

[0010] Water-based paint composition and kit thereof One embodiment of the water-based paint composition kit of the present disclosure (hereinafter also referred to as "Kit 1") comprises a first component and a second component, wherein the first component contains a non-aqueous epoxy compound (A1) and a silicate compound (B), and the second component contains an amine compound (C) and water. One embodiment of the aqueous coating composition kit of the present disclosure (hereinafter also referred to as "Kit 2") comprises a first agent, a second agent, and a third agent, wherein the first agent contains an aqueous epoxy compound (A2) and water, the second agent contains an amine compound (C), and the third agent contains a silicate compound (B). Hereinafter, Kit 1 and Kit 2 will be collectively referred to as "this kit."

[0011] The water-based paint composition obtained by mixing each component of Kit 1 is also referred to as "Composition 1." The water-based paint composition obtained by mixing each component of Kit 2 is also referred to as "Composition 2." Composition 1 and Composition 2 are collectively referred to as "the Composition." In this disclosure, "water-based paint composition" refers to a paint composition in which components such as epoxy compounds, amine compounds, and silicate compounds are dispersed and / or dissolved in water or a water-containing medium (hereinafter also referred to as "aqueous medium").

[0012] 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, more preferably 60 to 100% by mass. The aqueous medium may contain a medium other than water whose boiling point at normal pressure is less than 180°C. Examples of the medium other than water with a boiling point of less than 180°C under normal pressure include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol monopropyl ether. These may be used alone or in combination of two or more.

[0013] This kit 1 may be, for example, a two-component kit, and may have additional components in addition to the first and second components. This kit 2 may be, for example, a three-component kit, and may have additional components in addition to the first, second, and third components.

[0014] Each component such as the first component, the second component, and the third component is usually stored, preserved, transported, etc. in separate containers, and mixed together immediately before use.

[0015] [Non-aqueous epoxy compound (A1)] The first component of this kit 1 contains a non-aqueous epoxy compound (A1). The non-aqueous epoxy compound (A1) may be one kind or two or more kinds.

[0016] "Non-aqueous" in the non-aqueous epoxy compound (A1) means a state that is not freely miscible with water, a state that is substantially insoluble in water, and can also be said to be a non-aqueous dispersion type. Specifically, at 23°C, the epoxy compound and water are mixed so that the concentration of the epoxy compound becomes 3% by mass, stirred well, and left standing at 23°C for 1 hour. If the resulting mixture is not in a uniform state and 90% by mass or more of the epoxy compound mixed with water is separated, precipitated, or floating, the epoxy compound is defined as the non-aqueous epoxy compound (A1). It is preferable that the above epoxy compound has two or more epoxy groups in one molecule.

[0017] Furthermore, in some cases, it may be impossible to determine whether a non-aqueous epoxy compound (A1) was a non-aqueous epoxy compound after it has been mixed with other components that may be included in the first agent. However, even in such cases, if a non-aqueous epoxy compound is used as a raw material when preparing the first agent, etc., the first agent, etc. is said to contain the non-aqueous epoxy compound (A1). The same applies to aqueous epoxy compound (A2).

[0018] The non-aqueous epoxy compound (A1) is preferably a liquid epoxy compound that is liquid at room temperature (e.g., 15-25°C). Such a liquid epoxy compound is preferable because it is easy to uniformly disperse it in the first agent even if the first agent is an agent with a relatively small amount of solvent and contains components other than the non-aqueous epoxy compound (A1), and it also has good reactivity with the amine compound (C) described later.

[0019] The viscosity of the non-aqueous epoxy compound (A1) at 25°C, as measured with an E-type viscometer (TOKIMEC, FMD type, rotation speed: 60 rpm), is preferably 1,500 mPa·s or more, more preferably 3,000 mPa·s or more, preferably 120,000 mPa·s or less, more preferably 30,000 mPa·s or less, for example, between 1,500 and 120,000 mPa·s.

[0020] The epoxy equivalent of the solid content of the non-aqueous epoxy compound (A1) is preferably 500 or less, more preferably 170 to 280, and even more preferably 170 to 210, from the standpoint of reducing the viscosity of the paint composition, reducing the content of volatile organic compounds (VOCs) in the paint composition, and forming a coating film with excellent oil resistance, solvent resistance, chemical resistance, and corrosion resistance. The epoxy equivalent is calculated based on JIS K 7236:2001.

[0021] Examples of non-aqueous epoxy compounds (A1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, epoxidized oil-based epoxy resin, alkyl monoglycidyl ether, alkyl monoglycidyl ester, alkyl diglycidyl ether, alkyl diglycidyl ester, alkylphenol monoglycidyl ether, polyglycol monoglycidyl ether, and polyglycol diglycidyl ether. Preferred examples of the above alkyl group (alkyl) include alkyl groups having 3 to 15 carbon atoms, specifically, alkyl groups such as the neopentyl group and the 2-ethylhexyl group.

[0022] As the non-aqueous epoxy compound (A1), bisphenol A type epoxy resin or bisphenol F type epoxy resin is preferred because it can easily form a coating film with excellent corrosion resistance and adhesion to the substrate. Either bisphenol A type epoxy resin or bisphenol F type epoxy resin may be used, or both bisphenol A type epoxy resin and bisphenol F type epoxy resin may be used in combination.

[0023] The solid content of the non-aqueous epoxy compound (A1) in Composition 1 is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on 100% by mass of the solid content of Composition 1. The solid content of the non-aqueous epoxy compound (A1) in the first component of Kit 1 is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and even more preferably 50 to 80% by mass, based on 100% by mass of the solid content of the first component. When the content of the non-aqueous epoxy compound (A1) is within the above range, it is preferable because it allows for the easy formation of a coating film with excellent adhesion to the substrate, oil resistance, solvent resistance, chemical resistance, and corrosion resistance.

[0024] In this specification, components other than solvents such as organic solvents and water are referred to as "solids."

[0025] [Water-based epoxy compound (A2)] The first component of this kit 2 contains an aqueous epoxy compound (A2). The aqueous epoxy compound (A2) may be one type or two or more types.

[0026] Aqueous epoxy compounds (A2) refer to epoxy compounds that do not fall under non-aqueous epoxy compounds (A1). Specifically, if, at 23°C, an epoxy compound and water are mixed so that the epoxy compound concentration is 3% by mass, the mixture is thoroughly stirred, and then left to stand at 23°C for 1 hour, and more than 10% by mass of the epoxy compound mixed with water is dissolved or dispersed in the water without separation, precipitation, or suspension, then the epoxy compound is considered an aqueous epoxy compound (A2). Aqueous epoxy compounds (A2) are epoxy compounds that use water as the main solvent or dispersion medium, or epoxy compounds that are miscible with water (dilutable with water). More specifically, these include water-dispersible epoxy compounds, water-soluble epoxy compounds, and self-emulsifying epoxy compounds. Note that the above-mentioned water-miscible (dilutable with water) epoxy compounds refer to epoxy compounds that do not exhibit a significant increase in viscosity when mixed with water.

[0027] Furthermore, in the above mixture, if more than 10% by mass of the epoxy compound mixed with water is stably present in the water and the mixture is maintained in an emulsion state, then the epoxy compound shall be considered a water-dilutable epoxy compound. Also, in the above mixture, if more than 10% by mass of the epoxy compound mixed with water is stably present in the water and the epoxy compound mixed with water is present in a state where the average particle size measured by a laser diffraction particle size distribution analyzer (e.g., Mastersizer 3000 (manufactured by Spectris Co., Ltd.)) is less than 10 nm or no particles are observed, then the epoxy compound shall be considered a water-soluble epoxy compound.

[0028] Aqueous epoxy compounds (A2) can be synthesized by conventionally known methods, such as solution polymerization, suspension polymerization, emulsion polymerization, seed polymerization, miniemulsification polymerization, microemulsification polymerization, and soap-free emulsion polymerization. Alternatively, the epoxy compounds may be emulsified by known methods, such as phase inversion emulsification, D-phase emulsification, forced emulsification, gel emulsification, inversion emulsification, and high-pressure emulsification.

[0029] In the preparation of the first agent, it is preferable to use a mixture containing an aqueous epoxy compound (A2) and water. Specifically, the mixture is preferably an epoxy compound emulsion or an epoxy compound dispersion, and more preferably an epoxy compound emulsion. Examples of epoxy compound emulsions include emulsions in which oil droplets containing an epoxy compound are uniformly dispersed in an aqueous medium.

[0030] Epoxy compound emulsions can be prepared by forcibly emulsifying epoxy compounds in an aqueous medium, for example, by a phase inversion temperature emulsification method or a mechanical emulsification method. Examples of emulsifiers used include alkyl-type and alkylphenol-type nonionic surfactants; and anionic surfactants such as phosphate ester-type, alkylbenzene sulfonate-type, and sulfosuccinate-type surfactants. One or more of these emulsifiers may be used.

[0031] The solid content of the aqueous epoxy compound (A2) in the above mixture is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on 100% by mass of the above mixture, in order to obtain a paint composition that is superior in terms of ease of preparation, storage stability, etc. The above mixture may contain water, and may optionally contain conventionally known components such as surfactants.

[0032] The above epoxy compound preferably has two or more epoxy groups in one molecule. The epoxy compound described above may be a modified epoxy compound, taking into consideration the water resistance of the coating film to be formed and the reduction of the amount of emulsifier used. For example, this modification can be achieved by introducing an emulsifying segment into the molecule by bonding the epoxy compound with one or more other compounds, thereby modifying it into a self-emulsifying epoxy compound. More specifically, this can involve introducing at least one of the following into the epoxy compound: a polyoxyalkylene chain, a hydroxyl group, an amino group, and a carboxyl group. Note that one or more of these modified epoxy compounds may be used.

[0033] Specific examples of aqueous epoxy compounds (A2) include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, epoxidized oil-based epoxy resin, alkyl monoglycidyl ether, alkyl monoglycidyl ester, alkyl diglycidyl ether, alkyl diglycidyl ester, alkylphenol monoglycidyl ether, polyglycol monoglycidyl ether, and polyglycol diglycidyl ether. Preferred examples of the above alkyl group (alkyl) include alkyl groups having 3 to 15 carbon atoms, specifically, alkyl groups such as the neopentyl group and the 2-ethylhexyl group.

[0034] As the aqueous epoxy compound (A2), bisphenol A type epoxy resin or bisphenol F type epoxy resin is preferred because it can easily form a coating film with excellent corrosion resistance and adhesion to the substrate. Either bisphenol A type epoxy resin or bisphenol F type epoxy resin may be used, or both bisphenol A type epoxy resin and bisphenol F type epoxy resin may be used in combination.

[0035] The epoxy equivalent of the solid content of the aqueous epoxy compound (A2) is preferably 150 to 6,000, more preferably 170 to 3,000, from the viewpoint of easily forming a coating film with excellent low-temperature drying and curing properties, chemical resistance, and corrosion resistance. The epoxy equivalent is calculated based on JIS K 7236:2001.

[0036] The solid content of the aqueous epoxy compound (A2) in Composition 2 is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass, based on 100% by mass of the solid content of Composition 2. The solid content of the aqueous epoxy compound (A2) in the first component of Kit 2 is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on 100% by mass of the solid content of the first component. When the content of the aqueous epoxy compound (A2) is within the above range, it is preferable because it allows for the easy formation of a coating film with a good balance of corrosion resistance and adhesion to the substrate.

[0037] [Silicate compound (B)] This kit contains an agent that contains silicate compound (B). For example, the first agent of this kit 1 further contains silicate compound (B), and the third agent of this kit 2 contains silicate compound (B). The silicate compound (B) may be one type or two or more types.

[0038] One embodiment of this composition can form a coating film that exhibits excellent curability even under high humidity or low temperature conditions (including both high humidity and low temperature), is less prone to tack formation, and also has excellent walkability. The reason for these effects is presumed to be as follows. When drying a coating under high humidity or low temperatures, the evaporation rate of water from the coating is slow, and the coating remains wet for a long time. This causes non-aqueous components to rise to the surface of the coating due to their aversion to water, leading to tack formation. Additionally, uneven distribution of amine compounds and epoxy compounds can cause curing delays. On the other hand, in this composition, it is thought that the hydrolysis product of silicate compound (B) acts as a nucleus to promote the curing reaction between the amine compound and the epoxy compound. Furthermore, it is thought that the silicate compound (B) rises to the surface of the coating film during drying, thereby suppressing the rise of non-aqueous components. The silicate compound (B) that rises to the surface of the coating film undergoes condensation with other silicate compounds (B) and simultaneously reacts with the epoxy compound, amine compound, etc. For the reasons described above, it is presumed that the above effect was achieved by using this composition containing silicate compound (B) along with the above components. Furthermore, by using silicate compound (B), the coating film formed from this composition exhibits excellent chemical resistance (acid and alkali resistance).

[0039] Examples of silicate compounds (B) include silane compounds and low-level condensates of silane compounds. Examples of silane compounds include alkoxysilanes such as tetraalkoxysilanes and alkylalkoxysilanes.

[0040] Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. Examples of alkylalkoxysilanes include alkyltrialkoxysilanes. Examples of alkyltrialkoxysilanes include methyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; and ethyltrialkoxysilanes such as ethyltrimethoxysilane and ethyltriethoxysilane. The number of carbon atoms in the alkoxy group contained in the alkoxysilane is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the alkyl group contained in the alkylalkoxysilane is preferably 1 to 5, more preferably 1 to 3.

[0041] Low condensates of alkoxysilanes refer to condensates of alkoxysilanes having a degree of condensation of 2 to 20 (2 to 20 silicon atoms), preferably 3 to 18 (3 to 18 silicon atoms), more preferably 3 to 15 (3 to 15 silicon atoms), and even more preferably 3 to 10 (3 to 10 silicon atoms).

[0042] Among silicate compounds (B), low condensates of alkoxysilanes are preferred from the viewpoint of lowering the viscosity of the paint composition and balancing curability, and the compound represented by the following formula (B1) is more preferred.

[0043] [ka]

[0044] In the above formula (B1), R 1 and R 2 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X 1 and X 2 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents the number of repetitions. The alkyl group described above may or may not be substituted. Furthermore, the alkyl group may have a linear or branched structure.

[0045] Preferred silicate compounds (B) include tetramethoxysilane or its low condensates, tetraethoxysilane or its low condensates, tetra-n-propoxysilane, and tetra-n-butoxysilane. Among these, compounds with fewer carbon atoms in the alkyl group are preferred from the viewpoint of curing speed during drying of the coating film, and tetramethoxysilane or its low condensates and tetraethoxysilane or its low condensates are more preferred.

[0046] Furthermore, it is preferable to use two or more silicate compounds (B) in combination, as this allows for the formation of a coating film that is less prone to tack even when dried under high humidity or low temperatures, and also provides a paint composition with a long pot life. In one embodiment of the present disclosure, it is more preferable to use a silicate compound (Ba) which is tetraethoxysilane or a low condensate thereof in combination with at least one silicate compound (Bb) selected from tetramethoxysilane or a low condensate thereof, tetra-n-propoxysilane, and tetra-n-butoxysilane. In order to obtain a paint composition with excellent curing speed and long pot life, the content of the silicate compound (Bb) is preferably 1 to 100 parts by mass, more preferably 5 to 90 parts by mass, and even more preferably 15 to 80 parts by mass, per 100 parts by mass of silicate compound (Ba).

[0047] The number of repetitions n is preferably 2 to 20, more preferably 3 to 18, even more preferably 3 to 15, and particularly preferably 3 to 10, in order to obtain a paint composition with excellent curing speed.

[0048] The weight-average molecular weight (Mw) of silicate compound (B) is preferably 100 to 3,000, more preferably 150 to 2,000, and even more preferably 180 to 1,500. When Mw is above the lower limit, the curing rate of the coating film is fast and tack is less likely to occur, even under high humidity or low temperature conditions during drying. The above Mw is measured by gel permeation chromatography (GPC). The value obtained by GPC is a value (polystyrene equivalent) determined using a calibration curve created with polystyrene as the standard substance.

[0049] The specific gravity (at 25°C) of silicate compound (B) is preferably as low as possible, but is preferably 0.7 to 1.4, and more preferably 0.8 to 1.3. When the specific gravity is below the above upper limit, tack tends to be less likely to occur during drying of the coating film, even under high humidity or low temperatures.

[0050] The silicate compound (B) content in this composition is preferably 0.05 to 35% by mass, more preferably 0.5 to 25% by mass, and even more preferably 1 to 15% by mass, based on 100% by mass of the solid content of this composition.

[0051] The content of silicate compound (B) in the first component of Kit 1 is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 35 parts by mass, based on 100 parts by mass of the solid content of the non-aqueous epoxy compound (A1) in the first component.

[0052] The silicate compound (B) content in composition 2 obtained using kit 2 is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 35 parts by mass, per 100 parts by mass of the solid content of aqueous epoxy compound (A2).

[0053] When the silicate compound (B) content is within the above range, a coating film can be easily formed that exhibits excellent curing properties even under high humidity or low temperatures, is less prone to tack formation, and also has excellent walkability and chemical resistance.

[0054] [Amine compound (C)] The second component of this kit contains an amine compound (C). The amine compound (C) may be one type or two or more types.

[0055] Specific examples of amine compounds (C) include water-dilutable amine compounds and non-aqueous amine compounds. Furthermore, for example, when using a water-dilutable amine compound, it may be impossible to determine whether the water-dilutable amine compound was water-dilutable after mixing it with other components that may be included in the second agent. However, even in such cases, if a water-dilutable amine compound is used as a raw material when preparing the second agent, the second agent is said to contain a water-dilutable amine compound. The same applies to non-aqueous amine compounds.

[0056] A water-dilutable amine compound refers to an epoxy-curable amine compound that dissolves or disperses in a relatively large amount in the aqueous medium described above. Specifically, if, after mixing the amine compound with water at 23°C so that the solid content is 50% by mass, thoroughly stirring the mixture, and letting it stand at 23°C for 1 hour, at least 80% by mass of the solid content of the amine compound mixed with water remains uniformly in the water, then the amine compound is considered a water-dilutable amine compound. Furthermore, for components containing amine compounds with a solid content of less than 50% by mass, the solid content is adjusted to 50% by mass using an evaporator or the like. After that, it is evaluated in the same manner as above, and if the conditions are met, it is considered a water-dilutable amine compound.

[0057] Specific examples of the above-mentioned water-dilutable amine compounds include hydrophilic amine compounds obtained by reacting the following amine compounds used as curing agents for epoxy compounds with glycidyl ethers of polyalkylene glycols or polyoxyalkyleneamines, etc., amine compounds having an amide structure obtained using fatty acids and aliphatic amine compounds, or compounds obtained by forcibly dispersing the following amine compounds used as curing agents for epoxy compounds in water, after imparting emulsifying ability to them by neutralizing them with acid or mixing them with emulsifiers.

[0058] A non-aqueous amine compound is an epoxy-curable amine compound that is not freely miscible with water, and is essentially an epoxy-curable amine compound that is insoluble in water. Specifically, if an amine compound and water are mixed at 23°C so that the solid content is 3% by mass, the mixture is thoroughly stirred, and the resulting mixture is left to stand at 23°C for 1 hour, and the resulting mixture is not homogeneous, and 50% or more of the solid content of the amine compound mixed with water is separated, precipitated, or suspended, then the amine compound is considered a non-aqueous amine compound.

[0059] The amine compound used as a curing agent for the epoxy compound is not particularly limited as long as it is a tertiary amine (an amine compound having only a tertiary amino group) and an amine compound other than the flash last inhibitor described later, but examples include amine compounds having two or more amino groups in one molecule, and amine compounds such as aliphatic, alicyclic, aromatic, and heterocyclic are preferred.

[0060] Examples of the aliphatic amine compound include alkylene polyamine, polyalkylene polyamine, and alkylaminoalkylamine.

[0061] Examples of the alkylene polyamine include compounds represented by the formula: "H2N-R 1 -NH2" (R 1 is a divalent hydrocarbon group having 1 to 12 carbon atoms.), and specific examples include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and trimethylhexamethylenediamine.

[0062] Examples of the polyalkylene polyamine include compounds represented by the formula: "H2N-(C m H 2m NH) n H" (m is an integer from 1 to 10. n is an integer from 2 to 10, preferably an integer from 2 to 6.), and specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenetetramine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0063] Examples of the alkylaminoalkylamine include compounds represented by the formula: "R 2 2N-(CH2)p -NH2" (R 2 These are independently hydrogen atoms or C1-C8 alkyl groups (where at least one R) 2 A is an alkyl group having 1 to 8 carbon atoms, and p is an integer from 1 to 6. Examples of compounds represented by ) include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0064] Other aliphatic amine compounds include, for example, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylene polyamines (especially diethylene glycol bis(3-aminopropyl) ether), bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), mensendiamine (MDA), o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4-bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), and 1-[2'-(2''-aminoethylamino)ethyl]piperazine.

[0065] Specific examples of the above-mentioned alicyclic amine compounds include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine and 4,4'-methylenebis(2-methylcyclohexylamine)), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0066] Examples of the above-mentioned aromatic amine compounds include aromatic polyamine compounds having two or more primary amino groups bonded to aromatic rings such as benzene rings or naphthalene rings. Specific examples of these aromatic amine compounds include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and diethylmethylbenzenediamine.

[0067] Specific examples of the above heterocyclic amine compounds include 1,4-diazacycloheptane, 1,4-bis(3-aminopropyl)piperazine, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0068] Amine compounds used as curing agents for the epoxy compounds mentioned above can also include modified versions of the amine compounds, such as modified alicyclic polyamines, modified aliphatic polyamines, fatty acid modified products such as polyamidoamines, amine adducts with epoxy compounds, Mannich-modified amines (e.g., Mannich-modified amines having a phenol-derived skeleton (phenalkamine, phenalkamide, etc.)), Michael adducts, ketimines, and aldimines. Among these, modified alicyclic polyamines, modified aliphatic polyamines, polyamidoamines, amine adducts with epoxy compounds, and Mannich-modified amines having a phenol-derived skeleton are preferred.

[0069] The active hydrogen equivalent of the solid content of the amine compound (C) is preferably 20 to 200, more preferably 30 to 190, from the viewpoint of easily forming a coating film with excellent low-temperature drying and curing properties and corrosion resistance.

[0070] From the standpoint of easily forming a coating film with excellent corrosion resistance, coating strength, and low-temperature drying and curing properties, it is desirable to use the amine compound (C) in an amount such that the reaction ratio calculated by the following formula (1) is preferably 0.3 to 1.5, more preferably 0.4 to 1.2.

[0071] Reaction ratio = {(Amount of solid content of amine compound (C) / Active hydrogen equivalent of amine compound (C) solid content) + (Amount of solid content of component reactive with epoxy compound / Functional group equivalent of component reactive with epoxy compound)} / {(Amount of solid content of epoxy compound / Epoxy equivalent of epoxy compound solid content) + (Amount of solid content of component reactive with amine compound (C) / Functional group equivalent of component reactive with amine compound (C) solid content)} ... (1)

[0072] Here, examples of epoxy compounds in formula (1) above include a non-aqueous epoxy compound (A1) and an aqueous epoxy compound (A2). Examples of the "component that is reactive to the amine compound (C)" and the "component that is reactive to the epoxy compound" in formula (1) above include silane coupling agents. As the silane coupling agent mentioned above, a silane coupling agent having an amino group or an epoxy group as a reactive group can be used. Therefore, depending on the type of reactive group, it is necessary to determine whether the silane coupling agent is reactive with the amine compound (C) or with the epoxy compound, and to calculate the reaction ratio.

[0073] The "functional group equivalent" for each of the above components refers to the mass (g) per mole of functional group obtained by dividing the mass of 1 mole of these components by the number of moles of functional groups contained in it.

[0074] The solid content of amine compound (C) in this composition is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 15% by mass, based on 100% by mass of the solid content of this composition. The solid content of amine compound (C) in the second component of this kit is preferably 5 to 100% by mass, more preferably 7 to 99% by mass, and even more preferably 10 to 99% by mass, based on 100% by mass of the solid content of the second component. When the content of amine compound (C) is within the above range, a coating film with excellent corrosion resistance and drying properties can be easily formed.

[0075] In one embodiment, the second agent of Kit 1 contains a water-dilutable amine compound and water, preferably a water-dilutable amine compound, a non-aqueous amine compound, and water. When the second component of Kit 1 contains a water-dilutable amine compound and a non-aqueous amine compound, the solid content of the water-dilutable amine compound is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 60 parts by mass, based on 100 parts by mass of the solid content of the non-aqueous amine compound. The water content in the second component of this kit is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass, based on 100% by mass of the second component.

[0076] In one embodiment, the second agent of Kit 2 contains a non-aqueous amine compound. The water content in such a second agent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the second agent.

[0077] In one embodiment, the second agent of Kit 2 further contains water in addition to the amine compound (C). The second agent contains, for example, at least one selected from water-dilutable amine compounds and non-aqueous amine compounds, and water. The water content in such a second agent is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the second agent.

[0078] [water] To facilitate the preparation of this composition and improve its storage stability, this composition further contains water. Specifically, the second component of Kit 1 contains water, and the first component of Kit 2 contains water. The water used is not particularly limited, and tap water may be used, but it is preferable to use deionized water.

[0079] The water content in this composition is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 18 to 30% by mass, based on 100% by mass of the composition. The water content is measured according to the Karl Fischer method using a moisture meter (e.g., CA-310, manufactured by Nitto Seikou Analytech Co., Ltd.).

[0080] [Other ingredients] This composition may further contain components other than those described above (hereinafter also referred to as "other components"). Unless otherwise specified, each agent in this kit may further contain other components. Examples of other components include non-reactive diluents, silane coupling agents, pigments, (pigment) dispersants, defoaming agents, viscosity modifiers (anti-sagging agents, anti-settling agents, thixotropes), flash rust inhibitors, curing accelerators, dehydrating agents, divalent or higher polycarboxylic acids, and film-forming aids. Other ingredients may be used individually or in combination of two or more.

[0081] Other components can be conventionally known components, and commercially available products may also be used.

[0082] <Non-reactive diluent> This composition may contain a non-reactive diluent. It is preferable that this composition contains a non-reactive diluent, as this can improve the flexibility of the resulting coating film. A non-reactive diluent refers to a compound that does not have a functional group that is reactive to epoxy or amino groups.

[0083] The above-mentioned non-reactive diluents can be broadly selected from conventionally known non-reactive diluents, including liquid hydrocarbon resins such as low-boiling fractions obtained by thermal decomposition of naphtha (including modified products of said liquid hydrocarbon resins), cardanol and cardanol derivatives prepared from cashew nut shell liquid, petroleum resins, xylene resins, and coumarone indene resins. Specifically, examples include the liquid hydrocarbon resins and flexibility-imparting resins described in Japanese Patent Application Publication No. 2006-342360.

[0084] Among these, liquid hydrocarbon resins, cardanol, and cardanol derivatives are preferred, and phenol-modified hydrocarbon resins, cardanol, and cardanol derivatives are more preferred, due to their excellent compatibility with the epoxy compounds (non-aqueous epoxy compound (A1) or aqueous epoxy compound (A2)). Examples of the phenol-modified hydrocarbon resins mentioned above include resins obtained using diolefins, monoolefins, or α-methylstyrene contained in the cracked oil fractions of petroleum and coal, and phenols (phenol compounds), as described in Japanese Patent Publication No. 9-268209, Japanese Patent Publication No. 7-196793, etc.

[0085] More specifically, the above-mentioned phenol-modified hydrocarbon resins include C5-based (aliphatic) petroleum resins made from C5 fractions; C9-based (aromatic) petroleum resins made from C9 fractions; C5-C9 copolymer petroleum resins; dicyclopentadiene resins made from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in the C5 fraction; α-methylstyrene; and resins obtained by reacting these with phenols. Among these, resins obtained by addition polymerization of styrene, vinyltoluene, coumarone, indene, and α-methylstyrene, which are contained in the cracked oil fractions of petroleum and coal, with phenols are preferred.

[0086] The average molecular weight of the phenol-modified hydrocarbon resins mentioned above is typically 200 to 1,000, and their viscosity is typically 30 to 10,000 mPa·s / 25℃.

[0087] Organic solvents may be used as non-reactive diluents. The organic solvent is preferably an organic solvent with a boiling point of less than 180°C at normal pressure. Examples include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), ether solvents such as butyl cellosolve, ester solvents such as butyl acetate, alcohol solvents such as 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.

[0088] If this composition contains an organic solvent, it is preferable to use an organic solvent such that the VOC content in this composition falls within the following range. The first agent of this kit 1 is preferably a solvent-based agent containing an organic solvent, or a solvent-free agent. When preparing the first agent containing an organic solvent, it is preferable to use an organic solvent such that the content of the organic solvent is preferably 12% by mass or less, more preferably 10% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more, for example, 1 to 12% by mass, based on 100% by mass of the first agent.

[0089] If the composition contains a non-reactive diluent, the content of the non-reactive diluent is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the composition. When the content of the non-reactive diluent is within the above range, a paint composition with a long pot life can be easily obtained.

[0090] <Silane coupling agent> This composition may contain a silane coupling agent. By using a silane coupling agent, a low-viscosity paint composition can be easily obtained, further improving the adhesion of the resulting coating film to the substrate, as well as improving the corrosion resistance (water resistance, saltwater resistance, etc.) and heat resistance of the resulting coating film.

[0091] The silane coupling agent is not particularly limited, and conventionally known compounds can be used. However, it is preferable that the compound has at least two functional groups within the same molecule and can contribute to improving adhesion to the substrate and reducing the viscosity of the composition.

[0092] Silane coupling agents include, for example, those with the formula: "X-SiMe n Y 3-n It is preferable that the compound is represented by "[n is 0 or 1, X is a functional group that can react with organic matter (e.g., amino group, vinyl group, epoxy group, mercapto group, halogeno group, a group in which part of a hydrocarbon group is substituted with one of these groups, or a group in which part of a hydrocarbon group is substituted with an ether bond, etc., and part of that group is substituted with one of these groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., alkoxy groups such as methoxy and ethoxy groups)].

[0093] When using a silane coupling agent that is reactive with an amine compound (C), such as an epoxy group-containing silane coupling agent, it is preferable to incorporate the silane coupling agent into the first agent. Furthermore, when using a silane coupling agent that is reactive with epoxy compounds (non-aqueous epoxy compounds (A1) or aqueous epoxy compounds (A2)), such as an amino group-containing silane coupling agent, it is preferable to incorporate the silane coupling agent into the second component.

[0094] Among the silane coupling agents described above, it is preferable that the silane coupling agent contains an epoxy group, in which X is an epoxy group, a group in which part of a hydrocarbon group is substituted with an epoxy group, or a group in which part of a hydrocarbon group is substituted with an ether bond or the like and part of the group is substituted with an epoxy group.

[0095] If the composition contains a silane coupling agent, the amount of the silane coupling agent is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the solid content of the composition. When the silane coupling agent content is within the above range, the viscosity of the composition can be reduced, making it easy to obtain a low-viscosity paint composition with excellent paintability, and improving the adhesion, corrosion resistance, and heat resistance of the resulting coating film to the substrate.

[0096] <Pigments> This composition may contain pigments (excluding flash last inhibitors described later). Examples of the above-mentioned pigments include extender pigments, coloring pigments, and rust-preventive pigments.

[0097] In one embodiment, the second component of Kit 1 contains at least one selected from water-dilutable amine compounds and non-aqueous amine compounds, and a pigment. When the second component of Kit 1 is in this form, it is possible to form an anticorrosive coating film with excellent corrosion resistance, particularly under salt spray and high temperature and humidity conditions.

[0098] When this composition contains a pigment, the pigment mass concentration (PWC) in this composition is preferably 20-80%, more preferably 30-75%, in order to easily obtain a composition with excellent paintability, and to easily form an anticorrosive coating film with excellent adhesion to the substrate due to stress relaxation and water resistance. The above PWC refers to the percentage of the total mass of pigments relative to the mass of solids in this composition, and is represented by the following formula (2). PWC[%] = Total mass of all pigments in this composition / Mass of solids in this composition × 100 ... (2)

[0099] When this composition contains a pigment, the volume concentration of the pigment (PVC) in this composition is preferably 20-50%, more preferably 20-45%, even more preferably 20-40%, and particularly preferably 20-38%, in order to easily obtain a composition with superior paintability, and to easily form a coating film with superior adhesion to the substrate due to stress relaxation and superior water resistance.

[0100] The above PVC refers to the total volume concentration of pigments relative to the volume of solids in this composition, and is represented by the following formula (3). PVC[%] = Total volume of all pigments in this composition × 100 / Volume of solids in this composition ... Formula (3)

[0101] The volume of solids in the composition described above can be calculated from the mass and true density of the solids in the composition. The mass and true density of the solids may be measured values ​​or values ​​calculated from the raw materials used. The volume of the above-mentioned pigment can be calculated from the mass and true density of the pigment used. The mass and true density of the pigment may be measured values ​​or values ​​calculated from the raw materials used. For example, it can be calculated by separating the pigment from other components from the solid content of the composition and measuring the mass and true density of the separated pigment.

[0102] Body pigments There are no particular restrictions on the extender pigment, but it must be a pigment other than the coloring pigments and rust-preventive pigments listed below. Examples of the above-mentioned extender pigments include conventionally known talc, mica, barium sulfate (including precipitated barium sulfate and extirpated barium sulfate), potassium feldspar, kaolin, alumina white, clay, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silica. Among these, talc, mica, barium sulfate, and potassium feldspar are preferred.

[0103] If this composition contains extender pigments, the amount of extender pigments is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, relative to 100% by mass of the solid content of this composition, in order to easily form a coating film that is well balanced in terms of corrosion resistance, water resistance, adhesion to the substrate, and impact resistance.

[0104] Coloring pigments There are no particular restrictions on the coloring pigments, but they must be pigments other than the rust-preventive pigments listed below. Examples of the above-mentioned coloring pigments include conventionally known inorganic pigments such as carbon black, titanium dioxide (titanium white), iron oxide (red iron oxide), yellow iron oxide, and ultramarine, as well as organic pigments such as cyanine blue and cyanine green. Among these, titanium white, carbon black, and red iron oxide are preferred.

[0105] If the composition contains a coloring pigment, its content is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, based on 100% by mass of the solid content of the composition.

[0106] Rust-preventive pigments Examples of rust-preventive pigments include zinc powder, zinc alloy powder, zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, zinc cyanamide compounds, borate compounds, nitro compounds, and complex oxides. Among these, aluminum phosphate compounds are preferred.

[0107] When this composition contains a rust-preventive pigment, its content is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, relative to 100% by mass of the solid content of this composition, in order to easily form a coating film that is well balanced in terms of corrosion resistance, water resistance, adhesion to the substrate, and impact resistance.

[0108] <(Pigment) Dispersant> (Pigment) Dispersants are not particularly limited, but examples include various dispersants such as copolymers having compatible chains, such as fatty acids, polyaminos, polyethers, polyesters, polyurethanes, and polyacrylates, which have pigment-adsorbing groups (pigment affinity groups) such as carboxyl groups, phosphate groups, amino groups, groups of these salts, and ammonium bases.

[0109] If the composition contains a (pigment) dispersant, its content is preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass, relative to 100% by mass of the solid content of the composition, in order to easily form a coating film in which pigments, etc., are uniformly dispersed and to easily form a coating film with excellent crack resistance.

[0110] <Antifoaming agent> To suppress the generation of foam during the preparation or application of this composition, or to break any foam generated in this composition and form a coating with desired physical properties, an antifoaming agent may be added to this composition as needed.

[0111] If the composition contains an antifoaming agent, the amount is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on 100% by mass of the solid content of the composition, in order to sufficiently suppress the generation of foam and to easily form a coating film with the desired physical properties.

[0112] <Viscosity modifier> While there are no particular limitations on the viscosity modifier, it is preferable that the material can suppress the settling of pigments and other elements in the composition and improve its storage stability, or that the material can improve the anti-sagging properties of the composition during and after painting.

[0113] As the viscosity modifiers mentioned above, conventionally known viscosity modifiers can be used, such as organic clay waxes like stearate salts, lecithin salts, and alkyl sulfonates of Al, Ca, and Zn; polyethylene wax; amide viscosity modifiers; amide neutralized salt viscosity modifiers; mixtures of amide viscosity modifiers; hydrogenated castor oil wax; mixtures of hydrogenated castor oil wax and amide wax; synthetic fine silica powder; oxidized polyethylene wax; and urea viscosity modifiers. Among these, amide viscosity modifiers, amide neutralized salt viscosity modifiers, and mixtures of amide viscosity modifiers are preferred because they can further improve the anti-sagging properties of the composition during and after painting.

[0114] If the composition contains a viscosity modifier, the solid content of the viscosity modifier is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, based on 100% by mass of the solid content of the composition. When the viscosity modifier content is within the above range, a paint composition with excellent paintability can be easily obtained.

[0115] <Flash last suppressant> Examples of flash last inhibitors include nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite, and ammonium nitrite; benzoates such as sodium benzoate, potassium benzoate, calcium benzoate, and ammonium benzoate; phytes such as sodium phytate and potassium phytate; salts of fatty acids such as sebaciic acid and dodecanoic acid; phosphate derivatives such as alkyl phosphates and polyphosphates; tannates; metal sulfonates; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), and diethylenetriamine. Examples of chelating agents include amine-based chelating agents such as tetraacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their alkali metal salts; addition reaction products obtained using 4-methyl-γ-oxobenzenebutanoic acid and N-ethylmorpholine; intercalation compounds obtained by intercalating monoalkylamines, polyamines, and / or quaternary ammonium ions with layered phosphates such as aluminum dihydrogen tripolyphosphate; and hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds.

[0116] Among these, nitrites (e.g., metal salts such as sodium, potassium, and calcium, and ammonium salts) and benzoates (e.g., metal salts such as sodium, potassium, and calcium, and ammonium salts) are preferred due to their excellent flash-rust resistance and low cost. Nitrites are more preferred, and sodium nitrite is particularly preferred, because compositions exhibiting high flash-rust resistance can be easily obtained even with small amounts of use.

[0117] If the composition contains a flashlast inhibitor, the amount is preferably 0.01 to 2% by mass, more preferably 0.03 to 1% by mass, based on 100% by mass of the solid content of the composition, in order to easily obtain a composition with excellent flashlast resistance.

[0118] <Polycarboxylic acids with two or more valent values> Divalent or greater polycarboxylic acids are organic acids that have two or more carboxyl groups in a single molecule. It is preferable that the second component contains a divalent or higher polycarboxylic acid, as this allows for easy acquisition of a paint composition with a long pot life and easy formation of a coating film with excellent corrosion resistance.

[0119] There are no particular limitations on the divalent or greater polycarboxylic acid, but examples 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 a coating film with superior corrosion resistance.

[0120] The molecular weight of the above-mentioned divalent or greater polycarboxylic acid is preferably 500 or less, more preferably 300 or less, and even more preferably 200 or less, from the viewpoint that a paint composition with a good balance of pot life and drying properties can be easily obtained.

[0121] When this composition contains a divalent or greater polycarboxylic acid, the content of the divalent or greater polycarboxylic acid is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, for example 5 to 30 parts by mass, based on 100 parts by mass of solids of the amine compound (C), in order to easily obtain a paint composition with a long pot life and to easily form a coating film with excellent corrosion resistance.

[0122] <Membrane-forming aid> Because this composition contains water, it may freeze in winter, etc., and also to improve film-forming properties at low temperatures and the finished appearance of the resulting coating, it may contain a film-forming aid.

[0123] As film-forming aids, film-forming aids commonly used in water-based paint compositions, such as organic compounds with a boiling point of 180°C or higher at room temperature, can be used. Examples include linear or branched aliphatic alcohols having 5 to 15 carbon atoms; alcohols having aromatic rings such as benzyl alcohol; monoethers such as (poly)ethylene glycol or (poly)propylene glycol; (poly)ethylene glycol ether esters; and (poly)propylene glycol ether esters.

[0124] When this composition contains a film-forming aid, the amount of the film-forming aid is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on 100% by mass of the solid content of this composition, in order to easily form a coating film with excellent film-forming properties and appearance at low temperatures.

[0125] [This composition] The solid content of this composition, calculated from the solid content and blending amount of each raw material, is preferably 60-85% by mass, more preferably 65-82% by mass, and even more preferably 70-80% by mass.

[0126] The content of volatile organic compounds (VOCs) in this composition is preferably 100 g / L or less, more preferably 90 g / L or less, and even more preferably 80 g / L or less, in order to ensure that the composition has minimal impact on the natural environment and the painting work environment.

[0127] The VOC content in this composition can be measured according to ISO 11890-1.

[0128] <Method for preparing this composition> Composition 1 can be prepared by mixing (kneading) a first agent containing a non-aqueous epoxy compound (A1) and a silicate compound (B) with a second agent containing an amine compound (C) and water. Composition 2 can be prepared by mixing (kneading) a first agent containing an aqueous epoxy compound (A2) and water with a second agent containing an amine compound (C) and a third agent containing a silicate compound (B).

[0129] The first agent, the second agent, and the third agent, if necessary, can be prepared by mixing (kneading) the components to be incorporated into these agents. During this mixing (kneading), the components may be added and mixed all at once, or they may be added and mixed in multiple stages. When performing the above mixing (kneading), conventionally known devices such as mixers, dispersers, and agitators can be used. Examples of such devices include dispersers, mixing / dispersing mills, mortar mixers, rolls, paint shakers, and homogenizers. Furthermore, when performing the above mixing (kneading), heating or cooling may be carried out depending on the season, environment, etc.

[0130] ≪Coating films, painted products, and methods for manufacturing painted products≫ The coating film of this disclosure (hereinafter also referred to as "this coating film") is formed using this composition, specifically by drying (curing) this composition, and is usually formed on a substrate. The coated product of this disclosure includes a substrate and the coating film.

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

[0132] The above-mentioned substrate is not particularly limited, but a substrate that requires abrasion resistance and corrosion resistance is preferred in order to better demonstrate the effects of using this composition, for example, (steel) structures such as ships, offshore structures, plants, bridges, tanks, and containers.

[0133] The dry film thickness of this coating is not particularly limited, but is preferably 10 to 400 μm, more preferably 15 to 300 μm, in order to obtain a coating with sufficient abrasion resistance and corrosion resistance. For example, it may be 50 μm or more, 100 μm or more, or 130 μm or more. Conventional water-based paint compositions have a slow water evaporation rate, making it difficult to achieve the large film thicknesses described above. However, by using this composition, it is possible to form a paint film that does not experience curing delay and is less prone to tack when such large film thicknesses are achieved.

[0134] The method for forming this coating film may involve either forming the desired film thickness in a single coat, or forming the desired film thickness in two or more coats.

[0135] The above-mentioned painted product may further include at least one coating film selected from the group consisting of an undercoat film (primer 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 film for the purpose of weather resistance or aesthetics.

[0136] When this composition is used as a substitute for zinc primer, the coated product may include an intermediate coating or a topcoat on top of this coating.

[0137] Examples of undercoat coatings include coatings formed from various primer compositions such as epoxy resins. Examples of intermediate coatings include coatings formed from various intermediate coating compositions such as (meth)acrylic resins, epoxy resins, and urethane resins. Examples of topcoat coatings include coatings formed from various topcoat compositions such as (meth)acrylic resins, (meth)acrylic silicone resins, urethane resins, silicone resins, and fluororesin resins. The composition of this composition may be changed to form undercoat coatings, intermediate coatings, and topcoat coatings.

[0138] The method for manufacturing a painted product according to this disclosure is: Step [1]: A step of coating the composition onto a substrate, and Step [2]: A step of drying the painted composition to form a coating film. Includes.

[0139] <Process [1]> The painting method in step [1] is not particularly limited and includes conventionally known methods such as spray painting including airless spray painting and air spray painting, brush painting, and roller painting. Among these, spray painting is preferred because it can easily paint large surface areas of substrates such as the above-mentioned structures. When applying this type of coating, it is preferable to apply the coating so that the dry film thickness of the resulting coating falls within the above range.

[0140] The conditions for spray painting can be adjusted as appropriate depending on the desired dry film thickness. For example, in the case of airless spray painting, a primary (air) pressure of approximately 0.3 to 0.6 MPa, a secondary (paint) pressure of approximately 10 to 15 MPa, and a gun travel speed of approximately 50 to 120 cm / second are preferable.

[0141] The viscosity of this composition, suitable for spray coating, is preferably 6,000 to 20,000 mPa·s, and more preferably 8,000 to 12,000 mPa·s, measured at 23°C using a B-type viscometer (manufactured by Rion Co., Ltd., model VT-04F).

[0142] Furthermore, when applying this composition, the viscosity may be adjusted to an appropriate level for the paint composition, if desired. Water is preferred as the diluent used for such viscosity adjustment. In this case, it is preferable to use a diluent to achieve a paint viscosity suitable for each painting method. For example, when using airless spray painting, the amount of diluent used per 100 parts by mass of the composition is preferably 1 to 30 parts by mass.

[0143] <Process [2]> The drying conditions in step [2] are not particularly limited and may be set appropriately depending on the coating film formation method, substrate type, application, painting environment, etc.

[0144] This composition exhibits excellent curability and can be dried at low temperatures. Therefore, it may be cured by forced drying with heat and airflow if desired, but it is usually dried and cured at 1 to 35°C. On the other hand, the drying time varies depending on the drying method of the coating film. When drying within the above temperature range, it is usually 1 hour to 7 days, preferably 1 to 3 days, and when forced drying is used, it is usually 5 to 60 minutes, preferably 10 to 30 minutes.

[0145] [Example of behavior] This disclosure includes, for example, the following: <1> ~ <8> Regarding. <1> The first agent contains a non-aqueous epoxy compound (A1) and a silicate compound (B), A second agent containing an amine compound (C) and water, A water-based paint composition kit having the following features. <2> The content of silicate compound (B) in the first agent is 1 to 50 parts by mass per 100 parts by mass of the solid content of the non-aqueous epoxy compound (A1). <1> A water-based paint composition kit as described above. <3> The first agent contains an aqueous epoxy compound (A2) and water, A second agent containing an amine compound (C), A third agent containing silicate compound (B), A water-based paint composition kit having the following features. <4> The second agent further contains water. <3> A water-based paint composition kit as described above.

[0146] <5> <1> or <2> By mixing the first and second components in the water-based paint composition kit described above, or <3> or <4> A water-based paint composition obtained by mixing the first component, the second component, and the third component of the water-based paint composition kit described in [reference].

[0147] <6> <5> A coating film formed from the water-based paint composition described above. <7> base material and <6> A painted product including the coating film described above.

[0148] <8> On the base material, <5> A step of applying the water-based paint composition described in [1], and a step of drying the water-based paint composition applied to the substrate to form a paint film [2]. A method for manufacturing painted products, including [Examples]

[0149] The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the amounts in the table represent "parts by mass".

[0150] [Examples 1-15 and Comparative Examples 1-3] The first component was prepared by placing each component listed in the "First Component" column of Tables 1 and 2 into a container in the amounts (numerical value, parts by mass) specified in Tables 1 and 2, and stirring with a high-speed disperser at room temperature (23°C) for 30 minutes. Furthermore, the second component was prepared by placing each component listed in the "Second Component" column of Tables 1 and 2 into a separate container in the amounts (numerical value, parts by mass) listed in Tables 1 and 2, and stirring with a high-speed disperser until the temperature reached 45-50°C. The prepared first agent, second agent, and third agent listed in the column for third agent in Table 2 (if necessary) were mixed in the mixing ratio (mass%) listed in Tables 1 and 2 to prepare the water-based paint compositions listed in Tables 1 and 2. Table 3 provides a description of each component listed in Tables 1 and 2.

[0151] [Solid content] The solid content (amount of solids per 100% by mass of the composition) in the prepared water-based paint composition was calculated from the solid content and blending amount of each raw material. The results are shown in Tables 1 and 2.

[0152] [PWC] The pigment mass concentration (PWC) in the prepared water-based paint composition was calculated based on formula (2) above. The results are shown in Tables 1 and 2.

[0153] [PVC] The pigment volume concentration (PVC) in the prepared water-based paint composition was calculated based on formula (3) above. The results are shown in Tables 1 and 2.

[0154] [Reaction ratio] The reaction ratios in the prepared water-based paint compositions were calculated based on formula (1) above. The results are shown in Tables 1 and 2.

[0155] [Dry curability] The prepared water-based coating composition was applied to a glass plate measuring 348 mm × 25 mm × 2 mm (thickness) using a film applicator, so that the dry coating thickness was 150 μm. Under conditions of 5°C and 70% RH relative humidity, an RC-type drying time recorder (manufactured by Coating Tester Co., Ltd.) was used. The test needle of the RC-type drying time recorder was slowly moved across the coating film at a constant speed (a speed that sets the measurement time to 24 hours). The state of the coating film was determined from the trace left by the test needle, and the time from immediately after the formation of the coating film until it was semi-cured (semi-curing time) was determined. The results are shown in Tables 1 and 2. The partial curing time is specifically as follows: Figure 1 shows a schematic plan view (schematic explanatory diagram) of a glass plate 2 on which a coating film 1 has been formed, viewed from above on the side with the coating film 1. Position a is the position where the test needle is placed in contact with the coating 1 formed on the glass plate 2 and the movement of the test needle begins. Position b is the position where, when looking down from above the glass plate 2 on which the coating 1 is formed, the glass plate 2 is no longer visible (due to the coating 1), and position c is the position where the test needle slides along the surface of the coating 1 and no marks are left on the surface of the coating 1. The time required for the test needle to move from position a to position b was defined as the half-curing time (the time required for the test needle to move from position a to position c was defined as the complete curing time).

[0156] [Adhesive (Tack)] The prepared water-based coating composition was applied to tinplate (150mm x 70mm x 0.3mm (thickness)) using an applicator to achieve a dry film thickness of 200μm. The samples were left to stand at 5°C and 70% RH relative humidity. After 24 and 48 hours, the surface of the coating on the test pieces was pressed with a finger to evaluate the presence or absence of tackiness. The evaluation criteria are as follows.

[0157] <Evaluation Criteria> 5: I don't feel any stickiness. 4: It feels slightly sticky, but no fingerprints are left on the surface of the coating. 3: It is adhesive, and when you try to remove your finger from the test piece, the piece does not lift, but a mark is left on the surface of the coating where you touched it with your finger. 2: It is adhesive, and when you try to remove your finger from the test piece, the test piece lifts slightly before separating from your finger. 1: It is sticky, and when you try to remove your finger from the test piece, the test piece lifts up and does not come off your finger.

[0158] [Walkability] A 150mm x 70mm x 2.3mm (thickness) SS400 sandblasted steel plate (arithmetic mean roughness (Ra): 30-75 μm) was prepared. The prepared water-based coating composition was applied to the surface of this steel plate using an applicator, so that the dry film thickness was 200 μm. Steel plates coated with each water-based paint composition were dried for 24 hours and 48 hours under conditions of 5°C and 70% RH relative humidity. After each drying time, the test specimen was stepped on with a shoe and twisted with the heel of the shoe. The condition of the coating surface was then evaluated. The evaluation criteria were as follows:

[0159] <Evaluation Criteria> 5: The paint film is undamaged, and there is no dirt adhering to the surface of the paint film. 4: The paint film is not damaged, but there is some dirt adhering to the surface of the paint film. 3: There is no peeling of the paint film, but slight scuff marks remain on the surface of the paint film. 2: There is no peeling of the paint film, but there are signs of damage where the paint film has twisted. 1: The paint film has peeled off, exposing the surface of the underlying sandblasted steel plate.

[0160] [Pot Life] 300 g of each water-based paint composition prepared in Examples 1-12 and Comparative Example 1 was weighed into a container and adjusted with water so that the viscosity of each water-based paint composition at 23°C (Rion Viscometer: VT-04F, manufactured by Rion Co., Ltd.) was 2,000 mPa·s. Then, the viscosity (at 5°C) was measured after being held in a constant temperature bath at 5°C for 30 minutes and 60 minutes. The results are shown in Table 1.

[0161] [Chemical resistance] Test plates were prepared by applying the prepared water-based coating composition to 150 mm x 70 mm x 2.3 mm (thickness) SS400 sandblasted steel plates (arithmetic mean roughness (Ra): 30-75 μm) using an air spray so that the dry film thickness was 150 μm, and then drying them at 23°C for 7 days. The test plates were immersed in various chemicals, including 5% sulfuric acid and 5% sodium hydroxide aqueous solution, at 23°C for 30 days. The evaluation criteria for the test plates after immersion are as follows. Furthermore, a chemical resistance test result of 2 or higher indicates that the product is practically acceptable.

[0162] <Evaluation Criteria> 3: There is no rust on the steel plate, and the coating does not peel off, blister, crack, or soften from the steel plate. 2: There is no rust on the steel plate, and the paint film shows no peeling, blistering, or cracking from the steel plate, although slight softening is observed. 1: Rust has formed on the steel plate, or the paint film has peeled off from the steel plate, blistered, or cracked.

[0163] [Table 1]

[0164] [Table 2]

[0165] [Table 3] [Explanation of Symbols]

[0166] 1: Coating film 2: Glass plate 3: Traces left by the test needle a: Starting position of the test needle b: Position where the glass panel is no longer visible. c: The position where the test needle slides across the coating surface and no longer leaves any marks on the coating surface.

Claims

1. A first agent comprising a non-aqueous epoxy compound (A1) and a silicate compound (B), wherein the silicate compound (B) is at least one selected from alkoxysilanes and low condensates of the alkoxysilane having a degree of condensation of 2 to 20, the alkoxysilane is at least one selected from tetraalkoxysilanes and alkylalkoxysilanes, and the alkyl group contained in the alkylalkoxysilane has 1 to 5 carbon atoms, A second agent containing an amine compound (C) and water, A water-based paint composition kit having the following features.

2. The aqueous coating composition kit according to claim 1, wherein the content of silicate compound (B) in the first agent is 1 to 50 parts by mass per 100 parts by mass of the solid content of the non-aqueous epoxy compound (A1).

3. The first agent contains an aqueous epoxy compound (A2) and water, A second agent containing an amine compound (C), A third agent comprising a silicate compound (B), wherein the silicate compound (B) is at least one selected from alkoxysilanes and low condensates of the alkoxysilane having a degree of condensation of 2 to 20, the alkoxysilane is at least one selected from tetraalkoxysilanes and alkylalkoxysilanes, and the alkyl group contained in the alkylalkoxysilane has 1 to 5 carbon atoms, A water-based paint composition kit having the following features.

4. The second agent further contains water. A water-based paint composition kit according to claim 3.

5. A water-based paint composition obtained by mixing the first agent and the second agent in the water-based paint composition kit according to claim 1 or 2, or by mixing the first agent, the second agent and the third agent in the water-based paint composition kit according to claim 3 or 4.

6. A coating film formed from the water-based coating composition described in claim 5.

7. A coated article comprising a substrate and a coating film according to claim 6.

8. A step [1] of applying the water-based paint composition described in claim 5 to a substrate, and a step [2] of drying the water-based paint composition applied to the substrate to form a coating film. A method for manufacturing painted products, including

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