Coating material and method for forming a coating

Abstract

To provide a coating material that foams with increased temperature, forming a superior carbonized insulation layer; ensures superior adhesion between the substrate and the carbonized insulation layer; enables stable formation of the carbonized insulation layer; and guarantees superior heat-resistant protective performance.SOLUTION: A coating material forms a carbonized insulation layer at a temperature of 200°C or higher. The coating material comprises a binder and a heat-resistance imparting component. The binder comprises a copolymer resin from a group of vinyl monomers comprising (a1) alkyl acid vinyl monomers and (a2) aromatic-containing vinyl monomers.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel coating material and a method for forming a coating. [Background technology]

[0002] Various coating materials have been proposed to protect substrates such as steel, concrete, wood, and synthetic resins from fire. These coating materials expand upon temperature rise during a fire, forming a carbonized insulating layer. Known coating materials include those made by compounding synthetic resins with foaming agents, carbonizing agents, and flame retardants. The heat protection performance of such coating materials is often determined by the thickness of the coating, and to obtain the desired heat protection performance, it is important to apply the coating uniformly to the specified thickness. In particular, the selection of the synthetic resin is crucial.

[0003] For example, Patent Document 1 describes a synthetic resin obtained from a specific ethylenically unsaturated monomer as the resin. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication 2019-522701 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, when using a resin like the one described in Patent Document 1, problems such as the carbonized insulation layer (foamed layer) shrinking or peeling off from the substrate may occur when the temperature rises, and there was still room for improvement in order to obtain the desired heat-resistant protection performance. This invention has been made in view of the above problems, and aims to provide a coating material that, when the temperature rises, foams up to form an excellent carbonized insulation layer, has excellent adhesion between the substrate and the carbonized insulation layer, can form a stable carbonized insulation layer, and can ensure excellent heat-resistant protection performance. [Means for solving the problem]

[0006] To solve these problems, the present inventors conducted diligent research and found that by using a copolymer resin of vinyl monomers including (a1) alkylate vinyl monomer and (a2) aromatic vinyl monomer as a binder, excellent adhesion between the substrate and the carbonized insulation layer can be ensured even when the temperature rises, and excellent heat-resistant protective performance can be secured, leading to the completion of the present invention.

[0007] In other words, the present invention has the following features. 1. A coating material whose film forms a carbonized heat insulating layer at a temperature of 200°C or higher, The coating material includes a binder and a heat-resistant component. The binder contains a copolymer resin of vinyl monomers, including (a1) alkylate vinyl monomer and (a2) aromatic vinyl monomer. fruit, (a2) The aromatic vinyl monomer is styrene. A covering material characterized by the following features. 2. A coating material in which the film forms a carbonized heat insulating layer at a temperature of 200°C or higher, The coating material includes a binder and a heat-resistant component. The binder contains a copolymer resin of vinyl monomers comprising (a1) 3% to 60% by weight of alkylate vinyl monomer and (a2) 40% to 97% by weight of aromatic vinyl monomer. fruit, (a2) The aromatic vinyl monomer is styrene. A covering material characterized by the following features. 3. The coating material according to 1. or 2., characterized in that the heat-resistant component includes one or more selected from a foaming agent, a carbonizing agent, a flame retardant, and a filler. 4. A method for forming a coating by applying a coating material to a substrate, A method for forming a coating, characterized in that the coating material is the coating material described in 1. or 2. 5. A method for forming a coating by applying a coating material to a substrate, The covering material is the covering material described in 1. or 2., and is made in one step That's all. The coating is applied in multiple layers, and the dry film thickness per step is 300 μm or more. The final dry film thickness is 0.4-8 mm. A method for forming a coating, characterized by the following: [Effects of the Invention]

[0008] The coating material of the present invention foams up when the temperature rises to form an excellent carbonized heat insulating layer, and also exhibits excellent adhesion between the substrate and the carbonized heat insulating layer, ensuring excellent heat-resistant protection performance. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below based on its embodiments.

[0010] The present invention relates to a coating material whose film forms a carbonized heat insulating layer at a temperature of 200°C or higher, wherein the coating material comprises a binder and a heat-resistant component, and the binder comprises a copolymer resin of a group of vinyl monomers including (a1) alkylate vinyl monomer (hereinafter also referred to as "component (a1)") and (a2) aromatic vinyl monomer (hereinafter also referred to as "component (a2)"). The coating formed by the coating material of the present invention has excellent foaming properties at 200°C or higher (more preferably 250°C or higher), and by forming a carbonized heat insulating layer, it can enhance the heat-resistant protective performance of the substrate.

[0011] The binder of the present invention is characterized by comprising a copolymer resin of vinyl monomers including component (a1) and component (a2). By including such a copolymer resin as a binder, foaming occurs when the temperature rises, forming an excellent carbonized insulation layer. Furthermore, the adhesion between the substrate and the carbonized insulation layer is excellent, enabling the formation of a stable carbonized insulation layer and ensuring excellent heat-resistant protection. Although the details of the expression of such effects are unclear, when the temperature starts to rise, the component (a1) segment in the copolymer resin is thermally decomposed from the segment derived from an alkyl acid serving as a side chain, desorbs from the main chain, increases acidity, and maintains the main chain skeleton of the copolymer resin, which easily facilitates forming a state that is prone to foaming while maintaining adhesion to a substrate. Further, component (a2) has an effect of retaining the foamed shape, and it is believed that by including component (a1) and component (a2), foaming occurs to form an excellent carbonized heat-insulating layer, and excellent adhesion between the substrate and the carbonized heat-insulating layer is achieved, whereby excellent heat-resistant protection performance can be ensured.

[0012] Examples of component (a1) include vinyl versatate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl 2-ethylhexanoate, vinyl pivalate, vinyl crotonate, and vinyl benzoate, and one or two or more of these can be used. In the present invention, it is particularly preferable to include one or more selected from the group consisting of vinyl versatate, vinyl acetate, and vinyl 2-ethylhexanoate. Examples of component (a2) include styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, t-butoxystyrene, 1-vinylnaphthalene, and 2-vinylnaphthalene, and one or two or more of these can be used. In the present invention, it is particularly preferable to include styrene.

[0013] In addition to the above component (a1) and the above component (a2), the copolymer resin used in the present invention may optionally use (a3) a vinyl monomer other than the above (a1) and (a2) (hereinafter also referred to as "component (a3)"). Component (a3) is not particularly limited, and examples include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, and hydroxypentyl vinyl ether; hydroxy allyl ethers such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether; hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, and cinnamic acid, silyl group-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, and methyldimethoxysilylpropyl vinyl ether, amino group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate and dimethylaminopropyl (meth)acrylate, amide group-containing vinyl monomers such as (meth)acrylamide and ethyl (meth)acrylamide, carbonyl group-containing vinyl monomers such as diacetone acrylamide, nitrile group-containing vinyl monomers such as acrylonitrile, glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, vinyl monomers containing sulfonic acid such as vinyl sulfonic acid, Chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride, and chloroprene, Fluorine-containing vinyl monomers such as perfluoromethyl methacrylate, perfluoroisononylmethyl methacrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, trifluoroethyl acrylate, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, and vinylidene fluoride. Vinyl monomers such as ethylene, propylene, and isobutylene Methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 2-methylbutyl (meth)acrylate, 3-methylbutyl (meth)acrylate, (meth)acrylic Alkyl methacrylates such as n-hexyl acid, cyclohexyl acrylate, 2-ethylbutyl methacrylate, 2-methylpentyl methacrylate, 4-methylpentyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, n-lauryl methacrylate, etc. These are some examples, and one or more of these can be used.

[0014] The copolymer resin of the present invention can be produced by known vinyl polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, slurry polymerization, and dispersion polymerization, using the above components (a1) and (a2), and optionally the above component (a3) ​​in addition to these. Furthermore, the form of the resin is not particularly limited, and solvent-soluble resins, solvent-dispersible resins, solvent-free resins, powder resins, etc., can be appropriately set and used. For example, powder resins can be used by dissolving and / or dispersing them in a solvent, etc., as described later.

[0015] (a1) The mixing ratio of component is preferably 3% by weight or more and 60% by weight or less, more preferably 5% by weight or more and 55% by weight or less, and more preferably 7% by weight or more and 51% by weight or less, based on the total amount of vinyl monomer used in the production of the copolymer resin. (a2) The mixing ratio of component is preferably 40% by weight or more and 97% by weight or less, more preferably 45% by weight or more and 95% by weight or less, and more preferably 49% by weight or more and 93% by weight or less, based on the total amount of vinyl monomer used in the production of the copolymer resin. This range allows the material to foam up when the temperature rises, forming an excellent carbonized insulation layer. Furthermore, the adhesion between the substrate and the carbonized insulation layer is excellent, enabling the formation of a stable carbonized insulation layer and ensuring superior heat-resistant protection. Furthermore, when using component (a3), the mixing ratio of component (a3) ​​is preferably 0% by weight or more and less than 30% by weight, more preferably 0% by weight or more and less than 20% by weight, and more preferably 0% by weight or more and less than 10% by weight, relative to the total amount of vinyl monomer used in the production of the copolymer resin.

[0016] Furthermore, resins other than the copolymer resins mentioned above can also be used as binders. Examples of resins other than copolymer resins include vinyl polymer resins, urethane resins, epoxy resins, silicone resins, fluororesins, etc., that do not contain component (a1) or component (a2).

[0017] The coating formed from the above-mentioned binder component preferably exhibits an exothermic peak in differential thermal analysis (DTA method), with the maximum value of this exothermic peak occurring in the temperature range of 200 to 400°C (more preferably 250 to 380°C). In such cases, the foaming properties are further improved in the event of a temperature rise due to fire or other reasons, making it possible to form an excellent carbonized insulation layer and enhance the heat-resistant protection of the substrate.

[0018] In this invention, the differential thermal analysis of the coating was performed using a differential thermal analyzer (for example, the "Differential Thermal Balance Thermo plus EVO2 TG-DTA Series" manufactured by Rigaku Corporation, etc.). 3 ± 1 mg of the sample was placed in a platinum sample pan, α-alumina was used as the standard substance, and the temperature was varied from 100 to 900°C at a heating rate of 20°C / min.

[0019] In the coating material of the present invention, the heat-resistant component is a component that forms a carbonized insulating layer through interaction with the binder component (for example, at least one of the following: dehydration cooling effect, non-combustible gas generation effect, carbonization promotion effect, carbonized insulating layer formation effect, etc.) when the temperature rises, such as during a fire. The heat-resistant component preferably includes one or more selected from, for example, a foaming agent, a carbonizing agent, a flame retardant, and a filler.

[0020] The foaming agent imparts a foaming action to the coating due to a temperature rise, such as during a fire. Specifically, it imparts a foaming action when the temperature of the coating surface preferably reaches 200°C or higher. Examples of foaming agents include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, and thiourea. These can be used individually or in combination of two or more. The foaming agent content is preferably 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) per 100 parts by weight of solids of the binder.

[0021] The carbonizing agent provides the effect of forming a carbonized heat insulating layer by carbonizing and dehydrating the above-mentioned coating when the temperature rises due to a fire or other reasons. Examples of carbonizing agents include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, casein, and tris(2-hydroxyethyl) isocyanurate. These can be used individually or in combination of two or more. In the present invention, pentaerythritol and dipentaerythritol are particularly preferred because they have excellent dehydration cooling effect and carbonized heat insulating layer formation effect. The content of the carbonizing agent is preferably 10 to 200 parts by weight (more preferably 20 to 120 parts by weight) per 100 parts by weight of solid content of the above-mentioned binder.

[0022] Examples of flame retardants include organophosphorus compounds such as tricresyl phosphate and diphenylcresyl phosphate; chlorine compounds such as chlorinated polyphenyls, chlorinated polyethylenes, diphenyl chloride, triphenyl chloride, chlorinated paraffins, pentachloride fatty acid esters, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, and aluminum polyphosphate; and other inorganic compounds such as zinc borate and sodium borate. These can be used individually or in combination of two or more. In the present invention, the flame retardant preferably contains at least one phosphorus compound selected from, for example, melamine polyphosphate, meram polyphosphate, melamine-melam-melem polyphosphate double salt, or a composite compound of melamine-melam-melem polyphosphate and dimeram pyrosulfate, and it is also preferable to include ammonium polyphosphate in combination with these. The content of the flame retardant is preferably 30 to 800 parts by weight (more preferably 50 to 500 parts by weight) per 100 parts by weight of solids of the binder.

[0023] Examples of fillers include talc, calcium carbonate, sodium carbonate, aluminum oxide, titanium oxide, zinc oxide, silica, clay, volcanic ash, mica, silica sand, silica powder, quartz powder, and barium sulfate. These can be used individually or in combination of two or more. The filler content is preferably 3 to 200 parts by weight (more preferably 5 to 150 parts by weight) per 100 parts by weight of solids of the binder.

[0024] Furthermore, the present invention may also include metal hydrates, fibers, etc., in addition to the above components. Metal hydrates exhibit endothermic properties due to dehydration reactions, etc., when the temperature rises, and are different from the fillers mentioned above. Examples of such metal hydrates include aluminum hydroxide and magnesium hydroxide. These can be used individually or in combination of two or more. The average particle size of the metal hydrate is preferably 0.1 to 20 μm (more preferably 0.2 to 15 μm, even more preferably 0.3 to 8 μm, and most preferably 0.4 to 3 μm). The content of the metal hydrate is preferably 0.1 to 50 parts by weight (more preferably 0.2 to 30 parts by weight) per 100 parts by weight of solids of the binder.

[0025] In the present invention, it is preferable to use a filler and a metal hydrate in combination. In this case, the content of the metal hydrate is preferably 0.1 to 20% by weight (more preferably 0.3 to 15% by weight, and even more preferably 0.5 to 10% by weight) relative to the filler. In this case, foaming, especially shrinkage of the carbonized insulation layer at high temperatures, can be suppressed, and a stable carbonized insulation layer can be formed, thereby enhancing the effects of the present invention. The average particle size is measured by a laser diffraction particle size distribution analyzer.

[0026] The fibers enhance the ability to create thick coatings and suppress cracking of the film. Furthermore, the fibers can prevent the film from sagging during temperature increases due to fire or other factors, and can improve the thermal conductivity within the film. As a result, they exhibit excellent foaming properties, forming a uniform carbonized insulation layer and enhancing the heat-resistant protection performance of the substrate. Examples of such fibers include organic fibers such as acrylic fibers, acetate fibers, aramid fibers, copper ammonia fibers (cupro), nylon fibers, noboroid fibers, pulp fibers, viscose rayon, vinylidene fibers, polyester fibers, polyethylene fibers, polyvinyl chloride fibers, polyclar fibers, borinosic fibers, polypropylene fibers, and cellulose fibers; and inorganic fibers such as carbon fibers, rock wool fibers, glass fibers, silica fibers, alumina fibers, silica-alumina fibers, slag wool fibers, ceramic fibers, carbon fibers, and silicon carbide fibers. These can be used individually or in combination of two or more types.

[0027] In this invention, it is preferable to include inorganic fibers as the fibers, and among these, artificial mineral fibers such as rock wool fibers, slag wool fibers, glass fibers, and ceramic fibers are preferred. This further suppresses cracking of the coating. Furthermore, it makes it less likely for the coating to sag when the temperature rises due to fire or the like, and further enhances the thermal conductivity inside the coating. As a result, it exhibits uniform and excellent foaming properties even inside the coating (core), forming a carbonized insulation layer with more uniformity and superior strength, and further enhances the heat-resistant protective performance of the substrate.

[0028] Furthermore, the size of the fibers (fiber length and fiber diameter) can be set according to the performance of the coating material, the applicable substrate, the specifications of the applicator, etc. The average fiber length is preferably in the range of 10 to 1000 μm (more preferably 15 to 800 μm, even more preferably 20 to 600 μm), and the average fiber diameter is preferably in the range of 0.5 to 10 μm (even more preferably 1 to 8 μm). The aspect ratio (fiber length / fiber diameter) is preferably 3 to 300 (even more preferably 5 to 200). When the above ranges are met, the ability to coat thickly is increased, cracking of the coating becomes less likely, and when the temperature rises due to fire or the like, sagging of the coating is less likely to occur, and a stable carbonized heat insulating layer can be formed. The fiber content is preferably 0.5 to 30 parts by weight (more preferably 1 to 25 parts by weight, even more preferably 2 to 20 parts by weight) per 100 parts by weight of solid content of the binder.

[0029] Other additives may be used as long as they do not significantly impede the effects of the present invention. Examples include pigments, wetting agents, plasticizers, lubricants, preservatives, fungicides, algaecides, antibacterial agents, thickeners, leveling agents, dispersants, defoamers, crosslinking agents, silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants, halogen scavengers, diluents, absorbents, dehydrating agents, and solvents.

[0030] Examples of antioxidants include phosphorus-based, sulfur-based, or hindered-type phenolic antioxidants. These can be used individually or in combination of two or more. By including such antioxidants, deterioration of the coating can be suppressed not only under normal conditions but also when the temperature rises due to fire, etc., and the properties of the carbonized insulation layer formed by the temperature rise can be improved.

[0031] Furthermore, non-aqueous solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, and ketone solvents are preferred as solvents. Specifically, examples of aliphatic hydrocarbon solvents include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane, as well as terpine oil and mineral spirits. Examples of aromatic hydrocarbon solvents include toluene, xylene, and solvent naphtha; examples of ester solvents include ethyl acetate and butyl acetate; and examples of ketone solvents include methyl ethyl ketone and methyl isobutyl ketone. One or more of these solvents can be used.

[0032] The coating material of the present invention preferably has a heating residue of 70 to 98% by weight (more preferably 75 to 95% by weight, and even more preferably 80 to 93% by weight). When the heating residue of the coating material satisfies the above range, excellent thick-coating properties and good paintability can be obtained. This allows for sufficient heat-resistant protection. The heating residue of the coating material was measured according to the method of JIS K 5601-1-2, with a heating temperature of 105°C and a heating time of 60 minutes.

[0033] Furthermore, in this invention, the viscosity of the coating material is preferably 5 to 70 Pa·s (more preferably 7 to 60 Pa·s, even more preferably 10 to 50 Pa·s, and particularly preferably 15 to 40 Pa·s). When the viscosity of the coating material satisfies the above range, it exhibits excellent paintability and thick coating properties, and a uniform film can be formed. As a result, sufficient heat-resistant protection can be obtained. The viscosity of the coating material is the viscosity at 20 rpm (the indicator value at the 5th rotation) measured with a BH-type viscometer at a temperature of 23°C immediately after the coating material is prepared (in the case of a two-component type, after mixing the main agent and the hardener).

[0034] In this invention, by applying a coating material that satisfies the above-mentioned heating residue and viscosity range to form a coating, it becomes possible to increase the thickness of the coating, resulting in good adhesion to the substrate and stable formation of a uniform coating. Furthermore, the formed coating exhibits excellent foaming properties when the temperature rises due to fire or the like, forming a carbonized heat insulating layer that can maintain the heat-resistant protective performance of the substrate.

[0035] The coating material of the present invention is suitable as a foamed fire-resistant coating material for surface coating of structures such as buildings and civil engineering structures. Specifically, it can be applied to various substrates such as walls, columns, floors, beams, roofs, stairs, ceilings, and doors. Applicable substrates include, for example, concrete, mortar, siding boards, extruded boards, gypsum boards, perlite boards, bricks, plastics, wood, metals, steel frames (steel materials), glass, and porcelain tiles. These substrates may have a coating already formed on their surface, have undergone some kind of surface treatment (rust prevention treatment, flame retardant treatment, etc.), or have wallpaper attached.

[0036] When applying the coating material of the present invention to a substrate, application tools such as sprayers, rollers, brushes, and trowels can be used.

[0037] (Film formation method) The present invention provides a method for forming a coating by applying the coating material to a substrate. The coating method is not particularly limited and can be applied using various methods such as brush painting, roller painting, and spray painting (air spray, airless spray).

[0038] Furthermore, the coating material can be applied at temperatures ranging from -10 to 45°C, and even at high temperatures of 30°C or higher (and even 35°C or higher), it provides excellent workability and curing properties. In addition, while there are no particular limitations on humidity during application, it provides excellent workability, curing properties, and adhesion to the substrate even under high humidity conditions of 70% Rh or higher (and even 80% Rh or higher) (including during rainy weather). As a result, it can form a coating with excellent heat-resistant protection. Moreover, even if the curing (drying) environment of the coating material after application is under high humidity, it can achieve excellent curing properties and adhesion to the substrate, forming a coating with excellent heat-resistant protection.

[0039] When applying the coating material of the present invention to a substrate, it is sufficient to apply it in one to several layers using the method described above, but it is preferable to apply it so that the dry film thickness per layer is preferably 300 μm or more (more preferably 400 to 8000 μm). Even when the coating material of the present invention is applied so that the dry film thickness per layer exceeds 1000 μm, it is possible to obtain excellent curability and adhesion to the substrate, and to form a coating with excellent heat resistance and protective properties. Furthermore, the final film thickness formed can be appropriately set depending on the desired functionality, application area, etc., but is preferably about 0.4 to 8 mm.

[0040] (undercoating material) Furthermore, in the present invention, if necessary, the substrate can be surface-treated or an undercoat applied before applying the coating material. This improves adhesion to the substrate, corrosion resistance (rust prevention), etc. Surface treatment of the substrate can be performed, for example, by surface treatment with solvents or acids, or by scraping with a disc sander, wire wheel, scraper, wire brush, sandpaper, etc.

[0041] As undercoat materials, for example, sealers, primers, surface preparation materials, surfacers, putties, etc., as well as flat-type paints, can be applied. These may be clear or colored. Furthermore, they may be water-based or solvent-based, and can be appropriately selected depending on the area to be painted, with one or more types being used. As undercoat materials, it is preferable to include resin components such as acrylic resin, urethane resin, and epoxy resin, and in addition to the above resin components, various additives can be blended in an amount that does not affect the effects of the present invention. Examples of such additives include rust-preventive pigments, extender pigments, coloring pigments, plasticizers, preservatives, antifungal agents, antialgal agents, defoaming agents, leveling agents, pigment dispersants, settling inhibitors, sagging inhibitors, antioxidants, catalysts, crosslinking agents, etc.

[0042] The primer can be applied using various methods, such as brush painting, roller painting, or spray painting. The application amount is preferably 30 to 500 g / m². 2 (comfortably 50-300g / m 2 The number of coats of the primer can be set appropriately depending on the surface condition of the substrate, but it is preferably 1 to 2 times.

[0043] (Finishing material) The present invention allows for the lamination of a finishing material on a film formed by the above-mentioned coating material. The finishing material is not particularly limited as long as it does not hinder the film from foaming and forming a carbonized insulation layer when the temperature rises due to fire or the like, and known finishing materials can be laminated. Such finishing materials can be laminated by applying a topcoat or by attaching various sheet materials.

[0044] The topcoat material can be any type, such as clear or colored, glossy or matte, hard or elastic, thin or thick film. It can also be water-based or solvent-based, and can be appropriately selected according to the desired purpose. Furthermore, the topcoat material of the present invention preferably contains a resin component. Examples of such resins include solvent-soluble resins, non-aqueous dispersion resins, solvent-free resins, water-dispersible resins, and water-soluble resins. Examples of resin types include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, acrylic silicone resins, fluororesins, silicon resins, polyvinyl alcohols, cellulose derivatives, or composites thereof. These can be used individually or in combination of two or more. In particular, the present invention preferably contains one or more selected from urethane resins, epoxy resins, acrylic resins, and acrylic silicone resins.

[0045] Furthermore, the above resin component may also have crosslinking reactivity. When the resin component is a crosslinking-type resin, the water resistance, durability, and adhesion of the formed film are enhanced, and the occurrence of blistering and peeling of the film due to rain, condensation, etc., and a decrease in heat resistance can be suppressed. Such a crosslinking-type resin may be one that undergoes a crosslinking reaction on its own, or one that undergoes a crosslinking reaction by a separately mixed crosslinking agent. Such crosslinking reactivity can be imparted by combining reactive functional groups such as hydroxyl groups and isocyanate groups, carbonyl groups and hydrazide groups, epoxy groups and amino groups, aldo groups and semicarbazide groups, keto groups and semicarbazide groups, alkoxyl groups with each other, carboxyl groups and metal ions, carboxyl groups and carbodiimide groups, carboxyl groups and epoxy groups, carboxyl groups and aziridine groups, carboxyl groups and oxazoline groups, etc. Among these, it is preferable to include one or more crosslinking-type resins selected from hydroxyl group-isocyate group, carbonyl group-hydrazide group, epoxy group and amino group.

[0046] In addition to the resin component of the above-mentioned topcoat, other components such as coloring pigments, extender pigments, and aggregates can be mixed in. By appropriately incorporating such components, desired colors and textures can be achieved. The amount of coloring pigments, extender pigments, aggregates, etc. mixed in is not particularly limited as long as it does not hinder the effects of the above-mentioned coating material (foaming properties, heat protection properties, etc.), but preferably it is 1 to 2000 parts by weight (more preferably 5 to 1000 parts by weight) per 100 parts by weight of solid content of the resin component.

[0047] In this invention, it is particularly preferable to use pigments having infrared reflectivity and / or infrared transmittance as the coloring pigment and extender pigment. This further enhances effects such as heat resistance protection.

[0048] Examples of pigments that have infrared reflectivity include aluminum flakes, titanium dioxide, barium sulfate, zinc oxide, iron oxide, calcium carbonate, silicon dioxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, iron-chromium composite oxide, manganese-bismuth composite oxide, manganese-yttrium composite oxide, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, etc., and one or more of these can be used.

[0049] Examples of pigments that transmit infrared light include perylene pigments, azo pigments, lead yellow, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolone, phthalocyanine green, phthalocyanine blue, cobalt blue, induthlene blue, ultramarine, and Prussian blue. One or more of these can be used.

[0050] Furthermore, the topcoat material can also contain various additives that are normally used in paints. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, antialgal agents, antibacterial agents, dispersants, defoamers, adsorbents, UV absorbers, light stabilizers, antioxidants, fibers, destaining agents, hydrophilic agents, water repellents, coupling agents, catalysts, and the like.

[0051] In the film-forming method of the present invention, the topcoat material can be applied in layers, or two or more types of topcoat materials can be laminated and applied. When two or more types of topcoat materials are laminated, it is preferable that the first topcoat material (intermediate coat material) contains one or more resin components selected from urethane resin, epoxy resin, acrylic resin, and acrylic silicone resin (particularly preferably urethane resin, epoxy resin, etc.). This further enhances the adhesion between the layers of the covering material and the topcoat material. Furthermore, it is possible to form a topcoat material film with excellent film properties.

[0052] The topcoat material can be applied using any known application method, such as brush painting, roller painting, or spray painting. The application amount is preferably 30 to 5000 g / m². 2 (comfortably 50-3000g / m 2 The number of coats of the topcoat should be set appropriately depending on the surface condition of the substrate, but preferably 1 to 2 coats. Drying should preferably be carried out at room temperature.

[0053] Examples of the sheet materials mentioned above include decorative films, decorative sheets, sheet building materials, and wallpaper. Their thickness is preferably 0.01 to 30 mm (more preferably 0.05 to 20 mm). These can be attached using known adhesives (sealants). [Examples]

[0054] The following examples illustrate the features of the present invention. However, the present invention is not limited to these examples.

[0055] The product was manufactured using the raw materials shown in Table 1 and the formulation shown in Table 2.

[0056] (Examples) <Manufacturing of coating materials 1-11> Using the raw materials shown in Table 1, a coating material was obtained by mixing copolymer resin, heat-resistant components, and other components by conventional methods according to the formulation shown in Table 2.

[0057] [Table 1]

[0058] [Table 2]

[0059] <Manufacturing of test specimens> A steel plate (150mm long x 70mm wide x 1.6mm thick) that had been pre-painted with rust-preventive coating was spray-coated with a coating material to a dry film thickness of 1.5mm under standard conditions (temperature 23°C, relative humidity 50%). After curing for 16 hours, the same coating material was spray-coated again to a dry film thickness of 1.5mm and cured for 7 days. This was used as a test specimen, and the following evaluation was performed. The results are shown in Table 2. <Rating> Based on the ISO 5660-1 cone calorimeter method, an electric heater (CONEIII, manufactured by Toyo Seiki Co., Ltd.) was used to inflate the surface of the test specimen at 50 kW / m². 2 The foaming properties (foaming ratio) and the temperature of the back surface of the steel plate were measured when radiant heat was emitted for 30 minutes, and the density and adhesion were further evaluated. The evaluation criteria are as follows. <Rating 1 (Effervescence)> A: Expansion ratio of over 20 times B: Expansion ratio greater than 15 times and less than or equal to 20 times C: Foaming ratio more than 10 times and less than 15 times D: Expansion ratio of 10 times or less <Evaluation 2 (Surface Temperature)> A: Below 470℃ B: 470℃ or higher, but less than 500℃ C: 500°C or higher and lower than 550°C D: over 550°C <Evaluation 3 (Density) > A test specimen whose expansion ratio had been measured was cut, and the density of the carbonized heat-insulating layer in the cross-section was visually confirmed. The evaluation criteria were a 4-grade evaluation (excellent: A > B > C > D: poor), wherein "A" was assigned to those with high density and "D" was assigned to those with low density. <Evaluation 4 (Adhesion 1: Adhesion to base material) > In the above-mentioned heat resistance evaluation 2, the adhesion near the base material of the carbonized heat-insulating layer formed after radiating radiant heat for 30 minutes was checked. For the evaluation criteria, the presence or absence of lifting between the base material and the carbonized heat-insulating layer was visually evaluated, and a 4-grade evaluation (excellent: A > B > C > D: poor) was adopted, wherein "A" was assigned to those with no lifting and "D" was assigned to those with severe lifting.

[0060] <Evaluation 5 (Adhesion 2: Adhesion of coating material) > A two-component epoxy resin adhesive was used to bond a steel jig to the coating material layer side of a test specimen, and after the specimen was left to stand under standard conditions for one week, the adhesion strength was measured using an autograph (model AGX, manufactured by Shimadzu Corporation) according to the procedure of Section 7.10 of JIS A 6909:2014 "Finishing Coatings for Architecture" (loading speed: 1764N / min). The evaluation criteria are as follows. A: Adhesion strength of 0.4N / mm 2 or higher (fracture within the coating material layer of the test specimen) B: Adhesion strength of 0.4N / mm 2 or higher (interfacial fracture between the steel plate and the coating material layer of the test specimen) C: Adhesion strength of 0.2N / mm 2 or higher and 0.4N / mm 2 or lower (interfacial fracture between the steel plate and the coating material layer of the test specimen) D: Adhesion strength of 0.2N / mm 2 or lower (interfacial fracture between the steel plate and the coating material layer of the test specimen)

Claims

1. The coating material forms a carbonized heat insulating layer at a temperature of 200°C or higher. The coating material includes a binder and a heat-resistant component. The binder comprises a copolymer resin of vinyl monomers including (a1) alkylate vinyl monomer and (a2) aromatic vinyl monomer, (a2) The aromatic vinyl monomer is styrene. A covering material characterized by the following features.

2. The coating material forms a carbonized heat insulating layer at a temperature of 200°C or higher. The coating material includes a binder and a heat-resistant component. The binder comprises a copolymer resin of vinyl monomers, which includes (a1) 3% to 60% by weight of alkylate vinyl monomer and (a2) 40% to 97% by weight of aromatic vinyl monomer. (a2) The aromatic vinyl monomer is styrene. A covering material characterized by the following features.

3. The coating material according to claim 1 or 2, characterized in that the heat-resistant component includes one or more selected from a foaming agent, a carbonizing agent, a flame retardant, and a filler.

4. A method for forming a coating by applying a coating material to a substrate, A method for forming a coating, characterized in that the coating material is the coating material described in claim 1 or claim 2.

5. A method for forming a coating by applying a coating material to a substrate, The coating material is the coating material described in claim 1 or claim 2, and the method for forming a coating is characterized by applying it in one or more layers, with a dry film thickness of 300 μm or more per layer, and a final dry film thickness of 0.4 to 8 mm.

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