JP7366872B2 - Coating material and film forming method - Google Patents

Description

The present invention relates to a novel coating material and a method for forming a coating.

For the purpose of protecting base materials such as steel materials, concrete, wood, and synthetic resins from fire, various coating materials have been proposed that foam when the temperature rises during a fire to form a carbonized heat insulating layer. As such a coating material, one in which a foaming agent, a carbonizing agent, a flame retardant, etc. are blended with a synthetic resin is known. The heat-resistant protection performance of such coating materials is often determined by the thickness of the coating, and in order to obtain the desired heat-resistant protection performance, it is important to apply the coating uniformly to a predetermined thickness. Among these, the selection of synthetic resin is important.

For example, as a coating material for thick application, a coating material has been developed in which a flame retardant, a foaming agent, and a carbonizing agent are blended into a composition consisting of a polyol component and a polyisocyanate component (for example, Patent Document 1).

Japanese Patent Application Publication No. 5-70540

However, in the case of Patent Document 1, the foaming ratio of the coating is low when the temperature rises when compared to coating materials using acrylic resin or epoxy resin as the synthetic resin, and furthermore, the carbonized heat insulating layer (foamed layer) may ash or shrink. These problems arose, and there was still room for improvement in order to obtain the desired heat-resistant protection performance. In addition, it is necessary to respond to changes in the coating environment due to recent climate changes and rapid weather changes. However, depending on the coating environment, there may be variations in film performance, making it difficult to obtain sufficient heat-resistant protection performance. The present invention was developed in view of these problems, and it is possible to stably ensure coating performance regardless of the coating environment, and also to form a stable carbonized heat insulating layer when the temperature rises, providing excellent heat-resistant protection. The purpose is to provide a covering material that can ensure performance.

In order to solve these problems, the present inventors developed a coating material whose film forms a carbonized heat insulating layer when the temperature rises during a fire, etc., by including a specific film-forming component and a water-absorbing agent. In addition, the formed film exhibits excellent foaming properties when the temperature rises due to fire, etc., and forms a carbonized heat-insulating layer, improving the heat-resistant protection performance of the base material. It has been found that the present invention can be maintained, leading to the completion of the present invention.

That is, the present invention has the following features.
1. The film is a coating material that forms a carbonized heat insulating layer when the temperature rises,
The temperature rise of the coating is 200°C or more,
The coating material includes a polyol component, a polyisocyanate component, and a water absorbing agent,
the polyol component includes a polyether polyol,
The molecular weight of the polyether polyol is 3,000 or more and 20,000 or less.
A covering material characterized by:
2. Furthermore, 1. characterized by containing a foaming agent, a carbonizing agent, a flame retardant, and a filler. Covering material described in .
3. A film forming method in which a coating material is applied to a base material to form a film, the method comprising:
1. or 2. A method for forming a film, comprising applying the coating material according to the above using a spray gun.

The present invention is a coating material whose coating forms a carbonized heat insulating layer when the temperature rises, and the coating material contains a polyol component, a polyisocyanate component, and a water absorbing agent, so that the coating material has excellent coating performance regardless of the coating environment. can be stably secured. Furthermore, when the temperature rises due to a fire, etc., it has excellent foaming properties and suppresses the ashing and shrinkage of the carbonized heat insulating layer to form a stable carbonized heat insulating layer and improve the heat-resistant protection of the base material. can.

Hereinafter, the present invention will be described in detail based on its embodiments.

(Coating material)
The coating material of the present invention is characterized in that the coating forms a carbonized heat insulating layer when the temperature rises (heated) due to fire, etc., and contains a polyol component, a polyisocyanate component, and a water absorbing agent.

The coating material of the present invention contains a polyol component (A1) and a polyisocyanate component (A2) as essential components as the film-forming component (A). The polyol component (A1) and the polyisocyanate component (A2) are components that react to form a film.

In the present invention, it is preferable that the polyol component (A1) includes a polyether polyol (a1). The polyether polyol (a1) preferably has a molecular weight of 1,000 or more (more preferably 3,000 or more and 20,000 or less, even more preferably 5,000 or more and 18,000 or less, particularly preferably 6,000 or more and 15,000 or less, and most preferably 6,500 or more and 12,000 or less). be. By including such a polyether polyol (a1) as the polyol component (A1), excellent foaming properties can be achieved by increasing the temperature of the coating (preferably the coating surface temperature is 200°C or higher, more preferably 250°C or higher). This can improve the heat-resistant protection performance of the substrate. In the present invention, the molecular weight of the polyol component (A1) is a number average molecular weight (Mn), which is a so-called polystyrene equivalent molecular weight determined by gel permeation chromatography using a polystyrene polymer as a reference.

The polyether polyol (a1) can be produced by addition polymerization of polyhydric alcohols such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol derivatives, sorbitol, and neopentyl glycol, and alkylene oxides such as ethylene oxide and propylene oxide. This is obtained by In the present invention, a polymer obtained by addition polymerization of the polyhydric alcohol and ethylene oxide and/or propylene oxide is preferable, and a polymer obtained by adding ethylene oxide and/or propylene oxide to the terminal is more preferable. be. Furthermore, it is preferable that the above-mentioned polyether polyol includes a polyether polyol having three or more functional groups having active hydrogen atoms (the number of functional groups is three or more). In this case, the effects of the present invention can be easily obtained because the film has excellent curability and can be stably formed. A hydroxyl group is suitable as the functional group having an active hydrogen atom.

Such a polyether polyol (a1) preferably has a hydroxyl value of 3 to 150 mgKOH/g (more preferably 5 to 100 mgKOH/g, still more preferably 7 to 40 mgKOH/g, most preferably 10 to 30 mgKOH/g). It is. By using such a polyol component (a1), even more excellent foaming properties can be exhibited and the heat-resistant protection performance of the base material can be improved. In addition, in the present invention, the hydroxyl value is a value expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl group contained in 1 g of solid content (mgKOH/g), and "α to β" means "α or more β". "hereinafter" is synonymous with "below".

Further, the content of the polyether polyol (a1) is 50% by weight or more (more preferably 60 to 99% by weight, still more preferably 70 to 98% by weight) based on the total amount of the polyol component (A1). It is preferable.

In the present invention, it is preferable that the polyol component (A1) includes a fluorine-containing polyol (a2). As a result, as the temperature of the coating rises (preferably the surface temperature of the coating is 200°C or higher, more preferably 250°C or higher), it has excellent foaming properties, and suppresses ashing, shrinkage, etc. of the carbonized heat-insulating layer, resulting in stable It can form a carbonized heat insulating layer and enhance the heat-resistant protection of the base material.

Such fluorine-containing polyol (a2) is not particularly limited, but includes, for example, fluorine-containing monomers such as fluoroolefin monomers and fluoroalkyl group-containing acrylic monomers, hydroxyl group-containing vinyl monomers, and other materials as necessary. It is obtained by copolymerizing with a polymerizable monomer. Examples of the fluoroolefin monomer include perfluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene, vinyl fluoride, and vinylidene fluoride. Examples of the fluoroalkyl group-containing acrylic monomer include perfluoromethyl methacrylate, perfluoroisononylmethyl methacrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, and trifluoroethyl acrylate. These can be used alone or in combination of two or more. In the present invention, it is preferable to use one or more types selected from tetrafluoroethylene and chlorotrifluoroethylene, and more preferably chlorotrifluoroethylene.

Examples of hydroxyl group-containing vinyl monomers include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, and hydroxypentyl vinyl ether; ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether. hydroxyallyl ethers such as; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; One or more of these can be used.

Other polymerizable monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, Isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate (Meth)acrylic acid alkyl esters such as acrylate; amino acids such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylamino (meth)acrylate, aminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. Group-containing monomers; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester; (meth)acrylamide, ethyl ( Amide-containing monomers such as meth)acrylamide; Nitrile group-containing monomers such as (meth)acrylonitrile; Epoxy group-containing monomers such as glycidyl (meth)acrylate; Aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, and vinyltoluene; Acetic acid Examples include vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, and vinyl pivalate; olefin monomers such as ethylene and propylene, and one or more of these may be used as necessary.

Such a fluorine-containing polyol (a2) has a fluorine content in the solid content of the fluorine-containing polyol (a2) of 10 to 50% by weight (more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight). ) is preferable. Further, the hydroxyl value is preferably 5 to 100 mgKOH/g (more preferably 10 to 80 mgKOH/g). Further, the molecular weight [number average molecular weight (Mn)] is preferably 5,000 to 100,000 (more preferably 8,000 to 60,000). By including such fluorine-containing polyol (a2), the film exhibits excellent foaming properties and forms a carbonized heat insulating layer when the temperature rises due to fire etc., suppressing ashing and shrinkage even in high temperature atmosphere. It is possible to improve the heat-resistant protection performance of the base material.

The content of the fluorine-containing polyol (a2) is preferably 0.1 to 30% by weight (more preferably 0.5 to 20% by weight, still more preferably 0.5 to 20% by weight) in terms of solid content, based on the total amount of the polyol component (A1). 1 to 10% by weight). By satisfying this range, it is possible to enhance the heat-resistant protection performance of the base material and to ensure sufficient adhesion with the top coat material.

（式１）
例えば、イソシアヌル酸トリス（ヒドロキシアルキル）エステル等が使用できる。イソシアヌル酸トリス（ヒドロキシアルキル）エステルとしては、例えば、イソシアヌル酸トリス（２ヒドロキシエチル）、イソシアヌル酸トリス（２ヒドロキシプロピル）、イソシアヌル酸トリス（２ヒドロキシブチル）、イソシアヌル酸トリス（２,３ジヒドロキシプロピル）等のイソシアヌレート環と水酸基を有するアルキルエステルが挙げられる。 Furthermore, in the present invention, it is preferable that the polyol component (A1) contains a polyol compound (a3) having an isocyanurate ring. Examples of the polyol compound (a3) having an isocyanurate ring include compounds having an isocyanurate ring (formula 1) and two or more hydroxyl groups,

(Formula 1)
For example, isocyanuric acid tris(hydroxyalkyl) ester and the like can be used. Examples of tris(hydroxyalkyl) isocyanurate include tris(2hydroxyethyl) isocyanurate, tris(2hydroxypropyl) isocyanurate, tris(2hydroxybutyl) isocyanurate, and tris(2,3 dihydroxypropyl) isocyanurate. Examples include alkyl esters having an isocyanurate ring and a hydroxyl group.

Furthermore, as the polyol compound (a3) having an isocyanurate ring, for example, an acrylic polyol having an isocyanurate ring can also be used. As such a compound, for example, when producing an acrylic polyol, an isocyanuric acid derivative having a reactive functional group selected from a vinyl group, an acryloyl group, a thiol group, an alkoxysilyl group, a carboxyl group, a glycidyl group, etc. is reacted. It can be obtained by In this reaction, for example, a combination of a polymerizable unsaturated double bond and a vinyl group, an acryloyl group, or a thiol group, an alkoxysilyl group, a glycidyl group and a carboxyl group, an amino group and a glycidyl group, etc. may be used.

The polyol compound (a3) having an isocyanurate ring is preferably 0.01 to 20% by weight (more preferably 0.05 to 15% by weight, even more preferably 0.1 to 10% by weight) in the polyol component (A1). %). As a result, the heat resistance of the cured film of the film-forming component (A) can be further enhanced, and a stable carbonized heat insulating layer can be formed when the temperature rises due to fire, etc. It has excellent adhesion with the carbonized heat insulating layer and can prevent the carbonized heat insulating layer from falling off.

In addition to the above components (a1), (a2), and (a3), examples of the polyol component (A1) of the present invention include polyester polyols, acrylic polyols, epoxy-containing polyols, silicone-containing polyols, castor oil, and castor oil-modified polyols. Examples include polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, polypentadiene polyols, etc., and one or more types selected from these can be used.

Examples of the polyisocyanate component (A2) of the present invention include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone Diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc., or derivatives obtained by converting these into allophanate, biuret, dimerization (uretdiionization), trimerization (isocyanurate), adductization, carbodiimide, etc.; and Examples include blocked isocyanates in which the isocyanates are blocked with alcohols, phenols, ε-caprolactam, oximes, active methylene compounds, etc., and one or more types selected from these can be used. Note that the above-mentioned component (a3) is a different component from the above-mentioned (A2) component.

In the present invention, it is preferable that the polyisocyanate component (A2) contains hexamethylene diisocyanate (HMDI) and/or its derivatives (hereinafter also referred to as "HMDIs"). The content of the HMDIs is preferably 90% by weight or more (more preferably 95% by weight or more) based on the total amount of the polyisocyanate component (A2). Moreover, an embodiment in which the polyisocyanate component (A2) consists only of HMDIs is also suitable. Further, as the derivative, a biuret compound and/or an isocyanurate compound are preferable. In such a case, the formed film has excellent curability, exhibits better foaming properties when the temperature rises, and can enhance the heat-resistant protection of the base material.

The polyol component (A1) and the polyisocyanate component (A2) are mixed in an NCO/OH equivalent ratio of preferably 0.6 to 3.5 (more preferably 1 to 1). 3.0, more preferably 1.1 to 2.5). In such cases, it has excellent curing properties and can form a uniform film with the desired thickness, and has better foaming properties and forms a stable carbonized heat insulating layer when the temperature rises due to fire etc. It is possible to improve the heat-resistant protection performance of the base material. Furthermore, the formed film has excellent durability (for example, waterproofness, water permeability resistance, cracking resistance, ability to follow the substrate, etc.), and can maintain its initial appearance (aesthetics) for a long period of time. The effects of the present invention can be fully exhibited in response to temperature rises and the like.

In the present invention, as the film-forming component (A), in addition to the polyol component (A1) and the polyisocyanate component (A2), isocyanate is added as a component different from the component (a3) and the component (A2). A compound (A3) having a nurate ring can also be included. The compound (A3) having an isocyanurate ring is preferably one that reacts with the polyol component (A1) and/or the polyisocyanate component (A2) to form a film, such as an alkoxysilyl group, a carboxyl group, or a glycidyl group. Examples include isocyanuric acid derivatives having at least one reactive functional group such as. In this case, as the polyol component (A1) and/or the polyisocyanate component (A2), those having an alkoxysilyl group, a glycidyl group, a carboxyl group, an amino group, etc. may be used.

The compounding amount of the compound (A3) having an isocyanurate ring is preferably 0.1 to 30 parts by weight (more than (preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight). In such a case, the effects of the present invention can be fully exhibited.

In the present invention, a curing catalyst that promotes the reaction between the polyol component (A1) and the polyisocyanate component (A2) can be used in combination. A curing catalyst is a substance that has the effect of promoting the reaction and curing of isocyanate groups. Examples of the curing catalyst include amine catalysts, organometallic catalysts, and inorganic catalysts. For example, examples of the amine catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, hexamethylenediamine, or a mixture thereof with a derivative or a solvent. Examples of the organometallic catalyst include organometallic compounds such as dibutyltin dilaurate and dibutyltin diacetate; organometallic salts such as potassium acetate, zinc stearate, calcium stearate, lead stearate, aluminum stearate, and tin octylate. Examples of the inorganic catalyst include tin chloride. These can be used alone or in combination of two or more, and can also be used in combination with a solvent. In the present invention, it is particularly preferable to include an organometallic catalyst. In this case, curing can be accelerated and the curability of the film-forming component (A) can be increased, and the effects of the present invention can be enhanced.

The cured film formed from the film-forming component (A) has an exothermic peak in differential thermal analysis (DTA method), and the exothermic peak is in a temperature range of 200 to 400°C (more preferably 250 to 380°C). It is preferable to have a local maximum value. In such a case, when the temperature rises due to a fire or the like, the foamability is further improved, it is possible to form an excellent carbonized heat insulating layer, and the heat-resistant protection of the base material can be improved.

The mechanism of action is not limited, but for example, the cured film of the film-forming component (A) begins to soften as the temperature rises, and then decomposition reactions such as urethane bonds proceed. When the exothermic peak of the cured film of the film-forming component (A) has a maximum value within the above temperature range, the foaming and carbonization reactions can proceed efficiently with the film softened without much decomposition progressing. Therefore, it is considered that the foamability is improved and furthermore, the carbonized heat insulating layer can be stably formed. In particular, in the present invention, when the film-forming component (A) contains a fluorine-containing polyol as the polyol component (a1), the exothermic peak of the cured film can be shifted to the high temperature side. It is considered that this increases the flame retardancy of the cured film and suppresses decomposition at temperatures below 200°C, allowing the effects of the present invention to be fully exhibited.

In the present invention, the differential thermal analysis of the cured film of the film-forming component (A) is carried out using a cured film containing the polyol component (A1) and polyisocyanate component (A2) as a sample. In the differential thermal analysis method, measurement is performed using a differential thermal analyzer (for example, "Differential thermal balance Thermo plus EVO2 TG-DTA series" manufactured by Rigaku Co., Ltd.), and 3 ± 1 mg of the sample is placed in a platinum sample pan. Using α-alumina as a standard substance, the temperature was varied from 100 to 900°C at a heating rate of 20°C/min.

The coating material of the present invention can contain a heat resistance imparting component (B) as a component different from the film-forming component (A). The heat resistance-imparting component (B) interacts with the film-forming component (A) due to a temperature rise during a fire, etc. (e.g. dehydration cooling effect, nonflammable gas generation effect, carbonization promotion effect, carbonized heat insulation layer formation effect, etc.) Components that form a carbonized heat insulating layer by at least one of the following: for example, a blowing agent (b1), a carbonizing agent (b2), a flame retardant (b3), and a filler (b4).

The foaming agent (b1) imparts a foaming effect to the coating when the temperature rises in the event of a fire, etc., and specifically, it imparts a foaming effect when the temperature of the coating surface becomes preferably 200°C or higher. It is something. Examples of the blowing agent (b1) include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, thiourea, and the like. These can be used alone or in combination of two or more. The content of the blowing agent (b1) is preferably 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A). In addition,

The carbonizing agent (b2) has the effect of forming a carbonized heat insulating layer by carbonizing and dehydrating the film-forming component (A) and carbonizing it due to a temperature rise during a fire or the like. Examples of the carbonizing agent (b2) include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein. These can be used alone or in combination of two or more. In the present invention, pentaerythritol and dipentaerythritol are particularly preferred because they are excellent in dehydration cooling effect and carbonized heat insulating layer forming effect. The content of the carbonizing agent (b2) is preferably 10 to 200 parts by weight (more preferably 20 to 120 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A).

Examples of the flame retardant (b3) include organic phosphorus compounds such as tricresyl phosphate and diphenyl cresyl phosphate; chlorinated polyphenyl, chlorinated polyethylene, chlorinated diphenyl, triphenyl chloride, chlorinated paraffin, and pentachlorinated fatty acids. Chlorine compounds such as esters, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride; Antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, phosphorus Phosphorus compounds such as acid melamine, melamine polyphosphate, melam polyphosphate, melem polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, aluminum polyphosphate; and other inorganic compounds such as zinc borate and sodium borate. It will be done. These can be used alone or in combination of two or more. In the present invention, as the flame retardant (b3), for example, melamine polyphosphate, melam polyphosphate, melamine/melam/melem polyphosphate double salt, or a composite compound of melamine/melam/melem polyphosphate and dimelam pyrosulfate, etc. It is preferable to contain at least one or more phosphorus compounds selected from the following, and it is further preferable to contain these in combination with ammonium polyphosphate. The content of the flame retardant (b3) is preferably 100 to 1000 parts by weight (more preferably 200 to 800 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A).

Examples of the filler (b4) include talc, calcium carbonate, sodium carbonate, aluminum oxide, titanium oxide, zinc oxide, silica, clay, clay, shirasu, mica, silica sand, silica powder, quartz powder, barium sulfate, etc. It will be done. These can be used alone or in combination of two or more. The content of the filler (b4) is preferably 3 to 200 parts by weight (more preferably 5 to 150 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A).

Furthermore, in the present invention, metal hydrate (b5), fiber (b6), etc. can also be included in addition to the above components. The metal hydrate (b5) exhibits endothermic properties due to dehydration reaction and the like when the temperature rises, and is different from the filler (b4) described above. Examples of such metal hydrates (b5) include aluminum hydroxide, magnesium hydroxide, and the like. These can be used alone or in combination of two or more. Further, the average particle diameter of the metal hydrate (b5) 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). It is. The content of the metal hydrate (b5) is preferably 1 to 200 parts by weight (more preferably 10 to 100 parts by weight, still more preferably 25 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A). ~80 parts by weight).

In the present invention, it is preferable to use the filler (b4) and the metal hydrate (b5) together, and in this case, the weight ratio of the filler (b4) and the metal hydrate (b5) is 1:9 to 9:1. (more preferably 2:8 to 8:2). In this case, it is possible to suppress foamability, especially shrinkage of the carbonized heat insulating layer at high temperatures, and form a stable carbonized heat insulating layer, thereby enhancing the effects of the present invention. Note that the average particle diameter is measured by a laser diffraction particle size distribution measuring device.

The fibers (b6) can enhance the thick coating properties and suppress cracks in the coating. Furthermore, the fibers (b6) can make it difficult for the coating to sag when the temperature rises due to a fire or the like, and can improve the thermal conductivity inside the coating. As a result, it exhibits excellent foamability, forms a uniform carbonized heat insulating layer, and can enhance the heat-resistant protection performance of the base material. Examples of such fibers (b6) include acrylic fibers, acetate fibers, aramid fibers, copper ammonia fibers (cupro), nylon fibers, novoloid fibers, pulp fibers, viscose rayon, vinylidene fibers, polyester fibers, polyethylene fibers, Organic fibers such as polyvinyl chloride fiber, polyclar fiber, borinosic fiber, polypropylene fiber, cellulose fiber, carbon fiber, rock wool fiber, glass fiber, silica fiber, alumina fiber, silica-alumina fiber, slag wool fiber, ceramic fiber, carbon Examples include inorganic fibers such as fibers and silicon carbide fibers. These can be used alone or in combination of two or more.

In the present invention, it is preferable that the fibers (b6) include inorganic fibers, and among them, artificial mineral fibers such as rock wool fibers, slag wool fibers, glass fibers, and ceramic fibers are preferable. Thereby, cracking of the coating can be further suppressed. Furthermore, when the temperature rises due to a fire or the like, it is possible to make the coating less likely to sag, and to further improve the thermal conductivity inside the coating. As a result, it is possible to form a carbonized heat insulating layer that exhibits excellent foamability uniformly up to the inside of the coating (core), and has more uniformity and excellent strength, thereby further enhancing the heat-resistant protection performance of the base material.

Further, the size (fiber length and fiber diameter) of the fibers (b6) may be set according to the performance of the covering material, the application base material, the specifications of the applicator, etc., and the average fiber length is preferably 10 to 10. The average fiber diameter is preferably within the range of 1000 μm (more preferably 15 to 800 μm, even more preferably 20 to 600 μm), and preferably 0.5 to 10 μm (more preferably 1 to 8 μm). Further, the aspect ratio (fiber length/fiber diameter) is preferably 3 to 300 (more preferably 5 to 200). If the above range is met, the coating will be thicker, the formed film will be less likely to crack, and in the event of a temperature rise due to a fire, the film will be less likely to sag, and a stable carbonized heat insulating layer will be created. can be formed. The content of the fiber (b6) is preferably 0.5 to 30 parts by weight (more preferably 1 to 25 parts by weight, even more preferably 2 to 25 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A). 20 parts by weight).

It is preferable that the coating material of the present invention further contains a high boiling point compound (C). The high-boiling compound (C) is a high-boiling liquid compound that is liquid at 20°C and has a boiling point of 100°C or higher (more preferably 150°C or higher, even more preferably 200°C or higher). By including such a high boiling point compound (C), the dispersion stability etc. of the heat resistance imparting component (B) etc. can be improved. In addition, a good film with excellent adhesion can be formed, and in particular, the elasticity of the film can be improved and cracking of the film can be prevented. Furthermore, when the coating is exposed to high temperatures due to fire, etc., it contributes to appropriate softening of the coating, further increases foaming properties, suppresses the shedding (peeling) of the formed carbonized heat-insulating layer, and protects the base material. Heat-resistant protection performance can be improved.

The high boiling point compound (C) is not particularly limited as long as it satisfies the above, and examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dihexyl phthalate, and di-2-ethylhexyl phthalate. , diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, butylbenzyl phthalate, and other phthalate ester compounds; diethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, adipic acid Aliphatic dibasic acid ester compounds such as dioctyl, diisononyl adipate, diisodecyl adipate, bis(butyl diglycol) adipate, diethyl sebacate, dibutyl sebacate, dihexyl sebacate, di-2-ethylhexyl sebacate; adipic acid Adipic acid polyesters such as -1,3 butylene glycol polyester, adipic acid -1,2 propylene glycol polyester; dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di-2-ethylhexyl maleate, Maleate ester compounds such as diisononyl maleate and diisodecyl maleate; triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, -2-ethylhexyl diphenyl phosphate Phosphate ester compounds such as;

Trimethic acid ester compounds such as tris-2-ethylhexyl trimellitate; ricinoleic acid ester compounds such as methyl acetyl lidinolate; di-2-ethylhexyl epoxyhexahydrophthalate, diepoxystearyl epoxyhexahydrophthalate, epoxidized butyl fatty acids, Epoxy ester compounds such as epoxidized fatty acid 2-ethylhexyl, epoxidized soybean oil, and epoxidized linseed oil; Benzoic acid ester compounds such as benzoic acid glycol ester; 1-phenyl-1-xylylethane, 1-phenyl-1-ethyl Examples include aromatic hydrocarbon compounds such as phenylethane, lactones such as γ-butyrolactone, and mixtures of petroleum resins (aromatic hydrocarbon fraction polymers having 8 to 10 carbon atoms) and styryl xylene. These can be used alone or in combination of two or more.

In the present invention, it is preferable that the high boiling point compound (C) contains one or more selected from phthalic acid ester compounds, aliphatic dibasic acid ester compounds, and phosphoric acid ester compounds, and furthermore, the number of carbon atoms in the alkyl group is It is preferable to contain one or more selected from 4 to 11 (more preferably 5 to 10, still more preferably 6 to 9) phthalic acid ester compounds and aliphatic dibasic acid ester compounds. Specific examples thereof include diisononyl phthalate, diisononyl adipate, and the like.

The content of the high boiling point compound (C) is preferably 5 to 150 parts by weight (more preferably 10 to 100 parts by weight, still more preferably 15 to 15 parts by weight) based on 100 parts by weight of the solid content of the film-forming component (A). 80 parts by weight). When the above range is met, the dispersibility of the powder component increases, it has excellent thick coating properties, it has excellent foaming properties when the temperature rises due to fire, etc., and it has the effect of maintaining the heat-resistant protection performance of the base material. be able to fully demonstrate. Furthermore, excellent suitability for top coat materials can be obtained.

Furthermore, the coating material of the present invention is characterized by containing a water absorbing agent (D). The water-absorbing agent (D) has the effect of adsorbing moisture in the coating material and/or in the air. Moisture in the coating material and/or in the air tends to react with the polyisocyanate component (A2). For this reason, the coating method and coating environment, especially when spray painting the coating material or coating (film formation) under high humidity (even in rainy weather or under high temperature and high humidity), It is easily affected by moisture, and the reaction between the polyisocyanate component (A2) and the polyol component (A1) may be inhibited, resulting in decreased curability and adhesion to the substrate, and may even result in a decreased heat-resistant protection property. . In the present invention, the water absorbing agent (D) is blended to adsorb moisture in the coating material or in the air, thereby ensuring sufficient curability and adhesion to the substrate regardless of the coating method or coating environment. It is possible to secure a stable thickness and form a thick film stably.

The water absorbing agent (D) is not particularly limited as long as it achieves the above effects, and for example, water binding agents, dehydrating agents, and the like can be used. These can be used alone or in combination of two or more. Furthermore, the water absorbing agent (D) may be in any form such as pellets, powder, liquid, paste, etc.

The water binding agent has the effect of removing water from the coating material and/or from the air by reacting with water. Examples of such water binders include orthoformic acid alkyl esters such as methyl orthoformate, ethyl orthoformate, trimethyl orthoformate, triethyl orthoformate, and tributyl orthoformate; trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, etc. Trialkyl orthoborate such as trimethyl orthoborate, triethyl orthoborate, tributyl orthoborate; monoisocyanate compounds include phenyl isocyanate, p-chlorophenylisocyanate, benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, isocyanate ethyl methacrylate Monoisocyanate compounds such as tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrakis(2-ethoxybutoxy)silane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, diphenyldiethoxysilane and acid anhydrides such as maleic anhydride and phthalic anhydride.

The above-mentioned dehydrating agent has the effect of removing water from the coating material and/or the air by taking in water as crystal water, adsorbed water, etc. (water adsorption property). Furthermore, since the dehydrating agent can dehydrate adsorbed water when the temperature rises (at high temperatures), it can improve heat-resistant protection. Examples of such dehydrating agents include silica gel, synthetic zeolite, natural zeolite, synthetic clay, activated alumina, calcium oxide, magnesium sulfate, sodium sulfate, gypsum hemihydrate, anhydrite, crystalline gypsum, cement, activated carbon, and acrylic acid. Examples include partially crosslinked combined products (polymer water absorbing agents).

In the present invention, the above-mentioned dehydrating agents are preferred as the water absorbing agent (D). Among these, porous inorganic particles such as silica gel, synthetic zeolite, natural zeolite, and activated alumina are preferable, and powder form is preferable. In the present invention, powdered synthetic zeolite is particularly preferred. Types of synthetic zeolite include A type, X type, Y type, L type, mordenite type, and chabazide type, and A type zeolite is preferred in the present invention. The average pore diameter of the porous inorganic particles may be larger than the molecular diameter of water molecules (3.9 Å), but the upper limit is 30 Å or less (more preferably 10 Å or less, still more preferably 8 Å or less, (more preferably 5 Å or less). In this case, in addition to having excellent water adsorption properties, the above component (A) has excellent curing properties and adhesion to the substrate, and a uniform film can be formed. It is possible to fully exhibit the effect of maintaining the heat-resistant protection performance of the base material without impeding the properties (does not adsorb nonflammable gas etc.). In addition, when the water-absorbing agent (D) is in powder form, its average particle diameter is preferably 30 to 500 μm (more preferably 40 to 400 μm, still more preferably 50 to 300 μm).

The content of the water absorbing agent (D) is preferably 0.5 to 50 parts by weight (more preferably 1 to 50 parts by weight, even more preferably 1 .5 to 30 parts by weight).

Other additives may be used as long as they do not significantly impede the effects of the present invention, such as pigments, wetting agents, plasticizers, lubricants, preservatives, fungicides, algaecides, antibacterial agents, and thickeners. , leveling agents, dispersants, antifoaming agents, crosslinking agents, silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants, halogen scavengers, diluting solvents, and the like.

Among these, examples of the antioxidant include phosphorus-based, sulfur-based, or hindered phenol-based antioxidants. These can be used alone or in combination of two or more. By including such an antioxidant, it is possible to suppress the deterioration of the film not only in normal times but also when the temperature rises due to fire etc., and it is possible to improve the properties of the carbonized heat insulating layer that is formed due to the rise in temperature. .

The heating residue of the coating material of the present invention is preferably 70 to 98% by weight (more preferably 75 to 95% by weight, still more preferably 80 to 93% by weight). When the heating residue of the coating material satisfies the above range, it is possible to obtain excellent thick coating properties and good coating workability. Thereby, sufficient heat-resistant protection can be exhibited. Note that the heating residue of the coating material is a value measured by the method of JIS K 5601-1-2, the heating temperature is 105° C., and the heating time is 60 minutes).

Further, in the present invention, the viscosity of the coating material is preferably 5 to 70 Pa·s (more preferably 7 to 60 Pa·s, still more preferably 10 to 50 Pa·s, particularly preferably 15 to 40 Pa·s). When the viscosity of the coating material satisfies the above range, coating workability and thick coating properties are excellent, and a uniform coating can be formed. As a result, sufficient heat-resistant protection can be obtained. The viscosity of the coating material is determined by the viscosity at 20 rpm (5th rotation) measured with a BH-type viscometer at 23°C immediately after preparing the coating material (in the case of a two-component type, after mixing the main agent and curing agent). guideline value).

In the present invention, by applying the above-mentioned heating residue and a coating material satisfying the above-mentioned viscosity range to form a film, the film can be thickened, exhibiting good adhesion to the base material, and being uniform. A film can be stably formed. Furthermore, the formed coating exhibits excellent foaming properties and can form a carbonized heat-insulating layer to maintain the heat-resistant protection performance of the substrate when the temperature increases due to fire or the like.

The coating material of the present invention is preferably a two-component coating material having a main ingredient containing the polyol component (a1) and a curing agent containing the polyisocyanate component (a2). That is, the base agent and the curing agent may be stored in separate packages during distribution, and then mixed at the time of use (during application). In this case, the powder component (B), the high boiling point compound (C), and the curing catalyst may each be mixed into at least one of the base resin and the curing agent, but in the present invention, it is preferable to mix them with the base resin. Moreover, each component can also be added at the time of mixing the base agent and the curing agent.

The coating material of the present invention is suitable as a foamable fireproof coating material applied to the surface coating of structures such as buildings and civil engineering structures. Specifically, it can be applied to various base materials such as walls, columns, floors, beams, roofs, stairs, ceilings, and doors. Applicable base materials include, for example, concrete, mortar, siding board, extruded board, gypsum board, perlite board, brick, plastic, wood, metal, steel frame (steel material), glass, and porcelain tile. These base materials may have a coating already formed on their surface, have been subjected to some kind of base treatment (rust prevention treatment, flame retardant treatment, etc.), or have wallpaper pasted on their surface.

When applying the coating material of the present invention to a substrate, an application tool such as a spray, a roller, a brush, or a trowel can be used, for example. Among these, the coating material of the present invention is particularly suitable for spray coating because it can suppress the reaction between moisture in the air and the polyisocyanate component (A2) during application.

(Film formation method)
The film forming method of the present invention is to form a film by applying the above-mentioned coating material to a base material, and the above-mentioned coating material is preferably applied with a spray gun (more preferably an air-assisted airless spray gun). Apply using. An air-assisted airless spray gun sprays liquid coating material from the spray port under relatively high pressure to atomize the coating material, and then assists this atomized mist with compressed air from outside. This is an airless spray gun that controls the spread of mist. Such air-assisted airless spray guns include, but are not particularly limited to, air coat guns (for example, "GM4700AC" and "GM4100AC" manufactured by WAGNER), air curtain guns (for example, manufactured by Seiwa Sangyo Co., Ltd.), etc. "ACG-3T", etc.), air assist guns (eg, "G15", "G40" manufactured by GRACO, "AA1600M" manufactured by BINKS, etc.), etc. can be used.

In the present invention, for example, an airless coating machine is used to apply high pressure to the coating material, and the coating is applied using the air-assisted airless spray gun. In this case, the pressure of the airless paint sprayer is preferably 10 to 40 MPa (more preferably 15 to 35 MPa, still more preferably 18 to 33 MPa), and the air pressure supplied to the air-assisted airless spray gun is preferably 0. It is 1 to 2 MPa (more preferably 0.3 to 0.9 MPa). By applying the coating under these conditions, even coating materials with high solid content such as the coating materials mentioned above can be stably atomized, exhibit good mist spreadability, and produce a uniform coating. A film can be formed. At the same time, it is possible to prevent the mist from spreading too much, so the coating material has excellent coating efficiency, is less prone to loss due to scattering, and can form a thick film with fewer coating steps. Furthermore, these coating steps can be performed using a known airless coating machine and compressor, and there is no need to heat the coating material, and the coating process can be carried out at room temperature (preferably -10 to 45 degrees Celsius, more preferably -10 to 45 degrees Celsius). Since it can be carried out at a temperature of 0 to 40°C, it has excellent workability and work environment.

In addition, the coating material of the present invention can suppress the reaction between moisture in the air and the polyisocyanate component (A2) by containing the water absorbing agent (D), so that the coating material can be atomized under the above conditions. Even in the case where the film is thick, good curability can be ensured and a thick film can be efficiently formed. In addition, the coating material can be painted at temperatures of -10 to 45°C, and has good coating workability and curing properties even at high temperatures of 30°C or higher (and even 35°C or higher). I can do it. Furthermore, the humidity during painting is not particularly limited, but even under high humidity conditions (including rainy weather) with a humidity of 90% Rh or higher (and even 95% Rh or higher), good painting workability, curing properties, and base properties can be achieved. Adhesion to materials can be obtained. As a result, a film with excellent heat-resistant protection can be formed. In addition, even if the curing (drying) environment of the coating material after painting is high and humid, it is possible to obtain a coating with excellent curing properties and adhesion to the substrate, and has excellent heat-resistant protection properties. can be formed.

When applying the coating material of the present invention to a substrate, it may be applied in one step to several steps using the above method, but the dry film thickness per step is preferably 400 μm or more (more preferably It is preferable to apply the coating so that the thickness is 500 to 8000 μm). The thickness of the final film formed may be appropriately determined depending on the desired functionality, application site, etc., but is preferably about 0.4 to 8 mm. In addition, the coating material of the present invention has excellent curability because it forms a film through the reaction of the component (A1) and the component (A2), and is preferably dried at room temperature, and the interval to the next step is Preferably, it is carried out for 5 hours or more (more preferably 10 hours or more and within 30 days).

(undercoating material)
Furthermore, in the present invention, the base material may be subjected to surface treatment or an undercoat material may be applied before applying the above-mentioned coating material, if necessary. This can improve adhesion to the base material, corrosion resistance (rust prevention), and the like. As for the surface treatment of the base material, for example, surface treatment with a solvent, acid, etc., and cleaning with a disk sander, wire foil, scraper, wire brush, sandpaper, etc. can be performed.

As the undercoat material, for example, in addition to sealers, primers, base conditioners, surfacers, putty, etc., flat type paints can also be used. These may be either clear type or colored type. Further, it may be either water-based or solvent-based, and can be appropriately selected depending on the area to be coated, etc., and one type or two or more types can be used. The undercoat material preferably contains a resin component such as an acrylic resin, a urethane resin, or an epoxy resin, and in addition to the above-mentioned resin components, various additives may be blended to the extent that they do not affect the effects of the present invention. is possible. Examples of such additives include rust preventive pigments, extender pigments, coloring pigments, plasticizers, preservatives, antifungal agents, algaecides, antifoaming agents, leveling agents, pigment dispersants, antisettling agents, and sagging agents. Examples include inhibitors, antioxidants, catalysts, crosslinking agents, and the like.

The primer material can be applied using various methods such as brush coating, roller coating, and spray coating. The coating amount is preferably 30 to 500 g/m ² (more preferably 50 to 300 g/m ² ). The number of coats of the undercoat material may be appropriately set depending on the surface condition of the base material, etc., but is preferably 1 to 2 times.

(finishing material)
In the present invention, a finishing material layer can be laminated on the covering material layer (film) formed by the above-mentioned covering material. Such a finishing material layer is not particularly limited as long as it does not inhibit the formation of a carbonized heat insulating layer by foaming the coating material layer when the temperature rises due to a fire, etc., and any known finishing material may be used. can be stacked. Such a finishing material layer can be formed by applying a topcoat material or laminating various sheet materials.

As the above-mentioned top coating material, any of clear type or colored type, glossy type or matte type, hard type or elastic type, thin film type or thick film type can be used. Further, it may be either water-based or solvent-based, and can be appropriately selected depending on the desired purpose. Moreover, it is preferable that the top coating material of the present invention contains a resin component. Examples of the form of such resins include solvent-soluble resins, non-aqueous dispersible resins, non-solvent resins, water-dispersible resins, and water-soluble resins. Examples of the type of resin include acrylic resin, urethane resin, epoxy resin, vinyl chloride resin, vinyl acetate resin, acrylic silicone resin, fluorine resin, silicone resin, polyvinyl alcohol, cellulose derivative, etc., or composites thereof. It will be done. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to include one or more selected from urethane resin, epoxy resin, acrylic resin, and acrylic silicone resin.

Furthermore, the resin component may have crosslinking reactivity. When the resin component is a crosslinking reaction type resin, the water resistance, durability, and adhesion of the formed film are increased, and it is possible to suppress the occurrence of blistering and peeling of the film due to rain, dew condensation, etc., and a decrease in heat resistance performance. . Such a crosslinking-reactive resin may be one that causes a crosslinking reaction by itself, or one that causes a crosslinking reaction by a crosslinking agent that is mixed separately. Such crosslinking reactivity is caused by, for example, 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, carboxyl groups and metal ions, and carboxyl groups. It can be provided by combining reactive functional groups such as a group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an aziridine group, and a carboxyl group and an oxazoline group. Among these, it is preferable to contain one or more crosslinking-reactive resins selected from hydroxyl-isocyanate groups, carbonyl groups and hydrazide groups, and epoxy groups and amino groups.

As components other than the resin component of the top coating material, for example, coloring pigments, extender pigments, aggregates, etc. can be mixed. By appropriately blending these components, desired colors and textures can be expressed. The amount of the coloring pigment, extender pigment, aggregate, etc. to be mixed is not particularly limited as long as it does not impede the effects of the coating material (foaming properties, heat-resistant protection, etc.), but preferably the solid content of the resin component is 100 parts by weight. The amount is preferably 1 to 2,000 parts by weight (more preferably 5 to 1,000 parts by weight).

In the present invention, it is particularly preferable to use pigments that have infrared reflectivity and/or infrared transmittance as the coloring pigments and extender pigments. Thereby, effects such as heat-resistant protection properties can be further enhanced.

Examples of pigments with infrared reflective properties include aluminum flakes, titanium oxide, barium sulfate, zinc oxide, iron oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, and iron-chromium composites. 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 Examples include oxides, copper-manganese-chromium composite oxides, etc., and one or more of these can be used.

Examples of pigments that transmit infrared rays include perylene pigments, azo pigments, yellow lead, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolone, phthalocyanine green, phthalocyanine blue, cobalt blue, industhrene blue, and ultramarine blue. , dark blue, etc., and one or more of these can be used.

Furthermore, the top coat material can also contain various other additives that can be used in ordinary paints. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, algaecides, antibacterial agents, and dispersants. agents, antifoaming agents, adsorbents, ultraviolet absorbers, light stabilizers, antioxidants, fibers, antifoaming agents, hydrophilic agents, water repellents, coupling agents, catalysts, and the like.

In the film forming method of the present invention, the top coat material can be applied in layers, or two or more types of top coat materials can be layered and applied. When laminating two or more types of top coat materials, the first top coat material (intermediate coat material) is one or more selected from urethane resin, epoxy resin, acrylic resin, and acrylic silicone resin (especially preferably urethane resin, epoxy resin). It is preferable to include a resin component such as a resin or the like. Thereby, the adhesion between the coating material and the top coating material can be further improved. Furthermore, a top coat film with excellent film properties can be formed.

The top coat material may be applied by any known application method, for example, various methods such as brush painting, roller painting, and spray painting. The coating amount is preferably 30 to 5000 g/m ² (more preferably 50 to 3000 g/m ² ). The number of coats of the top coat material may be appropriately set depending on the surface condition of the base material, etc., but is preferably 1 to 2 times. Further, drying may preferably be carried out at room temperature.

Examples of the sheet materials include decorative films, decorative sheets, sheet building materials, wallpaper, and the like. Further, the thickness thereof is preferably 0.01 to 30 mm (more preferably 0.05 to 20 mm). These may be attached using a known adhesive (adhesive) or the like.

Examples are shown below to clarify the features of the present invention. However, the present invention is not limited to this range.

The following materials were used as each raw material.

・Polyol component (A1)
・Polyether polyol (a1)
(a1-1): Polyether polyol (addition polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight 10,000, number of functional groups 3, hydroxyl value 17 mgKOH/g, terminal ethylene oxide addition)
(a1-2): Polyether polyol (addition polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight 7000, number of functional groups 3, hydroxyl value 24 mgKOH/g, terminal ethylene oxide addition)
(a1-3) Polyether polyol (addition polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight 6000, number of functional groups 3, hydroxyl value 28 mgKOH/g, terminal ethylene oxide addition)
(a1-4): Polyether polyol (addition polymer of ethylene oxide and propylene oxide using propylene glycol as an initiator, number average molecular weight 5100, number of functional groups 3, hydroxyl value 33 mgKOH/g, terminal ethylene oxide addition)
(a1-5): Polyether polyol (addition polymer with propylene oxide using glycerin as an initiator, number average molecular weight 4000, number of functional groups 3, hydroxyl value 43 mgKOH/g, terminal propylene oxide addition)
(a1-6): Polyether polyol (addition polymer with propylene oxide using glycerin as an initiator, number average molecular weight 700, number of functional groups 3, hydroxyl value 225 mgKOH/g, terminal propylene oxide addition)

・Fluorine-containing polyol (a2)
(a2-1): Trifluoroethylene copolymer (chlorotrifluoroethylene-vinyl ether-hydroxyalkyl vinyl ether copolymer, fluorine content 27% by weight, hydroxyl value 52mgKOH/g, solid content 60% by weight, aromatic carbonization) (contains hydrogen solvent)
・Polyol compound (a3) having an isocyanurate ring
(a3-1) Tris(2-hydroxyethyl) isocyanurate (hydroxyl value 645mgKOH/g)

・Polyisocyanate component (A2)
(A2) Biuret type hexamethylene diisocyanate (NCO content 23.5%)

・Fire resistance imparting component (B)
(b1) Foaming agent: Melamine (b2) Carbonizing agent: Pentaerythritol (b3) Flame retardant: Ammonium polyphosphate (b4) Filler: Titanium oxide (b5) Metal hydrate: Aluminum hydroxide (average particle size: 1 μm)
(b6) Fiber: Rock wool fiber (average fiber length 125 μm, average fiber diameter 4.5 μm)
・High boiling point compound (C)
(c1) Diisononyl phthalate (boiling point 420°C)
・Water absorbing agent (D)
(D1) Powdered synthetic zeolite (average particle size 150 μm or less, type A, average pore size 4 Å)
(D2) Powdered synthetic zeolite (average particle diameter 150 μm or less, X type, average pore diameter 9 Å)
(D3) Synthetic silica gel (average particle size 40 μm, A type, average pore size 24 Å)
・Curing catalyst: Organometallic catalyst ・Additive 1: Dispersant, antifoaming agent, etc. ・Additive 2: Plasticizer, diluting solvent, etc.

(Coating material 1 to 6)
According to the formulation shown in Table 1, component (A1), component (B), component (D), and others (curing catalyst, additives 1 and 2) were mixed in a conventional manner to prepare a base material. Next, component (A2) was mixed to obtain coating materials 1 to 6. In Table 2, the mixing amounts of component (B), component (D), curing catalyst, and additives 1 and 2 are shown in parts by weight based on 100 parts by weight of the solid content of component (A).

(Test Examples 1A to 4A: Setting of coating conditions)
Coating material 1 was applied to the entire surface of the base material (plywood coated with anti-rust coating: 900 mm long x 900 mm wide x 6 mm thick) under the following conditions (dry film thickness 1.5 mm), and the coating workability was evaluated. did.
- Application conditions [I] Painting was performed at room temperature (25°C, 60% Rh) using an airless atomizer (pressure 20-21 MPa) and an air-assisted airless spray gun (supplied air pressure: 0.3 MPa).
[II] Painted at room temperature (25°C, 60% Rh) using an airless coating machine (pressure 20 to 21 MPa) and an air-assisted airless spray gun (supplied air pressure: 0.5 MPa).
[III] Painting was performed at room temperature (25°C, 60% Rh) using an airless coating machine (pressure 15 to 17 MPa) and an air-assisted airless spray gun (supplied air pressure: 0.5 MPa).
[IV] Painted at room temperature (25°C, 60% Rh) using an airless coating machine (pressure 15 to 18 MPa) and an airless spray gun (supplied air: none).

<Painting workability evaluation>
The atomization status of the coating material and coating stability at the time of preparing the above test specimens were evaluated. The evaluation criteria are as follows. Further, the results are shown in Table 2.
A: The atomization of the coating material was good and uniform coating was possible.
B: Atomization of the coating material was good, and almost uniform coating was possible.
C: The atomization of the coating material was somewhat insufficient, and some uneven coating (tail) occurred.
D: Atomization of the coating material was insufficient.

As a result of evaluating the coating workability of Coating Material 1 under each application condition, it was found that under coating conditions [I] and [II], the atomization of the coating material was good and uniform coating was possible.
Therefore, application conditions [I] The following tests were conducted using an airless paint sprayer (pressure 20 to 21 MPa) and an air-assisted airless spray gun (supplied air pressure: 0.3 MPa) and changing the painting environment.

(Examples 1 to 5, Comparative Example 1)
An airless coating machine (pressure 20-21 MPa) and an air-assisted airless spray gun (supply air pressure: 0.3 MPa) apply coating material to the entire surface of a steel plate (length 150 mm x width 70 mm x thickness 1.6 mm) that has been pre-painted to prevent rust. The test specimens were coated under the following coating environment (dry film thickness: 1.5 mm) and cured for 7 days, and the adhesion was evaluated. The results are shown in Table 3.
・Painting environment (coating and curing conditions)
[I] Room temperature (25°C, 60% Rh)
[V] High temperature and high humidity (30℃, 95%Rh)
[VI] High temperature and high humidity (35℃, 95%Rh)
(Reference example 1)
As a reference example, a test specimen was prepared by applying coating material 6 using a roller under the above-mentioned coating environment and curing, and similar evaluations were conducted. The results are shown in Table 3.

<Adhesion (adhesion strength) evaluation>
Using the above test specimen, the adhesion strength was measured according to the procedure of JIS A6909:2014 "Architectural Finish Coating Materials" 7.10. The evaluation criteria are as follows.
A: Adhesion strength 0.65N/mm ² or more B: Adhesion strength 0.5N/mm ² or more 0.65N/mm less than ² C: Adhesion strength 0.25N/mm ² or more 0.5N/mm less than ² D: Adhesive strength less than 0.25N/ ^mm2

In Examples 1 to 5, the coating workability was good under all coating environments, and good adhesion was obtained. In particular, in Examples 1 and 3, excellent adhesion was obtained even under high temperature and high humidity conditions (painting environments [V] and [VI]). On the other hand, Comparative Example 1 had poor adhesion under high temperature and high humidity conditions. As Reference Example 1, when applying with a roller, good adhesion was obtained under high temperature and high humidity (painting environment [V]), but poor adhesion was obtained under high temperature and high humidity (painting environment [VI]). The results were inferior.

(Covering materials 1, 3, 4, 7-25)
According to the formulations shown in Tables 4 to 6, components (A1), components (B) to (D), and others (curing catalyst, additives 1 and 2) were mixed in a conventional manner to prepare a base agent. Next, component (A2) was mixed to obtain coating materials 1, 3, 4, 7 to 25. In Tables 4 to 6, the mixing amounts of components (B) to (D), curing catalyst, and additives 1 and 2 are shown in parts by weight based on 100 parts by weight of the solid content of component (A).

(Test Examples 1B to 22B: Heat resistance evaluation)
The coating material was applied to the entire surface of a steel plate (length 150 mm x width 70 mm x thickness 1.6 mm) that had been previously coated with anti-rust coating under application conditions [V] (dry film thickness 1.5 mm), and was coated under high temperature and high humidity (30 mm). ℃, 95% Rh) for 7 days as test specimens, and the following evaluations were performed. The results are shown in Tables 4 to 6.
<Heat resistance evaluation 1>
ISO 5660-1 Based on the cone calorimeter method, the expansion ratio and the temperature on the back surface of the steel plate when 50 kW/m ² of radiant heat is radiated on the surface of the specimen for 15 minutes using an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.) was measured. Each evaluation standard is as follows.
(Foaming ratio)
AA: Foaming ratio more than 35 times A: Foaming ratio more than 25 times and less than 35 times B: Foaming ratio more than 20 times and less than 25 times C: Foaming ratio more than 15 times and less than 20 times D: Foaming ratio less than 15 times (backside temperature)
AA: Less than 430°C A: 430°C or more and less than 470°C B: 470°C or more and less than 500°C C: 500°C or more and less than 550°C D: More than 550°C

<Heat resistance evaluation 2>
ISO 5660-1 Based on the cone calorimeter method, the expansion ratio and the temperature on the back surface of the steel plate when 50 kW/m ² of radiant heat is radiated on the surface of the specimen for 30 minutes using an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.) was measured, and the compactness and ashability were further evaluated. The evaluation criteria for the expansion ratio and the temperature on the back surface of the steel plate are the same as those for heat resistance evaluation 1 above. The compactness evaluation and ashability evaluation criteria are as follows.

(Denseness evaluation)
The test specimen whose expansion ratio was measured was cut, and the denseness of the carbonized heat insulating layer in the cross section was visually confirmed. The evaluation criteria was a four-level evaluation (Excellent: A>B>C>D: Poor), with "A" indicating high density and "D" indicating low density.
(Ashing property evaluation)
In the above heat resistance evaluation 2, the cross section of the carbonized heat insulating layer formed after irradiating radiant heat for 30 minutes was checked, and the ratio of the ashed (white) portion was calculated. The evaluation criteria was a four-level evaluation (excellent: A>B>C>D: poor), with "A" indicating less ashing and "D" indicating progressing ashing.

<Heat resistance evaluation 3>
(Evaluation of fall prevention)
The test specimen was placed horizontally with the coating material on the bottom side, and a heater (heater temperature 680°C) was installed at a position 25 mm above the specimen. The temperature of the steel plate when it fell off was measured. Evaluation was performed in the following four stages.
A: Falling temperature 250°C or higher B: Falling temperature 220°C or higher but lower than 250°C C: Falling temperature 200°C or higher but lower than 220°C D: Dripping temperature lower than 200°C

<Thickening evaluation 1>
A coating material was applied to the entire surface of a steel plate (length 150 mm x width 70 mm x thickness 1.6 mm) with a wet film thickness of 3 mm using a film applicator, and was heated at room temperature (25°C) for 24 hours, then at 50°C. After curing for 24 hours, the dry film thickness was measured and changes in film thickness were confirmed. The evaluation criteria are as follows.
A: Film thickness reduction rate is less than 15% B: Film thickness reduction rate is 15% or more and less than 30% C: Film thickness reduction rate is 30% or more and less than 45% D: Film thickness reduction rate is 45% or more

<Thickening evaluation 2>
In film thickening evaluation 1, the state of the formed film was visually confirmed. The evaluation criteria was a four-level evaluation (excellent: A>B>C>D: poor), with "A" indicating that a uniform film was formed and "D" indicating that cracks were formed in the film.

Test Examples 1B, 2B, 4B to 6B, 11B to 14B, and 17B to 22B had excellent foaming properties and stable properties in both heat resistance evaluation 1 and heat resistance evaluation 2 (under high temperature by extending the heating test). It was possible to form a carbonized heat insulating layer and further suppress the shrinkage of the carbonized heat insulating layer, and it was possible to exhibit sufficient heat-resistant protection performance. Further, in Test Examples 17B to 22B, good results were also obtained in heat resistance evaluation 3 (falling prevention property). In particular, in Test Examples 19B to 22B, when the heating test was extended, the shrinkage of the carbonized heat insulating layer was sufficiently suppressed (there was little change in the expansion ratio), and even more excellent heat-resistant protection performance could be demonstrated. .

Claims (3)

The film is a coating material that forms a carbonized heat insulating layer when the temperature rises,
The temperature rise of the coating is 200°C or more,
The coating material includes a polyol component, a polyisocyanate component, and a water absorbing agent,
the polyol component includes a polyether polyol,
The molecular weight of the polyether polyol is 3,000 or more and 20,000 or less.
A covering material characterized by: The coating material according to claim 1, further comprising a blowing agent, a carbonizing agent, a flame retardant, and a filler. A film forming method in which a coating material is applied to a base material to form a film, the method comprising:
A method for forming a film, comprising applying the coating material according to claim 1 or 2 using a spray gun.