JP6836624B2 - Covering material - Google Patents

Description

The present invention relates to a novel coating material.

For the purpose of protecting a base material such as steel material, concrete, wood, or synthetic resin from a fire, various coating materials have been proposed that foam due to a temperature rise in the event of a fire or the like to form a carbonized heat insulating layer. As such a coating material, a synthetic resin mixed with a foaming agent, a carbonizing agent, a flame retardant, or the like is known. The heat resistance protection performance of such a coating material is often determined by the film thickness, and in order to obtain the desired heat resistance protection performance, it is important to apply the coating material so as to be uniform at a predetermined film thickness. Above all, the selection of synthetic resin is important.

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

Japanese Unexamined Patent Publication No. 5-70540

However, in the case of Patent Document 1, the expansion ratio of the film when the temperature rises is lower than that of the coating material using acrylic resin or epoxy resin as the synthetic resin, and further, the carbonized heat insulating layer (foamed layer) is incinerated or shrunk. There was still room for improvement in order to obtain the desired heat-resistant protective performance.
The present invention has been made in view of such a problem, and an object of the present invention is to provide a coating material capable of forming a stable carbonized heat insulating layer when the temperature rises and ensuring excellent heat resistance protection performance. And.

In order to solve such a problem, the present inventors include a specific polyol component and a polyisocyanate component as a film forming component in a coating material in which the film forms a carbonized heat insulating layer due to a temperature rise in the event of a fire or the like. As a result, it has been found that the above-mentioned problems can be solved and the heat-resistant protection performance of the base material can be improved, and the present invention has been completed.

That is, the present invention has the following features.
1. 1. The coating material is a coating material that forms a carbonized heat insulating layer as the temperature rises.
The temperature rise of the coating film is 200 ° C. or higher.
The coating material contains a polyol component (A1) and a polyisocyanate component (A2) as a film-forming component (A).
As the polyol component (A1), polyether polyol (a1) and a fluorine-containing polyol (a2) seen including,
The number average molecular weight of the polyether polyol (a1) is 1000 or more.
A coating material, wherein the fluorine-containing polyol (a2) contains at least a copolymer of a fluorine-containing monomer and a hydroxyl group-containing vinyl-based monomer.
2. 2. 1. The fluorine-containing polyol (a2) is contained in an amount of 0.1 to 30% by weight in terms of solid content with respect to the total amount of the polyol component (A1). The covering material described in.
3. 3. 1. The hydroxyl value of the fluorine-containing polyol (a2) is 5 to 100 mgKOH / g. Or 2. The covering material described in.

The present invention is a coating material in which the coating material forms a carbonized heat insulating layer by increasing the temperature, and the coating material contains a polyol component (A1) and a polyisocyanate component (A2) as a coating material (A). By containing the polyether polyol (a1) and the fluorine-containing polyol (a2) in combination as the polyol component, it has excellent foamability when the temperature rises due to a fire or the like, and the carbonized heat insulating layer is incinerated or shrunk. Can be suppressed to form a stable carbonized heat insulating layer, and the heat resistance of the base material can be enhanced.

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

The present invention is a coating material in which the coating material forms a carbonized heat insulating layer due to a temperature rise (heating) such as a fire, and the coating material has a polyol component (A1) and a polyisocyanate component (A1) as a coating material (A). A2) is included as an essential ingredient. The polyol component (A1) and the polyisocyanate component (A2) are components that react to form a film.

In the present invention, by containing the polyether polyol (a1) and the fluorine-containing polyol (a2) in combination as the polyol component (A1), the temperature of the coating film rises (preferably the coating film surface temperature is 200 ° C. or higher, more preferably 200 ° C. or higher). By 250 ° C. or higher), it is possible to have excellent foamability, suppress ashing and shrinkage of the carbonized heat insulating layer, form a stable carbonized heat insulating layer, and enhance the heat resistance of the base material.

The polyether polyol (a1) of the present invention has a molecular weight of preferably 1000 or more (more preferably 3000 or more and 20000 or less, further preferably 5000 or more and 18000 or less, particularly preferably 6000 or more and 15000 or less, and most preferably 6500 or more and 12000. Below). By including such a polyether polyol (a1) as the polyol component (A1), excellent foamability can be obtained by increasing the temperature of the coating film (preferably the coating film surface temperature is 200 ° C. or higher, more preferably 250 ° C. or higher). As shown, the heat-resistant protection performance of the base material can be enhanced. 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 above-mentioned polyether polyol (a1) is addition polymerization of polyhydric alcohols such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol derivative, sorbitol and neopentyl glycol and alkylene oxides such as ethylene oxide and propylene oxide. Is obtained by. In the present invention, a polymer obtained by addition polymerization of the above polyhydric alcohols and ethylene oxide and / or propylene oxide is preferable, and one having ethylene oxide and / or propylene oxide added to the end is more preferable. is there. Further, the above-mentioned polyether polyol preferably contains a polyether polyol having 3 or more functional groups (3 or more functional groups) having an active hydrogen atom. In this case, the curability is excellent and the film can be stably formed, so that the effect of the present invention can be easily obtained. A hydroxyl group is suitable as the functional group having an active hydrogen atom.

As such a polyether polyol (a1), the hydroxyl value is preferably 3 to 150 mgKOH / g (more preferably 5 to 100 mgKOH / g, further preferably 7 to 40 mgKOH / g, most preferably 10 to 30 mgKOH / g). Is. By using such a polyol component (a1), it is possible to exhibit more excellent foamability and enhance the heat-resistant protection performance of the base material. In the present invention, the hydroxyl value is a value (mgKOH / g) represented by the number of mg of potassium hydroxide equimolar to the hydroxyl group contained in 1 g of solid content, and "α to β" is "α or more". It is synonymous with "below β".

The content of the polyether polyol (a1) is preferably 70 to 99.9% by weight (more preferably 90 to 99% by weight) with respect to the total amount of the polyol component (A1).

In the present invention, by containing the fluorine-containing polyol (a2) as the polyol component (A1), the flame retardancy of the film-forming component (A) is enhanced, and the film is excellent when the temperature rises due to a fire or the like. It exhibits foamability, forms a carbonized heat insulating layer, can suppress ashing and shrinkage even in a high temperature atmosphere, and can enhance the heat resistance protection performance of the base material.

The fluorine-containing polyol (a2) is not particularly limited, but for example, a fluorine-containing monomer such as a fluoroolefin monomer or a fluoroalkyl group-containing acrylic monomer, a hydroxyl group-containing vinyl-based monomer, and other components, if necessary, are used. 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, perfluoroisononyl methyl methacrylate, 2-perfluorooctyl ethyl acrylate, 2-perfluorooctyl ethyl methacrylate, trifluoroethyl acrylate and the like. These can be used alone or in combination of two or more. In the present invention, it is preferable to use one or more selected from tetrafluoroethylene and chlorotrifluoroethylene, and more preferably chlorotrifluoroethylene.

Examples of the hydroxyl group-containing vinyl-based monomer 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. Hydroxyaryl ethers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, and the like. And one or more of these can be used.

Examples of other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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) (Meta) acrylic acid alkyl ester such as acrylate; Amino such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylamino (meth) acrylate, aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate 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 ( Amid-containing monomer such as meta) acrylamide; nitrile group-containing monomer such as (meth) acrylonitrile; epoxy group-containing monomer such as glycidyl (meth) acrylate; aromatic vinyl monomer such as styrene, methylstyrene, chlorostyrene, vinyltoluene; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl butylate, vinyl pivalate; olefin-based monomers such as ethylene and propylene can be mentioned, and one or more of these can be used as needed.

As such a fluorine-containing polyol (a2), the fluorine content in the solid content of the fluorine-containing polyol (a2) is 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 5000 to 100,000 (more preferably 8,000 to 60000). By containing such a fluorine-containing polyol (a2), when the temperature rises due to a fire or the like, the film exhibits excellent foamability and forms a carbonized heat insulating layer, and suppresses ashing and shrinkage even in a 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 with respect to the total amount of the polyol component (A1). 1 to 10% by weight). By satisfying this range, the effects of the present invention can be fully exerted.

（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。 Further, in the present invention, it is preferable to include the polyol compound (a3) having an isocyanurate ring as the polyol component (A1). Examples of the polyol compound (a3) having an isocyanurate ring include a compound having an isocyanurate ring (formula 1) and two or more hydroxyl groups.

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

Further, 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, 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 and the like is reacted at the time of producing an acrylic polyol. Can be obtained by In the reaction here, 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 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, still 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 a fire or the like. It has excellent adhesion to and can prevent the carbonized heat insulating layer from falling off.

The polyol component (A1) of the present invention includes, for example, polyester polyol, acrylic polyol, epoxy-containing polyol, silicone-containing polyol, castor oil, and castor oil modification, in addition to the above components (a1), (a2), and (a3). Examples thereof include polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, and polypentadiene polyols, and one or more 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), polypeptide MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and isophorone. Diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc., or allophanated, biuretized, dimerized (uretdione), trimerized (isocyanurate), adducted, carbodiimidated derivatives, etc.; and these. Examples thereof include blocked isocyanate obtained by blocking diisocyanate with alcohols, phenols, ε-caprolactam, oximes, active methylene compounds and the like, and one or more selected from these can be used. The above-mentioned component (a3) is a component different from the above-mentioned component (A2).

In the present invention, it is preferable that the polyisocyanate component (A2) contains hexamethylene diisocyanate (HMDI) and / or a derivative thereof (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) with respect to the total amount of the polyisocyanate component (A2). Further, it is also preferable that the polyisocyanate component (A2) is composed of only HMDIs. Further, as the derivative, a biuret form and / or an isocyanurate form is suitable. In such a case, the curability of the formed film is excellent, and when the temperature rises, more excellent foamability can be exhibited, and the heat resistance of the base material can be enhanced.

The mixture of the polyol component (A1) and the polyisocyanate component (A2) is preferably 0.6 to 3.5 (more preferably 1 to 1) in terms of the NCO / OH equivalent ratio of the polyol component (A1) and the polyisocyanate component (A2). The ratio is 2.5, more preferably 1.1 to 1.9). In such a case, it is excellent in curability, a uniform film with a desired thickness can be formed, and it has more excellent foamability against a temperature rise due to a fire or the like, and a stable carbonized heat insulating layer is formed. The heat-resistant protection performance of the base material can be improved. Further, the formed film has excellent durability (for example, waterproofness, water permeability resistance, crack resistance, substrate followability, etc.), can maintain the initial appearance (aesthetic appearance) for a long period of time, and is caused by a fire or the like. The effect of the present invention can be sufficiently exerted when the temperature rises or 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 as a component different from the (a3) component and the (A2) component. A compound (A3) having a nurate ring can also be included. The compound (A3) having an isocyanurate ring is preferably reacted with the polyol component (A1) and / or the polyisocyanate component (A2) to form a film, for example, an alkoxysilyl group, a carboxyl group, or a glycidyl group. Examples thereof 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 and the like may be used.

The blending amount of the compound (A3) having an isocyanurate ring is preferably 0.1 to 30 parts by weight (more than 100 parts by weight) with respect to 100 parts by weight of the solid content of the polyol component (A1) and the polyisocyanate component (A2). It is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight). In such a case, the effect of the present invention can be fully exerted.

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. The curing catalyst is a substance having an action of accelerating the reaction of isocyanate groups to cure. Examples of the curing catalyst include various types such as amine catalysts, organometallic catalysts, and inorganic catalysts. For example, examples of the amine-based catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, hexamethylenediamine, a derivative thereof, or a mixture with 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 and the like. These can be used alone or in combination of two or more, and can also be mixed with a solvent. In the present invention, it is particularly preferable to include an organometallic catalyst. In this case, the curing property of the film-forming component (A) can be enhanced as well as the curing can be promoted, and the effect of the present invention can be enhanced.

The cured film formed from the film-forming component (A) has an exothermic peak in a differential thermal analysis method (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 maximum value of. In such a case, when the temperature rises due to a fire or the like, the foamability is further improved, an excellent carbonized heat insulating layer can be formed, and the heat resistance and protection of the base material can be enhanced.

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 a decomposition reaction such as a urethane bond proceeds. When the exothermic peak of the cured film of the film-forming component (A) has a maximum value in the above temperature range, the foaming and carbonization reactions can efficiently proceed in a state where the film is softened without much progress of decomposition. Therefore, it is considered that the foamability is improved and the carbonized heat insulating layer can be stably formed. In particular, in the present invention, the film-forming component (A) contains a fluorine-containing polyol as the polyol component (a1), so that the exothermic peak of the cured film can be shifted to the high temperature side. As a result, it is considered that the flame retardancy of the cured film can be enhanced, decomposition at less than 200 ° C. can be suppressed, and the effects of the present invention can be fully exhibited.

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

Further, in the coating material of the present invention, as components different from the film forming component (A), for example, a foaming agent (B), a carbonizing agent (C), a flame retardant (D), and a filler (E) Etc. can be included.

Examples of the foaming agent (B) 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 foaming agent (B) is preferably 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) with respect to 100 parts by weight of the solid content of the film-forming component (A). The foaming agent (B) of the present invention imparts a foaming action to the coating film due to a temperature rise in the event of a fire or the like. Specifically, when the temperature of the coating film surface is preferably 200 ° C. or higher. It imparts a foaming action.

Examples of the carbonizing agent (C) include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, casein and the like. These can be used alone or in combination of two or more. In the present invention, pentaerythritol and dipentaerythritol are particularly preferable because they are excellent in dehydration cooling effect and carbonized heat insulating layer forming effect. The content of the carbonizing agent (C) is preferably 10 to 200 parts by weight (more preferably 20 to 120 parts by weight) with respect to 100 parts by weight of the solid content of the film-forming component (A). The carbonizing agent (C) of the present invention imparts an action of forming a carbonized heat insulating layer by dehydrating and carbonizing the film-forming component (A) together with carbonization due to a temperature rise in the event of a fire or the like.

Examples of the flame retardant (D) include organophosphorus compounds such as tricresyl phosphate and diphenyl cresyl phosphate; chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin, and pentachloride fatty acid. Chlorine compounds such as esters, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride; antimony compounds such as antimon trioxide and antimon pentachloride; phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, phosphorus Phosphorus compounds such as melamine acid, 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. Be done. These can be used alone or in combination of two or more. In the present invention, the flame retardant (D) includes, for example, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate / melamine / melem double salt, or a composite compound of melamine polyphosphate / melamine / melem double salt and dimerum pyrosulfate. It is preferable to contain at least one phosphorus compound selected from the above, and further, it is also preferable to contain ammonium polyphosphate in combination with these. The content of the flame retardant (D) is preferably 100 to 1000 parts by weight (more preferably 200 to 800 parts by weight) with respect to 100 parts by weight of the solid content of the film-forming component (A).

Examples of the filler (E) include talc, calcium carbonate, sodium carbonate, aluminum oxide (alumina), titanium oxide, zinc oxide, silica, clay, clay, silas, mica, silica sand, silica stone powder, quartz powder, and barium sulfate. And so on. These can be used alone or in combination of two or more. The content of the filler (E) is preferably 3 to 200 parts by weight (more preferably 5 to 150 parts by weight) with respect to 100 parts by weight of the solid content of the film-forming component (A).

Further, in the present invention, metal hydrate (F), fiber (G) and the like can be included in addition to the above components. The metal hydrate (F) exhibits endothermic properties due to a dehydration reaction or the like when the temperature rises, and is different from the filler (E). Examples of such a metal hydrate (F) include aluminum hydroxide and magnesium hydroxide. These can be used alone or in combination of two or more. The average particle size of the metal hydrate (F) is preferably 0.1 to 20 μm (more preferably 0.2 to 15 μm, further preferably 0.3 to 8 μm, and most preferably 0.4 to 3 μm). Is. The content of the metal hydrate (F) is preferably 1 to 200 parts by weight (more preferably 10 to 100 parts by weight, still more preferably 25) with respect to 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 (E) and the metal hydrate (F) in combination. In this case, the filler (E) and the metal hydrate (F) have a weight ratio of 1: 9 to 9: 1. (More preferably 2: 8 to 8: 2). In this case, foamability, particularly shrinkage of the carbonized heat insulating layer under high temperature can be suppressed, and a stable carbonized heat insulating layer can be formed, so that the effect of the present invention can be enhanced. The average particle size is measured by a laser diffraction type particle size distribution measuring device.

The fiber (G) can enhance the thick coating property and suppress the cracking of the coating film. In addition, the fiber (G) can prevent the coating film from sagging when the temperature rises due to a fire or the like, and can enhance the thermal conductivity inside the coating film. As a result, excellent foamability can be exhibited, a uniform carbonized heat insulating layer can be formed, and the heat resistant protection performance of the base material can be enhanced. Examples of such fibers (G) include acrylic fibers, acetate fibers, aramid fibers, copper ammonia fibers (cupla), nylon fibers, novoloid fibers, pulp fibers, biscous rayon, vinylidene fibers, polyester fibers, polyethylene fibers, and the like. Organic fibers such as polyvinyl chloride fiber, polyclar fiber, bolinosic 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 thereof include fibers and inorganic fibers such as silicon carbide fibers. These can be used alone or in combination of two or more.

In the present invention, it is preferable that the fiber (G) contains an inorganic fiber, and among them, artificial mineral fibers such as rock wool fiber, slag wool fiber, glass fiber, and ceramic fiber are preferable. As a result, cracking of the coating film can be further suppressed. Further, when the temperature rises due to a fire or the like, it is possible to prevent the coating film from sagging and the like, and it is possible to further enhance the thermal conductivity inside the coating film. As a result, it is possible to form a carbonized heat insulating layer that uniformly exhibits excellent foamability to the inside of the coating film (core portion) and has more uniform and excellent strength, and further enhances the heat resistance protection performance of the base material.

The size of the fiber (G) (fiber length and fiber diameter) may be set according to the performance of the coating material, the applicable base material, the coating tool, and the like, and the average fiber length is preferably 10 to 10. It is preferably in the range of 1000 μm (more preferably 15 to 800 μm, still more preferably 20 to 600 μm) and the average fiber diameter is preferably in the range of 0.5 to 10 μm (more preferably 1 to 8 μm). The aspect ratio (fiber length / fiber diameter) is preferably 3 to 300 (more preferably 5 to 200). When the above range is satisfied, the thick coating property is enhanced, the formed film is less likely to crack, and when the temperature rises due to a fire or the like, the film is less likely to sag, and a stable carbonized heat insulating layer can be provided. Can be formed. The content of the fiber (G) is preferably 0.5 to 30 parts by weight (more preferably 1 to 25 parts by weight, still more preferably 2 to 2) with respect to 100 parts by weight of the solid content of the film-forming component (A). 20 parts by weight).

The coating material of the present invention preferably further contains a high boiling point compound (H). The high boiling point compound (H) is a liquid at 20 ° C. and is a high boiling point liquid compound having a boiling point of 100 ° C. or higher (more preferably 150 ° C. or higher, still more preferably 200 ° C. or higher). By including such a high boiling point compound (H), the dispersion stability of the powder components such as the component (B) to the component (G) can be improved. In addition, a good film having excellent adhesion can be formed, and in particular, the elasticity of the film can be improved to prevent the film from cracking. Further, when the coating film is exposed to a high temperature due to a fire or the like, it contributes to appropriate softening of the coating film, further enhances foamability, suppresses detachment (peeling) of the formed carbonized heat insulating layer, and suppresses the formation of the carbonized heat insulating layer. Heat resistance protection performance can be improved.

The high boiling point compound (H) is not particularly limited as long as it satisfies the above conditions, and for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate. , Phthalate compounds such as diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, butylbenzyl phthalate; diethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, adipate Alibo 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-based polyesters such as -1,3 butylene glycol-based polyester and -1,2 propylene glycol-based polyester; dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di-2-ethylhexyl maleate, Maleic acid ester compounds such as diisononyl maleate and diisodecyl maleate; triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricredyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, -2 ethylhexyl diphenyl phosphate Phthalate compounds such as;

Trimetate acid ester compounds such as tris-2-ethylhexyl trimerite; ricinoleic acid ester compounds such as methylacetyl lysinolate; di-2-ethylhexyl epoxyhexahydrophthalate, diepoxystearyl epoxyhexahydrophthalate, butyl epoxidized fatty acid, Epoxy ester compounds such as epoxidized fatty acid 2-ethylhexyl, epoxidized soybean oil, and epoxidized flaxseed oil; benzoic acid ester compounds such as benzoic acid glycol ester; 1-phenyl-1-xylylethane, 1-phenyl-1-ethyl Examples thereof include aromatic hydrocarbon compounds such as phenylethane, lactones such as γ-butyrolactone, and a mixture of petroleum resin (aromatic hydrocarbon distillate polymer having 8 to 10 carbon atoms) and styrylxylene. These can be used alone or in combination of two or more.

In the present invention, the high boiling point compound (H) preferably contains at least one selected from a phthalate ester compound, an aliphatic dibasic acid ester compound, and a phosphoric acid ester compound, and further, the number of carbon atoms of the alkyl group is high. It is preferable to contain one or more selected from 4 to 11 (more preferably 5 to 10, more preferably 6 to 9) phthalate compounds and aliphatic dibasic acid ester compounds. As specific examples thereof, for example, diisononyl phthalate, diisononyl adipate and the like are suitable.

The content of the high boiling point compound (H) is preferably 5 to 150 parts by weight (more preferably 10 to 100 parts by weight, still more preferably 15 to 100 parts by weight) with respect to 100 parts by weight of the solid content of the film-forming component (A). 80 parts by weight). When the above range is satisfied, the dispersibility of the powder component is enhanced, the thick coating property is excellent, and when the temperature rises due to a fire or the like, the powder component has excellent foamability and the effect of maintaining the heat-resistant protection performance of the base material. Can be fully demonstrated.

In addition, the additive may be any additive that does not significantly impair the effects of the present invention, for example, pigments, wetting agents, plasticizing agents, lubricants, preservatives, fungicides, algae-proofing agents, antibacterial agents, and thickeners. , Leveling agent, dispersant, antifoaming agent, cross-linking agent, silane coupling agent, ultraviolet absorber, light stabilizer, antioxidant, halogen trapping agent, diluting solvent and the like.

Among these, examples of the antioxidant include phosphorus-based, sulfur-based, and hindered-type phenol-based antioxidants. These can be used alone or in combination of two or more. By including such an antioxidant, deterioration of the coating film can be suppressed not only in normal times but also when the temperature rises due to a fire or the like, and the properties of the carbonized heat insulating layer formed by the temperature rise can be improved. ..

The coating material of the present invention is preferably a two-component coating material having a main agent containing the polyol component (a1) and a curing agent containing the polyisocyanate component (a2). That is, the main agent and the curing agent may be stored in separate packages at the time of distribution, and these may be mixed at the time of use (at the time of application). In this case, the foaming agent (B), the carbonizing agent (C), the flame retardant (D), and the filler (E) (furthermore, the metal hydrate (F), the fiber (G), high The boiling point compound (H) and the curing catalyst) may be mixed with at least one of the main agent and the curing agent, respectively, but in the present invention, they are preferably mixed with the main agent. In addition, each component can be added when the main agent and the curing agent are mixed.

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, pearlite board, brick, plastic, wood, metal, steel frame (steel material), glass, porcelain tile and the like. These base materials may be those on which a film has already been formed, those on which some kind of base treatment (rust prevention treatment, flame retardant treatment, etc.) has been applied, those on which wallpaper is attached, and the like.

When the coating material of the present invention is applied to a base material, for example, a coating tool such as a spray, a roller, a brush, or a trowel may be used to apply the coating material in one or several steps. It is preferable to apply the mixture so that the dry film thickness per step is preferably 400 μm or more (more preferably 500 to 5000 μm). As a result, a thick film can be formed with a small number of coating steps. The film thickness to be finally formed may be appropriately set according to the desired functionality, application site, etc., but is preferably about 0.4 to 5 mm.

In the present invention, in order to protect the coating film formed by the covering material, a finishing material layer can be further laminated if necessary. The finishing material layer is not particularly limited as long as the film formed from the above-mentioned coating material does not foam when the temperature rises due to a fire or the like and does not hinder the formation of the carbonized heat insulating layer. Known finishing materials can be laminated. Such a finishing material layer can be laminated by applying various topcoat materials or by adhering various sheet materials. As the topcoat material, for example, a coating material such as an acrylic resin-based, a urethane resin-based, an acrylic silicon resin-based, a fluororesin-based, an epoxy resin-based, or a vinyl acetate resin-based coating material can be used. These can be used by one kind or two or more kinds, and two or more kinds of covering materials can be laminated and applied. The topcoat material may be applied by a known application method, and for example, a coating tool such as a spray, a roller, or a brush can be used. Further, examples of the sheet material include a decorative film, a decorative sheet, a sheet building material, a wallpaper, and the like, which may be attached via a known adhesive (adhesive) or the like.

Examples are shown below to further 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.

-Film forming component (A)
・ Polyol component (A1)
The polio ether polyol (a1), the fluorine-containing polyol (a2), and the polyol compound (a3) having an isocyanurate ring are mixed in the weight ratio shown in Table 1 and combined with the polyol components (A1-1) to (A1-13). did.

-Polyether polyol (a1)
(A1-1): Polyether polyol (polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight 10000, number of functional groups 3, hydroxyl value 17 mgKOH / g, addition of terminal ethylene oxide)
(A1-2): Polyether polyol (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, addition of terminal ethylene oxide)
(A1-3) Polyether polyol (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, addition of terminal ethylene oxide)
(A1-4): Polyether polyol (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, addition of terminal ethylene oxide)
(A1-5): Polyether polyol (polymer with propylene oxide using glycerin as an initiator, number average molecular weight 4000, number of functional groups 3, hydroxyl value 43 mgKOH / g, addition of terminal propylene oxide)
(A1-6): Polyether polyol (polymer with propylene oxide using glycerin as an initiator, number average molecular weight 700, number of functional groups 3, hydroxyl value 225 mgKOH / g, addition of terminal propylene oxide)

-Fluorine-containing polyol (a2)
(A2-1): Ethylene trifluoropolymer (chlorotrifluoroethylene-vinyl ether-hydroxyalkyl vinyl tatetel copolymer, fluorine content 27% by weight, hydroxyl value 52 mgKOH / g, solid content 60% by weight, aromatic Contains hydrocarbon polymer)
(A2-2): Tetrafluoroethylene copolymer (tetrafluoroethylene-vinyl ether-hydroxyalkyl vinyl tether copolymer, fluorine content 36% by weight, hydroxyl value 60 mgKOH / g, solid content 60% by weight, butyl acetate solvent Contains)
-A polyol compound having an isocyanurate ring (a3)
(A3-1) Trichloroisocyanurate (2 hydroxyethyl) (hydroxyl value 645 mgKOH / g)

-Polyisocyanate component (A2)
(A2-1) Biuret-type hexamethylene diisocyanate (NCO content 23.5%)
(A2-2) Isocyanurate-type hexamethylene diisocyanate (NCO content 23.1%)

-Effervescent agent (B): Melamine-Carbide (C): Pentaerythritol-Flame retardant (D1): Ammonium polyphosphate-Flame retardant (D2): Melamine polyphosphate-Melam-Melem double salt-filler (E) : Titanium oxide / metal hydrate (F): Aluminum hydroxide (average particle size: 1 μm)
-Fiber (G): Rock wool fiber (average fiber length 125 μm, average fiber diameter 4.5 μm)
-High boiling point compound (H): Diisononyl phthalate (boiling point 420 ° C)
-Curing catalyst (I): Organic metal catalyst-Additive 1: Dispersant, defoamer, etc.-Additive 2: Plasticizer, diluting solvent, etc.

(Coating material 1-23)
According to the formulations shown in Tables 2 and 3, components (A1), components (B) to (I), and additives 1 and 2 were mixed by a conventional method to prepare a main ingredient. Next, the component (A2) was mixed to obtain coating materials 1 to 23. In Tables 2 and 3, the mixing amount of the components (B) to (I) and the additives 1 and 2 is shown in parts by weight with respect to 100 parts by weight of the solid content of the component (A).

(Examples 1 to 22, Comparative Example 1)
A coating material was spray-coated (dry film thickness 1.5 mm) on the entire surface of a pre-rust-prevented steel sheet (length 150 mm x width 70 mm x thickness 1.6 mm) and cured at room temperature (25 ° C.) for 7 days. The following evaluations were carried out using the test specimens.

<Heat resistance evaluation 1>
Based on the ISO 5660-1 cone calorimeter method, using an electric heater (CONEIII, manufactured by Toyo Seiki Co., Ltd.), ^{the foaming ratio when radiant heat of 50 kW / m 2} is radiated to the surface of the specimen for 15 minutes, and the temperature of the back surface of the steel sheet. Was measured. Each evaluation standard is as follows. The results are shown in Tables 2 and 3.
(Expansion magnification)
AA: Foaming magnification over 35 times A: Foaming magnification over 25 times over 35 times B: Foaming magnification over 20 times over 25 times C: Foaming magnification over 15 times over 20 times D: Foaming magnification 15 times or less (back surface 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>
Based on the ISO 5660-1 cone calorimeter method, the foaming magnification and the temperature of the back surface of the steel sheet when radiant heat of ^{50 kW / m 2} is radiated to the surface of the test piece for 30 minutes using an electric heater (CONEIII, manufactured by Toyo Seiki Co., Ltd.). Was measured, and the denseness and incineration property were further evaluated. The evaluation criteria for the foaming ratio and the temperature on the back surface of the steel sheet are the same as those for the heat resistance evaluation 1. The criteria for evaluating the density and incineration are as follows. The results are shown in Tables 2 and 3.

(Evaluation of precision)
The test piece whose foaming ratio was measured was cut, and the denseness of the carbonized heat insulating layer in the cross section was visually confirmed. The evaluation criteria were a four-stage evaluation (excellent: A>B>C> D: inferior), with high precision being "A" and low precision being "D".
(Evaluation of incineration)
In the above heat resistance evaluation 2, the cross section of the carbonized heat insulating layer formed after radiating radiant heat for 30 minutes was confirmed, and the ratio of the ashed (white) portion was calculated. The evaluation criteria were a four-stage evaluation (excellent: A>B>C> D: inferior), with less ashing being "A" and more ashing being "D".

The coating materials 1 to 10 and 14 to 22 (Examples 1 to 10 and 14 to 22) are excellent in foamability in both the heat resistance evaluation 1 and the heat resistance evaluation 2 (under a high temperature in which the heating test is extended). It was possible to stably 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 resistance protection performance. In particular, in the coating materials 14 to 22 (Examples 14 to 22), when the heating test is extended, the shrinkage of the carbonized heat insulating layer is sufficiently suppressed (the change in the foaming ratio is small), and the heat resistance protection performance is even better. Was able to demonstrate. In Comparative Example 1, the foamability was insufficient, and further, when the heating test was extended, the shrinkage of the carbonized heat insulating layer was remarkable.

Next, in the heat resistance evaluations 1 and 2, the following evaluations were made in the coating materials 1 to 4, 7, 8, 14 to 22 (Examples 1 to 4, 7, 8, 14 to 22) showing excellent foamability. Was carried out.
<Heat resistance evaluation 3>
(Evaluation of dropout prevention)
The covering material of the test piece is installed horizontally so that it is on the lower side, a heater (heater temperature 680 ° C.) is installed at a position 25 mm above the test piece, the test piece is heated by the heater, and the covering material is removed from the steel plate. The temperature of the steel sheet when it fell off was measured. The evaluation was performed in the following four stages. The results are shown in Tables 2 and 3.
A: Dropping temperature 250 ° C or higher B: Dropping temperature 220 ° C or higher and lower than 250 ° C C: Dropping temperature 200 ° C or higher and lower than 220 ° C D: Dropping temperature less than 200 ° C

Further, the following evaluations were carried out in the covering materials 14 to 22 (Examples 14 to 22).
<Thickening evaluation 1>
A coating material is applied to the entire surface of a pre-rust-prevented steel sheet (length 150 mm x width 70 mm x thickness 1.6 mm) with a film applicator at a wet film thickness of 3 mm, and at room temperature (25 ° C) for 24 hours, then 50 ° C. After curing for 24 hours, the dry film thickness was measured and the change in film thickness was 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 the thickening evaluation 1, the state of the formed film was visually confirmed. The evaluation criteria were a four-stage evaluation (excellent: A>B>C> D: inferior) in which a uniform film was formed as "A" and a film with cracks was evaluated as "D". The results are shown in Table 4.

Claims (3)

The coating material is a coating material that forms a carbonized heat insulating layer as the temperature rises.
The temperature rise of the coating film is 200 ° C. or higher.
The coating material contains a polyol component (A1) and a polyisocyanate component (A2) as a film-forming component (A).
As the polyol component (A1), polyether polyol (a1) and a fluorine-containing polyol (a2) seen including,
The number average molecular weight of the polyether polyol (a1) is 1000 or more.
A coating material, wherein the fluorine-containing polyol (a2) contains at least a copolymer of a fluorine-containing monomer and a hydroxyl group-containing vinyl-based monomer. The coating material according to claim 1, wherein the fluorine-containing polyol (a2) is contained in an amount of 0.1 to 30% by weight in terms of solid content with respect to the total amount of the polyol component (A1). The coating material according to claim 1 or 2, wherein the fluorine-containing polyol (a2) has a hydroxyl value of 5 to 100 mgKOH / g.