The present invention relates to a coating composition kit and its use.
Background technology
[0002]
　Inorganic zinc rich paint is a paint composition containing an inorganic resin such as a hydrolyzed condensate of silicate as a binder component and a large amount of zinc powder. For example, a one-component, one-powder type paint composition kit is known. There is. Inorganic zinc rich paint can prevent corrosion of steel materials by sacrificial anticorrosion action by zinc and formation of highly barrier oxide film in corrosive environment, and is widely used for anticorrosion of large steel structures such as ships and bridges. in use.
[0003]
　An example of an inorganic zinc rich paint contains a hydrolyzed condensate of silicate as a binder component, and is known to be cured by moisture.
　By the way, the inorganic zinc rich paint may be applied to the bolted joint portion of the steel material in order to increase the sliding frictional force of the joint surface. In such a case, the slip coefficient is generally 0.4 to 0.5, but Patent Document 1 discloses a zinc rich coating composition having a slip coefficient of more than 0.5.
Prior art literature
Patent documents
[0004]
Patent Document 1: Japanese Patent Application Laid-Open No. 2003-306638
Outline of the invention
Problems to be solved by the invention
[0005]
　As a result of the study by the present inventors, in order to increase the slip coefficient of the coating film of the inorganic zinc rich paint, an attempt was made to produce a paint composition kit having a mixed powder in which zinc powder and an extender pigment or a special pigment are mixed. In this case, it was found that the powder had to be classified at the time of production, and depending on the pigment, poor mixing of the powders was likely to occur, the classification was difficult and time consuming, and the cost was high, which was uneconomical.
[0006]
　On the other hand, in a paint composition kit having a first agent containing a binder component and a second agent containing zinc powder, if the pigment is dispersed in the first agent, there is a problem that the storage stability is deteriorated. I understand. For example, if the high hardness pigment described in Patent Document 1 is added to the first agent in order to increase the slip coefficient of the coating film, the storage stability is deteriorated. The inorganic zinc rich paint may need to be stored for a long period of 12 months, and the deterioration of the storage stability of the first agent becomes a problem.
[0007]
　An object of the present invention is to provide a coating composition kit capable of forming a coating film having excellent long-term storage stability and, for example, an excellent slip coefficient at a bolted joint of a steel material.
Means to solve problems
[0008]
　The present inventors have diligently studied to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by a coating composition kit having the following constitution, and have completed the present invention.
　The present invention relates to, for example, the following [1] to [10].
[0009]
　[1] A coating composition having a first agent containing a siloxane-based binder (A), kaolin (B) and a pigment (C) having a Mohs hardness of 5 or more, and a second agent containing zinc powder (X). Thing kit.
[0010]
　[2] The coating composition kit according to the above [1], wherein the siloxane-based binder (A) has a weight average molecular weight (Mw) of 500 to 10,000.
　[3] The coating material according to the above [1] or [2], wherein the siloxane-based binder (A) is a condensate of at least one compound (A1) selected from tetraalkoxysilane and alkyltrialkoxysilane. Composition kit.
[0011]
　[4] The coating composition kit according to any one of the above [1] to [3], wherein the pigment (C) contains at least one selected from yellow iron oxide, potassium feldspar and silica.
　[5] A coating composition obtained by at least mixing the first agent and the second agent in the coating composition kit according to any one of [1] to [4].
[0012]
　[6] A method for producing a coating composition, comprising a step of mixing at least the first agent and the second agent in the coating composition kit according to any one of [1] to [4].
　[7] A coating film formed from the coating composition according to the above [5].
[0013]
　[8] A base material with a coating film having the base material and the coating film according to the above [7].
　[9] The base material with a coating film according to the above [8], wherein the base material is a steel material constituting a steel structure.
[0014]
　[10] A steel material with a coating film having the steel material and the coating film according to the above [7] formed on the joint surface of the bolted joint portion of the steel material.
The invention's effect
[0015]
　According to the present invention, it is possible to provide a coating composition kit capable of forming a coating film having excellent long-term storage stability and, for example, an excellent slip coefficient at a bolted joint of a steel material.
Embodiment for carrying out the invention
[0016]
　Hereinafter, embodiments for carrying out the present invention will be described in detail.
　In the present specification, the paint composition kit according to one embodiment of the present invention is also referred to as "the paint composition kit of the present embodiment", and at least the first agent and the second agent in the paint composition kit of the present embodiment are used. The coating composition obtained by mixing is also referred to as "the coating composition of the present embodiment", and the coating film formed from the coating composition of the present embodiment is also referred to as "the coating film of the present embodiment".
[0017]
　In the present specification, the "slip coefficient" is measured based on "Appendix 7 Slip Coefficient Evaluation Test Method" of "Guidelines for Designing Steel Structure Joints" (3rd Edition, Architectural Institute of Japan, 2012). The slip coefficient.
[0018]
　 [Paint Composition Kit and Paint Composition]
　The paint composition kit of the present embodiment has a first agent and a second agent.
　The first agent contains a siloxane-based binder (A), kaolin (B), and a pigment (C) having a Mohs hardness of 5 or more.
[0019]
　The second agent contains zinc powder (X).
　The coating composition kit of the present embodiment is a packaged kit, and in one embodiment, it is a one-component, one-powder type kit composed of a liquid first agent and a powdered second agent.
[0020]
　 << First Agent >> In the
　present embodiment, the first agent containing the siloxane-based binder (A) contains kaolin (B) and the pigment (C) having a Mohs hardness of 5 or more, so that the second agent is prepared. Occasionally, the step of mixing and classifying zinc powder (X) with kaolin (B) and a pigment (C) having a Mohs hardness of 5 or more is not required.
　The first agent is preferably liquid.
[0021]
　
　The first agent contains a siloxane-based binder (A). The siloxane-based binder (A) is usually a condensate of silicate, and specifically, is a compound obtained by hydrolyzing and condensing the silicate.
[0022]
　Examples of the siloxane-based binder (A) include a condensate of at least one compound (A1) selected from tetraalkoxysilane and alkyltrialkoxysilane, and specific examples thereof include the compound (A1) and /. Alternatively, a partially hydrolyzed condensate of the low condensate thereof may be mentioned.
[0023]
　Examples of the tetraalkoxysilane include tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, and tetra-sec-butyl orthosilicate. Examples of the alkyltrialkoxysilane include methyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane.
[0024]
　Examples of the low condensate of the compound (A1) include a low condensate of the tetraalkoxysilane such as methylpolysilicate and ethylpolysilicate. The low condensate refers to a condensate having a degree of condensation of 2 to 20 (the number of silicon atoms is 2 to 20).
[0025]
　As the low condensate, a low condensate of tetraethyl orthosilicate is preferable, and as the low condensate of tetraethyl orthosilicate, for example, "ethyl silicate 45", "ethyl silicate 40" and "ethyl silicate 48" (hereinafter, corcoat). (Co., Ltd.), "Sylicate 45" and "Sylicate 40" (above, manufactured by Tama Chemical Industry Co., Ltd.), "TES40WN" (above, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.). As the siloxane-based binder (A), a partially hydrolyzed condensate of ethyl silicate 40 (trade name; manufactured by Corcote Co., Ltd.) is particularly preferable.
[0026]
　The weight average molecular weight (Mw) of the siloxane-based binder (A) contained in the first agent is usually 500 to 10,000, preferably 700 to 9,000, and more preferably 800 to 5,000. When the Mw of the siloxane-based binder (A) is 500 or more, the drying property of the coating composition of the present embodiment tends to be high, and the corrosion resistance of the coating film of the present embodiment tends to be high. On the other hand, when the Mw of the siloxane-based binder (A) is 10,000 or less, the storage stability of the first agent is good, and the coating composition of the present embodiment is applied when the thick film is coated. Film cracking tends to be less likely to occur.
[0027]
　The weight average molecular weight (Mw) of the siloxane-based binder (A) can be measured by a gel permeation chromatography (GPC) method. The value obtained by the GPC method is a value (polystyrene conversion value) obtained by using a calibration curve prepared using polystyrene as a standard substance.
[0028]
　The first agent can contain one kind or two or more kinds of siloxane-based binders (A).
　The siloxane-based binder (A) can be produced by using a conventionally known method, and for example, the compound (A1) and / or a low condensate thereof is placed in an organic solvent in an appropriate amount of water and, if necessary. It can be produced by performing a partial hydrolysis condensation reaction so that the weight average molecular weight (Mw) becomes a desired value in the presence of a catalyst.
[0029]
　Examples of the organic solvent include the organic solvents described in the column described later.
　The amount of water used is usually 5 to 11 parts by mass, preferably 5.5 to 9 parts by mass with respect to 100 parts by mass of the compound (A1) and / or a low condensate thereof.
[0030]
　Examples of the catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, and nitrate; formic acid; organic tin compounds such as dibutyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dimalate, dioctyltinmalate, and tin octylate; Phosphoric acid or phosphate esters such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; diisopropoxybis. Organic titanate compounds such as (acetylacetate) titanium, diisopropoxybis (ethylacetoacetate) titanium; organic aluminum compounds such as tris (ethylacetacetate) aluminum, tris (acetylacetonate) aluminum; tetrabutylzirconeate, tetrakis ( Examples thereof include organic zirconium compounds such as acetylacetonate) zirconium, tetraisobutylzirconate, and butoxitris (acetylacetonate) zirconium. Among these, inorganic acids are preferable, and hydrochloric acid is more preferable, from the viewpoint of good storage stability of the first agent.
[0031]
　When a catalyst is used, the amount used is usually 0.01 to 2.0 parts by mass, preferably 0.02 to 1. It is 0 parts by mass.
[0032]
　A boron compound described later can be used in the production of the siloxane-based binder (A). By introducing a structure derived from a boron compound into the siloxane-based binder (A), the drying curability of the coating composition of the present embodiment can be improved.
[0033]
　Examples of the boron compound include boric acid and boron trioxide.
　When a boron compound is used, the amount used is usually 0.3 to 11 parts by mass, preferably 1.5 to 7 parts by mass with respect to 100 parts by mass of the compound (A1) and / or its low condensate. Is.
[0034]
　For the content ratio of the siloxane-based binder (A), the mass of the siloxane-based binder (A) is converted into the mass of SiO 2 (that is, the mass of the siloxane-based binder (A) is converted into the siloxane-based binder (that is, the mass of the siloxane-based binder (A)). substance of Si atoms contained in the a) (mol) and SiO same amount 2 in terms of mass), when the solid content of the coating composition of the present embodiment is 100 mass%, is generally 1 to 15 mass% It is preferably 2 to 10% by mass, more preferably 3 to 8% by mass.
[0035]
　Further, for the content ratio of the siloxane-based binder (A), the mass of the siloxane-based binder (A) is converted into the mass of SiO 2 (that is, the mass of the siloxane-based binder (A) is the siloxane-based bond. substances of Si atoms contained in (a) (mol) and SiO same amount 2 in terms of mass), when the solid content of the first agent and 100 wt%, usually 10 to 70% by weight, preferably Is 20 to 60% by mass, more preferably 30 to 50% by mass.
[0036]
　When the content ratio of the siloxane-based binder (A) is within the above range, the coating film of the present embodiment is excellent in corrosion resistance, crack resistance, and adhesion to the substrate.
　The solid content of the coating composition or the first agent of the present embodiment is the residue of the coating composition containing a volatile component such as a solvent or the first agent heated under the following conditions in a hot air dryer (heating). Remaining). The heating residue of the coating composition and the first agent can be measured according to the standard of JIS K 5601 1-2 (heating temperature: 125 ° C., heating time: 60 minutes).
[0037]
　The hydrolysis rate of the siloxane-based binder (A) is preferably 35 to 75%, more preferably 38 to 55%. When the hydrolysis rate of the siloxane-based binder (A) is within the above range, the first agent having better storage stability can be obtained, and the drying property and the thickened film can be obtained. A coating composition having better crack resistance can be obtained.
[0038]
　The hydrolysis rate (%) is that when the siloxane-based binder (A) is a partially hydrolyzed condensate of the compound (A1) and / or a low condensate thereof, tetraalkoxysilane, alkyltrialkoxysilane and the above. It means the reaction rate of the reactive group (alkoxy group) contained in the low condensate, and can be calculated by the following formula 1.
[0039]
　Hydrolysis rate (%) = (W / 18 × 2 / (S / E)) × 100 (Equation 1) In
　Equation 1, W is the mass (g) of water used in the preparation of the siloxane-based binder (A). Yes, S is the mass (g) of the tetraalkoxysilane, the alkyltrialkoxysilane and the low condensate, and E is the reaction group equivalent of the tetraalkoxysilane, the alkyltrialkoxysilane and the low condensate.
[0040]
　
　The first agent contains kaolin (B). Although the reason is not clear, when the pigment (C) having a Mohs hardness of 5 or more is included in the first agent containing the siloxane-based binder (A) in order to improve the slip coefficient of the coating film, its long-term storage stability is achieved. However, by further including kaolin (B) in the first agent, the first agent exhibits excellent long-term storage stability, and the kneadability between the first agent and the second agent becomes good. As a result, a stable supply of the coating composition becomes possible. Here, as an index of storage stability, for example, pigment sedimentation property and / or gelation can be mentioned.
[0041]
　Kaolin (B) is usually clay are naturally occurring (mineral name: kaolinite (Formula: Al 2 O 3 · 2SiO 2 · 2H 2 O)) is a layered type of inorganic pigment made from. Kaolin (B) usually has a scaly, thin, flat shape. The kaolin (B) is not particularly limited, and examples thereof include wet kaolin, dry kaolin, and calcined kaolin.
[0042]
　The median diameter of kaolin (B) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm. As used herein, the median diameter is measured by laser diffraction.
[0043]
　The first agent can contain one or more kaolins (B).
　The content ratio of kaolin (B) is usually 5 to 80% by mass, preferably 10 to 50% by mass, based on 100% by mass of the solid content of the first agent. When the content ratio of kaolin (B) is 5% by mass or more, the storage stability of the first agent tends to be better, while when it is 80% by mass or less, the slip of the coating film of the present embodiment tends to be better. The coefficient tends to be difficult to decrease.
[0044]
　The content of kaolin (B) is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the solid content of the coating composition of the present embodiment.
[0045]
　 The first agent contains a pigment (C) having a Mohs hardness of 5 or more (hereinafter, also referred to as “pigment (C)”). When the first agent contains the pigment (C), the slip coefficient of the coating film of the present embodiment is increased.
[0046]
　The Mohs hardness of the pigment (C) is 5 or more, preferably 5 or more and 8 or less, and more preferably 5.5 or more and less than 7.5. The Mohs hardness can be measured according to a 10-step Mohs hardness meter.
[0047]
　Examples of the pigment (C) include iron oxides such as yellow iron oxide, red iron oxide, and black iron oxide; feldspars such as potash feldspar, orthoclase, slightly oblique feldspar, soda feldspar, and ash feldspar; silica and feldspar. Yellow iron oxide, potassium feldspar, and silica are preferable because they have a high slip coefficient and excellent storage stability.
[0048]
　The shape of the pigment (C) is not particularly limited, but various shapes such as spherical, needle-shaped, plate-shaped, scaly-shaped, and fibrous-shaped can be used. In one embodiment, the median diameter of the pigment (C) is 0.1-50 μm.
[0049]
　Yellow iron oxide is usually needle-shaped particles. The median diameter of yellow iron oxide is preferably 0.1 to 30 μm, more preferably 0.2 to 20 μm.
　Potassium feldspar is a particle having a shell-like fracture, which is usually obtained by crushing from orthoclase. The median diameter of potassium feldspar is preferably 1 to 50 μm, more preferably 2 to 30 μm.
[0050]
　As the silica, fine powder silica having an average primary particle size of 1 μm or less is preferable. The average primary particle size of the fine powder silica is preferably 5 to 100 nm. The specific surface area of ​​the fine powder silica is preferably 50 m 2 / g or more. The fine powdered silica may be surface-treated or untreated. In the present specification, the average primary particle diameter of nano size is an average value of the number of major diameters of primary particles observed by an electron microscope.
[0051]
　In one embodiment, the pigment (C) preferably contains fine powdered silica, more preferably yellow iron oxide and / or potassium feldspar, and finely powdered silica, from the viewpoint of the slip coefficient of the coating film.
[0052]
　The first agent can contain one kind or two or more kinds of pigments (C).
　The content ratio of the pigment (C) is usually 5 to 70% by mass, preferably 10 to 50% by mass, based on 100% by mass of the solid content of the first agent. When the content ratio of the pigment (C) is 5% by mass or more, the slip coefficient of the coating film of the present embodiment tends to be high, while when it is 70% by mass or less, the storage stability of the first agent is high. It tends to be difficult to decrease.
[0053]
　The content of the pigment (C) is preferably 1 to 10% by mass, more preferably 2 to 6% by mass, based on 100% by mass of the solid content of the coating composition of the present embodiment.
[0054]
　
　The first agent can contain a curing accelerator (D).
　Examples of the curing accelerator (D) include boron compounds such as boric acid and boron trioxide, oxalic acid, ferric chloride, and zinc chloride. Among these, boron compounds such as boric acid and boron trioxide are preferable from the viewpoint of storage stability and crack resistance.
[0055]
　The curing accelerator (D) acts as a curing catalyst when, for example, the coating composition applied on the substrate is cured to form a coating film.
　The first agent can contain one kind or two or more kinds of curing accelerators (D).
[0056]
　When the curing accelerator (D) is used, the content ratio thereof is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on 100% by mass of the solid content of the first agent. When the content ratio of the curing accelerator (D) is within the above range, the storage stability of the siloxane-based binder (A) is improved, and the drying property of the coating composition of the present embodiment and the crack resistance of the coating film are also improved. It tends to be excellent.
[0057]
　
　The first agent may contain an organic resin (E) other than the siloxane-based binder (A) as long as the object and effect of the present invention are not impaired. Examples of the organic resin (E) include butyral resins such as polyvinyl butyral resin and acrylic resins.
[0058]
　Examples of the polyvinyl butyral resin include Eslek BM-1, Eslek BM-2, and Eslek BL-1 (trade name; manufactured by Sekisui Chemical Co., Ltd.), and examples of the acrylic resin include Dianal BR-106 (Dianal BR-106). Product name; manufactured by Mitsubishi Chemical Corporation).
[0059]
　The first agent can contain one kind or two or more kinds of organic resins (E).
　When the organic resin (E) is used, the content ratio thereof is preferably 0 in 100% by mass of the solid content of the first agent from the viewpoint of suppressing the coating workability of the coating composition and the crack resistance of the coating film. It is 1 to 10% by mass, more preferably 0.5 to 8% by mass.
[0060]
　
　The first agent can contain a generally known thickener (F). The thickener (F) can improve the kneadability between the first agent and the second agent described later.
[0061]
　As the thickener (F), a conventionally known thickener can be used without limitation. Examples of the thickener (F) include organic thickeners such as polyamide wax, polyethylene wax, and polyethylene oxide wax; and inorganic substances such as bentonite (organic bentonite) whose surface is treated with bentonite, quaternary ammonium salt, and the like. Examples include system thickeners.
[0062]
　The first agent can contain one or more thickeners (F).
　When the thickener (F) is used, the content ratio thereof is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the solid content of the coating composition of the present embodiment. %.
[0063]
　
　The first agent usually contains an organic solvent for dilution, improvement of storage stability, improvement of pot life, and the like.
[0064]
　Examples of the organic solvent include at least one organic solvent (S1) selected from a glycol ether solvent, a ketone solvent and an acetate ester solvent. The storage stability of the siloxane-based binder (A) is improved in the first agent containing the organic solvent (S1) as compared with the first agent containing no organic solvent (S1). It is presumed that this is because the silanol group that the siloxane-based binder (A) may have is stabilized by hydrogen bonding with the oxygen atom of the organic solvent (S1), and the condensation reaction thereof is suppressed.
[0065]
　Examples of the glycol ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether is preferable. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and methyl ethyl ketone is preferable. Examples of the acetic acid ester solvent include ethyl acetate and butyl acetate, and ethyl acetate is preferable. Among these, glycol ether-based solvents are preferable, and propylene glycol monomethyl ether is more preferable.
[0066]
　The first agent can contain one kind or two or more kinds of organic solvents (S1).
　The first agent may contain an organic solvent (S2) other than the organic solvent (S1) in order to adjust the drying property of the painted composition.
[0067]
　Examples of the organic solvent (S2) include organic solvents usually used in the coating field, such as alcohol solvents, aromatic solvents, and cellosolve solvents. Examples of the alcohol solvent include methanol, ethanol, isopropanol and butanol. Examples of the aromatic solvent include benzene, xylene and toluene. Examples of the cellosolve-based solvent include methyl cellosolve, ethyl cellosolve, and butyl cellosolve.
[0068]
　The first agent can contain one kind or two or more kinds of organic solvents (S2).
　The content ratio of the organic solvent in the first agent is not particularly limited, but is usually 10 to 80% by mass, preferably 25 to 60% by mass.
[0069]
　 The first agent is, for example, a siloxane-based binder (A), kaolin (B), a pigment (C) having a Mohs hardness of 5 or more, and, if necessary, the above-mentioned components (D) to ( F), obtained by mixing an organic solvent or the like.
[0070]
　 << Second agent >>
　
　The second agent contains zinc powder (X). The shape, size, and the like of the zinc powder (X) are not particularly limited, and conventionally known zinc powders (X) can be used.
[0071]
　Examples of the zinc powder (X) include metallic zinc powder and zinc alloy powder. Examples of the zinc alloy include alloys of zinc with at least one selected from aluminum, magnesium and tin. Examples of the shape of the particles constituting the zinc powder (X) include various shapes such as spherical and scaly.
[0072]
　The median diameter of the zinc powder (X) is 1 to 30 μm.
　The second agent can contain one or more zinc powders (X).
　The content ratio of the zinc powder (X) is usually 30 to 98% by mass, preferably 50 to 97% by mass, and more preferably 65 to 95% by mass in the solid content of 100% by mass of the coating composition of the present embodiment. be. When the content ratio of the zinc powder (X) is within the above range, the coating film of the present embodiment is excellent in rust prevention for a long period of time. Therefore, the coating composition of the present embodiment is useful as a so-called inorganic zinc rich paint.
[0073]
　 << Other Ingredients >>
　The first agent and / or the second agent, or the coating composition of the present embodiment, is other than the pigment dispersant, kaolin (B) and pigment (C) for the purpose of ensuring various coating properties. Other components such as extender pigments, coloring pigments, rust preventive pigments, and adhesion-imparting agents can be further contained. The other components may be used alone or in combination of two or more.
[0074]
　 [Usage form of paint composition kit, manufacturing method
　of paint composition ] In one embodiment, the paint composition kit of this embodiment is separately produced by a paint manufacturer in which the first agent and the second agent are produced, respectively. It is provided to a painter, and the painter mixes the first agent and the second agent before painting, and paints the obtained coating composition. The coating composition kit of the present embodiment may further include, for example, a third agent or the like containing at least one component selected from the above-mentioned components and the like.
[0075]
　In this embodiment, kaolin (B) and pigment (C) are included in the first agent. When these pigments are included in the second agent containing zinc powder (X), a step of mixing and classifying the pigment powder is required, and a step of classifying the powders after storage may be required. This embodiment simplifies the manufacturing process because, in one embodiment, the second agent does not require a step of mixing zinc powder (X), kaolin (B), a pigment (C), or the like, or a step of classifying. can.
[0076]
　The coating composition of the present embodiment can be obtained by at least mixing the first agent and the second agent in the coating composition kit of the present embodiment. For example, the first agent and the second agent are sufficiently stirred and homogenized using a stirrer.
[0077]
　The coating composition of the present embodiment is excellent in drying property. By using the coating composition, it is possible to form a coating film having excellent corrosion resistance and crack resistance in a thick film and having a high slip coefficient.
[0078]
　The coating film of the present embodiment is formed from the coating composition of the present embodiment and is useful as an anticorrosion / rust preventive coating film. The base material with a coating film of the present embodiment has a base material and the coating film of the present embodiment. For example, by coating the surface of the base material with the coating composition of the present embodiment and curing it, the coating film of the present embodiment and the base material with a coating film can be obtained.
[0079]
　Examples of the base material include conventionally known base materials such as steel materials, and specific examples thereof include ship structures such as ships, civil engineering structures such as bridges and tanks, plant structures such as oil drilling plants, and pipes. Steel structures such as lines; building structures such as houses and buildings; outdoor appliances such as guard fences and industrial machinery. The coating composition of the present embodiment is coated on the surface of these substrates as the first anticorrosion coating film. Usually, the base material on which the coating composition of the present embodiment is coated is blasted under the condition corresponding to the rust removal degree Sa2 1/2 or more in ISO 8501-1. Further, if necessary, an undercoat paint, an intermediate coat paint, and a top coat paint are applied onto the paint film obtained from the paint composition of the present embodiment.
[0080] [0080]
　In one embodiment, the base material specifically includes a steel material that can be bolted, and the coating composition of the present embodiment is applied to a joint surface in a bolted joint portion of the steel material. On this bonding surface, no other paint is applied onto the coating film coated with the coating composition of the present embodiment, and the bonding surfaces coated with the coating film composed of the coating composition of the present embodiment are bonded to each other. Therefore, a frictional force having a slip coefficient of 0.5 or more is exhibited.
[0081]
　Examples of the coating method of the coating composition of the present embodiment usually include air spray and airless spray. The curing method of the coating composition after coating is not particularly limited, and a conventionally known curing method can be applied. For example, when the coating composition applied on the substrate is left in the air (while heating as necessary), the solvent volatilizes and the siloxane-based binder (A) becomes water or air in the coating composition. It cures by hydrolyzing and condensing with the water (moisture) inside. In one embodiment, the coating conditions are usually 5-40 ° C.
[0082]
　The average dry film thickness of the coating film of the present embodiment is preferably 40 μm or more, more preferably 40 to 120 μm. The average dry film thickness of the coating film may be less than 40 μm, which is a thin film, depending on the condition of the substrate to be coated and the application. When the coating film of the present embodiment is a thick film having an average dry film thickness of more than 120 μm, it has excellent crack resistance even if it is more than 120 μm and 200 μm or less, for example.
[0083]
　The slip coefficient of the coating film of the present embodiment is preferably 0.5 or more, more preferably 0.55 or more, and the upper limit is not particularly limited, but may be 0.8. A coating film with a high slip coefficient of 0.5 or more eliminates the need to increase the size of reinforcing materials such as splicing plates used for joints of steel materials for safety reasons, for example, during bolt tightening joint work, and bolts to be tightened. It is preferable in terms of work cost because it is not necessary to increase the number.
Example
[0084]
　Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, "parts by mass" will be referred to as "parts" unless otherwise specified.
[0085]
　The details of each component described in the table are as follows.
-Alkyl silicate "Ethyl silicate 40": manufactured by Corcote Co., Ltd.
-Zinc powder "F-500": manufactured by Honjo Chemical Co., Ltd.
-Kaolin "ASP 200": manufactured by BASF Japan Co., Ltd.
-Tark "FC-1 talc" : Fukuoka Tarku Kogyo Co., Ltd.
, Mica "Mica Powder 325 Mesh": Fukuoka Taruku Kogyo Co., Ltd.
, Calcium Carbonate
"Calcine 200M-C": Maruo Calcium Co., Ltd. , Yellow Iron Oxide "TSY-" 1 ”: Toda Kogyo Co., Ltd.
・ Cali feldspar“ UNISPAR PG-K10 ”:
　　　Sibelco Malaysia Sdn Bhd
・ Fine powder silica“ AEROSIL R972 ”: Nippon Aerosil Co., Ltd.
・ Acrylic resin“ Dianal BR-106 ”: Polyamyl feldspar
resin "ESREC BM-2" manufactured by Mitsubishi Chemical Co.,
Ltd .: Polyamide wax "Disparon A630-20X" manufactured by Sekisui Chemical Co., Ltd .:
Organic bentonite "BENTONE SD-2" manufactured by Kusumoto Kasei Co., Ltd .: Elementis Specialties, Inc. Made
[0086]
　 [Preparation Example]
　28.00 parts of ethyl silicate 40, 39.42 parts of propylene glycol monomethyl ether (PGM), 6.92 parts of ethanol (industrial ethanol), and 1.56 parts of deionized water. , 0.10 part of 35% hydrochloric acid as a catalyst was charged in the container (1), and further 1.00 part of boron trioxide was charged in the container (1), stirred at 25 ° C. for 1 hour and 30 minutes, and then 16 Allowed to cool for hours.
[0087]
　Further, in another container (2), 1.00 parts of acrylic resin and 5.00 parts of xylene were charged and stirred at 25 ° C. for 30 minutes to prepare an acrylic resin varnish.
　Next, 10.00 parts of kaolin, 6.00 parts of yellow iron oxide, and 1.00 parts of fine powdered silica were charged in a container (1) that had been allowed to cool for 16 hours while stirring at 25 ° C. Finally, 6.00 parts of acrylic resin varnish prepared in advance in the container (2) was charged, and the mixture was stirred at 25 ° C. until uniform to prepare the first agent (I-1).
[0088]
　Further, the same operation as the preparation of the first agent (I-1) was performed except that the type and the amount of each raw material charged were changed as shown in Tables 1-1 and 1-2, and the first agent (I-) was prepared. 2) to (I-16) and (cI-1) to (cI-4) were prepared.
[0089]
　
　Initial agents (I-1) to (I-16), (cI-1) to (cI) in the initial stage (about 1 day after preparation) The weight average molecular weight (Mw) of the siloxane-based binder (A) in -4) was measured by a gel permeation chromatography (GPC) method.
[0090]
　The measurement conditions of GPC are as follows. A small amount of each of the first agents was taken and diluted with tetrahydrofuran, and the obtained solution was filtered through a membrane filter to obtain a GPC measurement sample.
・ Equipment: 2695 Separation Module
　　　　　　(Alliance GPC Multi System) manufactured by Japan Waters Corp.
・ Column: TSKgel Super H4000
　　　　　　　　　　　　TSKgel Super H2000
　　　　　　　　　　　　TSKgel Super H2000 manufactured by Tosoh Co., Ltd.
　　　　　　　　　　　　Measured by connecting the above three modules in series.
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 0.6 ml / min
・ Detector: Shodex RI-104
・ Column constant temperature bath temperature: 40 ° C.
・ Standard substance: Polystyrene
[0091]
　 The hydrolysis rate of the siloxane-based binder (A) was calculated based on the above-mentioned formula 1.
[0092]
　 [Examples 1 to 16, Comparative Examples 1 to 4]
　The ratios (parts by mass ) of the second agent and the first agent stored at 23 ° C. for 1 month after preparation are shown in Tables 1-1 and 1-2. ) Was placed in a polyethylene container and dispersed with a high-speed disperser for 10 minutes to prepare a coating composition.
[0093]
[Table 1-1]

[0094]
[Table 1-2]

[0095]
　 [Evaluation test]
　
　The first agents (I-1) to (I-16) and (cI-1) to (cI-4) obtained in the preparation examples were stored at 23 ° C. for 12 months. From the later state, the storage stability was evaluated according to the criteria shown in Table 2.
[0096]
　In addition, the siloxane-based binder (A) in the first agents (I-1) to (I-16) and (cI-1) to (cI-4) that have passed 1 month, 6 months, and 12 months at 23 ° C. The weight average molecular weight (Mw) of the above was measured by the above-mentioned GPC method.
[0097]
　
　Each coating composition obtained in Examples and Comparative Examples is applied to a sandblasted steel plate (150 mm × 70 mm × 2.3 mm, Sa2 1/2 or more) by air spray so that the dry film thickness becomes 75 μm. Then, while drying under the conditions of 25 ° C. and 70% relative humidity, the coating film was rubbed 50 times with methyl ethyl ketone (MEK) every hour, and the time until the coating film became insoluble was measured and shown in Table 2. The dryness was evaluated according to the criteria of.
[0098]
　
　Each coating composition obtained in Examples and Comparative Examples is applied to a sandblasted steel sheet (150 mm × 70 mm × 2.3 mm, Sa2 1/2 or more) by air spray so that the dry film thickness is 75 μm. Then, it was dried for 7 days at 25 ° C and 70% relative humidity to prepare a test coating plate, and it occurred on the test coating plate (general part, cut part) after outdoor exposure (Otake City, Hiroshima Prefecture) for 2 years. The degree of rust and blistering was evaluated according to the criteria shown in Table 2.
[0099]
　 On a
　sandblasted steel sheet (150 mm × 70 mm × 2.3 mm, Sa2 1/2 or more), each coating composition obtained in Examples and Comparative Examples was sprayed with an air spray so that the dry film thickness was 200 μm. The coating was applied and dried at 25 ° C. and 70% relative humidity for 7 days to prepare a crack resistance test coating plate, the surface condition was observed, and the crack resistance was evaluated according to the criteria shown in Table 2.
[0100]
　 The
　coating compositions obtained in Examples and Comparative Examples were applied to both sides of the grid blasted SM490 plate by air spray so that the dry film thickness was 75 μm, and dried for 1 month. And obtained a coating test piece. The prepared coating test piece was tightened with a Torcia type high-strength TC bolt (M22), the slip coefficient was measured using a tensile tester, and the evaluation was made according to the criteria shown in Table 2.
[0101]
[Table 2]

The scope of the claims
[Claim 1]
　A paint composition kit comprising a first agent containing a siloxane-based binder (A), kaolin (B) and a pigment (C) having a Mohs hardness of 5 or more, and a
　second agent containing zinc powder (X)
.
[Claim 2]
　The coating composition kit according to claim 1, wherein the siloxane-based binder (A) has a weight average molecular weight (Mw) of 500 to 10,000.
[Claim 3]
　The coating composition kit according to claim 1 or 2, wherein the siloxane-based binder (A) is a condensate of at least one compound (A1) selected from tetraalkoxysilane and alkyltrialkoxysilane.
[Claim 4]
　The coating composition kit according to any one of claims 1 to 3, wherein the pigment (C) contains at least one selected from yellow iron oxide, potassium feldspar and silica.
[Claim 5]
　A coating composition obtained by at least mixing the first agent and the second agent in the coating composition kit according to any one of claims 1 to 4.
[Claim 6]
　A method for producing a coating composition, comprising the step of mixing at least the first agent and the second agent in the coating composition kit according to any one of claims 1 to 4.
[Claim 7]
　A coating film formed from the coating composition according to claim 5.
[Claim 8]
　A base material with a coating film having the base material and the coating film according to claim 7.
[Claim 9]
　The base material with a coating film according to claim 8, wherein the base material is a steel material constituting a steel structure.
[Claim 10]
　A steel material with a coating film having the steel material and the coating film according to claim 7 formed on the joint surface of the bolted joint portion of the steel material.