JP2019199605A - Covering material - Google Patents

Abstract

To provide a covering material that has excellent foamability and can maintain the heat-resistant protective performance of a base material.SOLUTION: A covering material forms a covering film that will form a carbonized insulation layer with a temperature rise. The covering material has covering film-forming components (A): a polyol component (A1) and a polyisocyanate component (A2). The polyol component (A1) comprises polyetherpolyol (a1) and fluorine-containing polyol (a2).SELECTED DRAWING: None

Description

  The present invention relates to a novel coating material.

  For the purpose of protecting base materials such as steel, concrete, wood, and synthetic resin from fire, various coating materials that foam and form a carbonized heat insulating layer by a temperature rise during a fire have been proposed. As such a covering material, a synthetic resin blended with a foaming agent, a carbonizing agent, a flame retardant and the like is known. Such a coating material often has a heat-resistant protective performance determined by the film thickness, and in order to obtain the desired heat-resistant protective performance, it is important to apply it uniformly with a predetermined film thickness. Among them, the selection of a 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 blended with a composition composed of a polyol component and a polyisocyanate component has been developed (for example, Patent Document 1).

JP-A-5-70540

However, in the case of the above-mentioned patent document 1, the foaming ratio of the coating at the time of temperature rise is lower than that of a covering material using an acrylic resin or an epoxy resin as a synthetic resin, and further, ashing and shrinkage of the carbonized heat insulating layer (foamed layer) However, there is still room for improvement in order to obtain the desired heat-resistant protection 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 temperature rises and ensuring excellent heat-resistant 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 for a coating material in which the coating forms a carbonized heat insulation layer by a temperature rise during a fire or the like. As a result, the inventors have found that the above-mentioned problems can be solved and the heat-resistant protection performance of the substrate can be improved, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. The coating is a coating material that forms a carbonized thermal insulation layer by increasing the temperature,
The coating material includes a polyol component (A1) and a polyisocyanate component (A2) as a film forming component (A),
A coating material comprising a polyether polyol (a1) and a fluorine-containing polyol (a2) as the polyol component (A1).
2. 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 | covering material as described in.

The present invention is a coating material in which the coating forms a carbonized heat insulating layer by increasing the temperature, and the coating includes a polyol component (A1) and a polyisocyanate component (A2) as the coating-forming component (A), By including polyether polyol (a1) and fluorine-containing polyol (a2) in combination as the polyol component, it has excellent foaming properties at the time of temperature increase due to fire, etc., and ashing / shrinking of the carbonized heat insulation layer, etc. It is possible to form a stable carbonized heat insulating layer while suppressing the heat resistance of the substrate.

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

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

In the present invention, as the polyol component (A1), by including the polyether polyol (a1) and the fluorine-containing polyol (a2) in combination, the temperature rise of the coating (preferably the coating surface temperature is 200 ° C. or more, more preferably (250 ° C. or higher) can have excellent foamability and can suppress the ashing / shrinkage of the carbonized heat insulation layer to form a stable carbonized heat insulation layer, thereby improving the heat resistance of the substrate.

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. The following). By including such a polyether polyol (a1) as the polyol component (A1), an excellent foaming property can be obtained by increasing the temperature of the coating (preferably the coating surface temperature is 200 ° C. or higher, more preferably 250 ° C. or higher). As shown, the heat resistance protection performance of the substrate can be enhanced. In the present invention, the molecular weight of the polyol component (A1) is a number average molecular weight (Mn), and is a so-called polystyrene equivalent molecular weight obtained by gel permeation chromatography using a polystyrene polymer as a reference.

The polyether polyol (a1) is, for example, an addition polymerization of a polyhydric alcohol such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol derivative, sorbitol, or neopentylglycol, and an alkylene oxide such as ethylene oxide or propylene oxide. Is obtained. In the present invention, a polymer obtained by addition polymerization of the above polyhydric alcohols with ethylene oxide and / or propylene oxide is preferable, and one having ethylene oxide and / or propylene oxide added to the terminal is more preferable. is there. Further, the polyether polyol preferably includes a polyether polyol having three or more functional groups having active hydrogen atoms (functional group number of 3 or more). In this case, since it is excellent in curability and can form a film stably, the effect of this invention is easy to be acquired. A hydroxyl group is suitable as the functional group having an active hydrogen atom.

Such polyether polyol (a1) preferably has a hydroxyl value of 3 to 150 mgKOH / g (more preferably 5 to 100 mgKOH / g, more preferably 7 to 40 mgKOH / g, most preferably 10 to 30 mgKOH / g). It is. By using such a polyol component (a1), more excellent foaming properties can be exhibited, and the heat resistance protection performance of the substrate can be enhanced. In the present invention, the hydroxyl value is a value (mgKOH / g) expressed by 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”.

Moreover, it is preferable that content of the said polyether polyol (a1) is 70-99.9 weight% (more preferably 90-99 weight%) with respect to the whole quantity of a polyol component (A1).

  In the present invention, by including 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 / shrinkage even in a high-temperature atmosphere, and can enhance the heat-resistant protection performance of the substrate.

Such a fluorine-containing polyol (a2) is not particularly limited, but for example, a fluorine-containing monomer such as a fluoroolefin monomer and a fluoroalkyl group-containing acrylic monomer, a hydroxyl group-containing vinyl monomer, and other substances as required. 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 at least one selected from tetrafluoroethylene and chlorotrifluoroethylene, more preferably chlorotrifluoroethylene.

Examples of the hydroxyl group-containing vinyl 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, triethylene glycol monoallyl ether Hydroxyallyl ethers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, hydroxyl-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, etc. 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, 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) (Meth) acrylic acid alkyl esters such as acrylate; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylamino (meth) acrylate, aminoethyl (meth) ) Amino group-containing monomers such as acrylate and diethylaminoethyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester, etc. Carboxyl group-containing monomers; Amide-containing monomers such as (meth) acrylamide and ethyl (meth) acrylamide; Nitrile group-containing monomers such as (meth) acrylonitrile; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Styrene, methylstyrene, chloro Aromatic vinyl monomers such as styrene and vinyltoluene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate; Olefin monomers such as ethylene and propylene Etc., and one or two or more of these can be used if necessary.

  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. Moreover, it is preferable that a hydroxyl value is 5-100 mgKOH / g (more preferably 10-80 mgKOH / g). Furthermore, it is preferable that molecular weight [number average molecular weight (Mn)] is 5000-100000 (more preferably 8000-60000). By including such a fluorine-containing polyol (a2), when the temperature rises due to a fire or the like, the film exhibits excellent foaming properties to form a carbonized heat insulating layer, and suppresses ashing and shrinkage even in a high temperature atmosphere It is possible to improve the heat resistance protection performance of the substrate.

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) 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 sufficiently 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。 Furthermore, in this invention, it is preferable that the polyol compound (a3) which has an isocyanurate ring is included as a polyol component (A1). 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 can be used. Examples of the isocyanuric acid tris (hydroxyalkyl) ester include isocyanuric acid tris (2 hydroxyethyl), isocyanuric acid tris (2 hydroxypropyl), isocyanuric acid tris (2 hydroxybutyl), isocyanuric acid tris (2,3 dihydroxypropyl). And alkyl esters having an isocyanurate ring and a hydroxyl group.

  Moreover, as a polyol compound (a3) which has an isocyanurate ring, the acrylic polyol etc. which have an isocyanurate ring can be used, for example. As such a compound, for example, when an acrylic polyol is produced, 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. Can be obtained. For example, a combination of a polymerizable unsaturated double bond and a vinyl group, an acryloyl group, or a thiol group or an alkoxysilyl group, a glycidyl group and a carboxyl group, an amino group and a glycidyl group, or the like may be used for the reaction here.

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 increased, and a stable carbonized heat insulating layer can be formed when the temperature rises due to a fire or the like. The adhesion of the carbonized heat insulating layer can be suppressed.

As the polyol component (A1) of the present invention, in addition to the component (a1), the component (a2) and the component (a3), for example, polyester polyol, acrylic polyol, epoxy-containing polyol, silicone-containing polyol, castor oil, castor oil modified Examples thereof include polyol, polycarbonate polyol, polylactone polyol, polybutadiene polyol, polypentadiene polyol, and the like, 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), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and isophorone. Diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI and the like, or allophanatized, biuretized, dimerized (uretodione), trimerized (isocyanurate), adducted, carbodiimidized derivatives, etc .; and these Blocked isocyanates and the like blocked with alcohols, phenols, ε-caprolactam, oximes, active methylene compounds, etc., and one or more selected from these may be used. Kill. In addition, the above-mentioned (a3) component is a component different from the said (A2) component.

In the present invention, it is preferable that hexamethylene diisocyanate (HMDI) and / or a derivative thereof (hereinafter also referred to as “HMDIs”) is included as the polyisocyanate component (A2). 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). Moreover, the aspect in which a polyisocyanate component (A2) consists only of HMDI is also suitable. Moreover, as a derivative | guide_body, a biuret body and / or an isocyanurate body are 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-resistant protective property of the substrate can be enhanced.

The mixing of the polyol component (A1) and the polyisocyanate component (A2) is preferably 0.6 to 3.5 (more preferably 1 to 5) in terms of the NCO / OH equivalent ratio of the polyol component (A1) and the polyisocyanate component (A2). 2.5, more preferably 1.1 to 1.9). In such a case, it is excellent in curability and can form a uniform film with a desired thickness, and has a more excellent foaming property for a temperature rise due to a fire, etc., and forms a stable carbonized heat insulating layer. Thus, the heat resistance protection performance of the substrate can be enhanced. Furthermore, the formed film is excellent in durability (for example, waterproofness, water permeability, crack resistance, base followability, etc.) and can maintain the initial appearance (aesthetics) over a long period of time, and may be caused by fire or the like. The effect of the present invention can be sufficiently exerted for temperature rise 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), the component (a3) and the component (A2) are different from the component (A3). A compound (A3) having a nurate ring may also be included. The compound (A3) having an isocyanurate ring preferably reacts with the polyol component (A1) and / or the polyisocyanate component (A2) to form a film. For example, an alkoxysilyl group, a carboxyl group, a glycidyl group And isocyanuric acid derivatives having at least one reactive functional group such as In this case, what has an alkoxy silyl group, a glycidyl group, a carboxyl group, an amino group etc. should just be used as the said polyol component (A1) and / or the said polyisocyanate component (A2).

  The compounding amount of the compound (A3) having an isocyanurate ring is preferably 0.1 to 30 parts by weight (more than 100 parts by weight of the solid content of the polyol component (A1) and the polyisocyanate component (A2)). Preferably it is 0.5-20 weight part, More preferably, it is 1-15 weight part. In such a case, the effects of the present invention can be sufficiently exerted.

In this invention, the curing catalyst which accelerates | stimulates reaction of a polyol component (A1) and a polyisocyanate component (A2) can be used together. A curing catalyst is a substance having an action of promoting the curing by reaction of isocyanate groups. Examples of the curing catalyst include various types such as an amine catalyst, an organometallic catalyst, and an inorganic catalyst. For example, examples of the amine catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, hexamethylenediamine, a derivative thereof, and 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. These can be used by 1 type (s) or 2 or more types, and can also be mixed and used for a solvent. In the present invention, it is particularly preferable to include an organometallic catalyst. In this case, curing can be promoted and the curability of the film-forming component (A) can be enhanced, so that the effect of the present invention can be enhanced.

The cured film formed from the film forming component (A) has an exothermic peak in the differential thermal analysis method (DTA method), and the exothermic peak is in the 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, an excellent carbonized heat insulating layer can be formed, and the heat resistance protection of the substrate can be enhanced.

Although the action mechanism is not limited, for example, the cured film of the film-forming component (A) starts to soften as the temperature rises, and then a decomposition reaction such as urethane bonding 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 reaction can proceed efficiently in a state where the film is softened without much decomposition. Therefore, it is considered that the foamability is improved, and further, 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. Thereby, the flame retardance of a cured film can be improved, decomposition | disassembly at less than 200 degreeC can be suppressed, and it is thought that the effect of this invention can fully be exhibited.

In the present invention, the differential thermal analysis method for the cured film of the film forming component (A) is measured using a cured film containing the polyol component (A1) and the polyisocyanate component (A2) as a sample. The differential thermal analysis method is a measurement using a differential thermal analyzer (for example, “Differential Thermal Balance Thermo plus EVO2 TG-DTA Series” manufactured by Rigaku Corporation, etc.), and 3 ± 1 mg of a sample on a platinum sample pan. Measured by 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 a component 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 derivatives thereof, dicyandiamide and derivatives thereof, azobistetrasome and derivatives thereof, azodicarbonamide, urea and thiourea. 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). In addition, the foaming agent (B) of the present invention imparts a foaming action to the coating by a temperature rise during a fire or the like, and specifically, when the temperature of the coating surface is preferably 200 ° C. or higher. It gives a foaming action.

Examples of the carbonizing agent (C) 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 preferable in that they are excellent in dehydration cooling effect and carbonized heat insulation layer forming action. 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). In addition, the carbonizing agent (C) of this invention provides the effect | action which forms a carbonization heat insulation layer by carrying out dehydration carbonization with carbonization of the said film formation component (A) by the temperature rise at the time of a fire etc.

Examples of the flame retardant (D) include organic phosphorus 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 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 melamine acid, melamine polyphosphate, melam polyphosphate, melem polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, aluminum aluminum phosphate; and other inorganic compounds such as zinc borate and sodium borate It is done. These can be used alone or in combination of two or more. In the present invention, as the flame retardant (D), for example, melamine polyphosphate, melam polyphosphate, melamine polyphosphate / melam / melem double salt, or a compound compound of melamine / melam / melem polyphosphate and dimelam pyrosulfate, etc. It is preferable to contain at least one phosphorus compound selected from the group consisting of ammonium polyphosphate and these in combination. 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, shirasu, mica, quartz sand, quartzite powder, quartz powder, and barium sulfate. Etc. 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).

Furthermore, in this invention, in addition to the said component, a metal hydrate (F), a fiber (G), etc. can also be included. 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 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, still more preferably 0.3 to 8 μm, most preferably 0.4 to 3 μm). It 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 parts per 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, since the foaming property, in particular, the shrinkage of the carbonized heat insulation layer under high temperature can be suppressed and a stable carbonized heat insulation layer can be formed, the effect of the present invention can be enhanced. The average particle diameter is measured by a laser diffraction particle size distribution measuring device.

A fiber (G) can improve thick coating property and can suppress the crack of a film. In addition, the fiber (G) can make it difficult to cause sagging of the film when the temperature rises due to a fire or the like, and can increase the thermal conductivity inside the film. As a result, excellent foamability is exhibited, a uniform carbonized heat insulating layer can be formed, and the heat resistance protection performance of the substrate can be enhanced. Examples of such fibers (G) include acrylic fibers, acetate fibers, aramid fibers, copper ammonia fibers (cupra), nylon fibers, novoloid fibers, pulp fibers, viscose rayon, vinylidene fibers, polyester fibers, polyethylene fibers, Organic fiber such as polyvinyl chloride fiber, polyclar fiber, vorinic 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 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, the fiber (G) preferably contains an inorganic fiber, and among them, artificial mineral fibers such as rock wool fiber, slag wool fiber, glass fiber, and ceramic fiber are preferred. Thereby, the crack of a film can be suppressed further. Further, when the temperature rises due to a fire or the like, it is possible to make it difficult to cause sagging of the coating, and to further increase the thermal conductivity inside the coating. As a result, it is possible to form a carbonized heat insulation layer having uniform foaming ability even inside the coating (core part), having a more uniform and superior strength, and further improving the heat resistance protection performance of the substrate.

The size of the fiber (G) (fiber length and fiber diameter) may be set according to the performance of the coating material, the application base material, the application tool, etc., and the average fiber length is preferably 10 to 10%. The average fiber diameter is preferably in the range of 1000 μm (more preferably 15 to 800 μm, more preferably 20 to 600 μm), and preferably 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 coatability is increased, and it is difficult to cause cracking of the formed film, and when the temperature rises due to a fire or the like, it is difficult to cause sagging of the film. 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, further preferably 2 to 2 parts by weight) with respect to 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 (H). The high boiling point compound (H) is a liquid at 20 ° C. and a high boiling point liquid compound having a boiling point of 100 ° C. or higher (more preferably 150 ° C. or higher, more preferably 200 ° C. or higher). By including such a high boiling point compound (H), the dispersion stability and the like of powder components such as the component (B) to the component (G) can be enhanced. In addition, it is possible to form a good film with excellent adhesion, in particular, to improve the elasticity of the film and prevent cracking of the film. In addition, when the coating is exposed to high temperatures due to a fire or the like, it contributes to appropriate softening of the coating and further enhances foaming properties, suppresses the falling (peeling) of the formed carbonized thermal insulation layer, and the like. Heat protection performance can be improved.

The high boiling point compound (H) is not particularly limited as long as it satisfies the above conditions. 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, butyl benzyl phthalate; diethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, adipic acid Aliphatic dibasic acid esters such as dioctyl, diisononyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, diethyl sebacate, dibutyl sebacate, dihexyl sebacate, di-2-ethylhexyl sebacate Compound: Adipic acid polyester such as adipic acid-1,3 butylene glycol polyester, adipic acid-1,2 propylene glycol polyester; dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di maleate Maleic ester compounds such as 2-ethylhexyl, diisononyl maleate, diisodecyl maleate; triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, phosphorus Phosphoric acid ester compounds such as acid-2-ethylhexyldiphenyl;

Trimetic acid ester compounds such as tris-2-ethylhexyl trimellitate; 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 linseed oil; benzoic acid ester compounds such as benzoic glycol ester; 1-phenyl-1-xylylethane, 1-phenyl-1-ethyl Examples thereof include aromatic hydrocarbon compounds such as phenylethane, lactones such as γ-butyrolactone, mixtures of petroleum resins (aromatic hydrocarbon fraction polymer having 8 to 10 carbon atoms) and styrylxylene, and the like. These can be used alone or in combination of two or more.

In the present invention, the high-boiling compound (H) preferably contains at least one selected from a phthalate ester compound, an aliphatic dibasic acid ester compound, and a phosphate ester compound. It is preferable to contain 1 or more types chosen from 4-11 (more preferably 5-10, still more preferably 6-9) phthalic acid ester compounds and aliphatic dibasic acid ester compounds. Specific examples thereof include, for example, diisononyl phthalate and diisononyl adipate.

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 coating property is excellent, and the temperature rises due to a fire or the like, the foam has excellent foaming properties and maintains the heat resistance protection performance of the substrate. Can be fully demonstrated.

  Other additives may be used as long as they do not significantly inhibit the effects of the present invention. For example, pigments, wetting agents, plasticizers, lubricants, preservatives, antifungal agents, antialgae agents, antibacterial agents, and thickeners. , Leveling agents, dispersants, antifoaming agents, crosslinking agents, silane coupling agents, UV absorbers, light stabilizers, antioxidants, halogen scavengers, diluent 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 deterioration of the coating not only during normal times but also during a temperature rise due to a fire or the like, and it is possible to improve the properties of the carbonized heat insulating layer formed by the temperature rise. .

  The coating material of the present invention is preferably a two-pack type 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) (further, the metal hydrate (F), fiber (G), high Each of the boiling point compound (H) and the curing catalyst) may be mixed with at least one of the main agent and the curing agent, but in the present invention, it is preferably mixed with the main agent. Moreover, each component can also be added at the time of mixing of a main ingredient and a hardening | 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, doors and the like. Examples of applicable substrates include concrete, mortar, siding board, extruded board, gypsum board, perlite board, brick, plastic, wood, metal, steel frame (steel), glass, porcelain tile, and the like. These base materials may be those with a coating already formed on the surface, those with some base treatment (rust prevention treatment, flame retardant treatment, etc.), those with wallpaper attached, and the like.

  When the coating material of the present invention is applied to a substrate, for example, it may be applied in one or several steps using a coating tool such as a spray, a roller, a brush, or a trowel. It is preferable to apply so that the dry film thickness per step is preferably 400 μm or more (more preferably 500 to 5000 μm). Thereby, a thick film can be formed with few coating processes. The film thickness finally formed may be appropriately set depending on desired functionality, application site, and the like, but is preferably about 0.4 to 5 mm.

In this invention, in order to protect the film formed with the said coating | covering material, a finishing material layer can also be laminated | stacked further as needed. Such a finishing material layer is not particularly limited as long as the coating formed from the coating material foams when the temperature rises due to a fire or the like and does not hinder the formation of the carbonized heat insulating layer, A known finishing material can be laminated. Such a finishing material layer can be laminated by applying various top coating materials or by sticking various sheet materials. As the top coating material, for example, a coating material such as acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, epoxy resin, or vinyl acetate resin can be used. These can be used alone or in combination of two or more, and two or more coating materials can be laminated and applied. The top coat material may be applied by a known application method, and for example, a coating instrument such as a spray, a roller, or a brush can be used. Examples of the sheet material include a decorative film, a decorative sheet, a sheet building material, wallpaper, and the like. These may be attached via a known adhesive (adhesive) or the like.

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

The following were used as each raw material.

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

-Polyether polyol (a1)
(A1-1): Polyether polyol (ethylene oxide and propylene oxide polymer 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 (polymer of ethylene oxide and propylene oxide using glycerol as an initiator, number average molecular weight 7000, functional group number 3, hydroxyl value 24 mgKOH / g, terminal ethylene oxide addition)
(A1-3) Polyether polyol (ethylene oxide and propylene oxide polymer using glycerin as an initiator, number average molecular weight 6000, functional group number 3, hydroxyl value 28 mgKOH / g, terminal ethylene oxide addition)
(A1-4): Polyether polyol (ethylene oxide and propylene oxide polymer using propylene glycol as an initiator, number average molecular weight 5,100, functional group number 3, hydroxyl value 33 mgKOH / g, terminal ethylene oxide addition)
(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, terminal propylene oxide addition)
(A1-6): Polyether polyol (polymer with propylene oxide using glycerol 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): Ethylene trifluoride copolymer (chlorotrifluoroethylene-vinyl ether-hydroxyalkyl vinyl tathel copolymer, fluorine content 27 wt%, hydroxyl value 52 mg KOH / g, solid content 60 wt%, aromatic Contains hydrocarbon solvent)
(A2-2): Tetrafluoroethylene copolymer (tetrafluoroethylene-vinyl ether-hydroxyalkyl vinyl tathel copolymer, fluorine content 36 wt%, hydroxyl value 60 mg KOH / g, solid content 60 wt%, butyl acetate solvent Contains)
-Polyol compound having an isocyanurate ring (a3)
(A3-1) Isocyanuric acid tris (2hydroxyethyl) (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%)

-Foaming agent (B): Melamine-Carbonizing agent (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): Organometallic catalyst ・ Additive 1: Dispersant, antifoaming agent, etc. ・ Additive 2: Plasticizer, diluent solvent, etc.

(Coating materials 1 to 23)
According to the formulations shown in Tables 2 and 3, the main component was prepared by mixing (A1) component, (B) component to (I) component, and additives 1 and 2 by a conventional method. Subsequently, (A2) component was mixed and the coating materials 1-23 were obtained. In Tables 2 and 3, the mixing amount of the (B) component to the (I) component 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 (A) component.

(Examples 1 to 22, Comparative Example 1)
A coating material was sprayed on the entire surface of a steel plate (length 150 mm × width 70 mm × thickness 1.6 mm) that had been pre-rusted and coated (dry film thickness 1.5 mm), and cured at room temperature (25 ° C.) for 7 days. The following evaluation was 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 magnification when the surface of the test body was irradiated with radiant heat of 50 kW / m ² for 15 minutes, and the steel plate back surface temperature Was measured. Each evaluation standard is as follows. The results are shown in Tables 2 and 3.
(Foaming ratio)
AA: Foaming ratio over 35 times A: Foaming ratio over 25 times over 35 times or less B: Foaming ratio over 20 times over 25 times C: Foaming ratio over 15 times over 20 times D: Foaming ratio over 15 times (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: Over 550 ° C.

<Heat resistance evaluation 2>
Based on the ISO 5660-1 cone calorimeter method, using an electric heater (CONEIII, manufactured by Toyo Seiki Co., Ltd.), the foaming magnification when the radiant heat of 50 kW / m ² is radiated to the surface of the test body for 30 minutes, and the steel plate back surface temperature Was measured, and the denseness and ashing property were further evaluated. The evaluation criteria of the expansion ratio and the steel plate back surface temperature are the same as in the heat resistance evaluation 1 described above. The evaluation criteria for denseness and ashing properties are as follows. The results are shown in Tables 2 and 3.

(Denseness evaluation)
The test body for which the 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 were a four-level evaluation (excellent: A>B>C> D: inferior), with “A” indicating a high density and “D” indicating a low density.
(Ashing property evaluation)
In the 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 incinerated (white) portion was calculated. Evaluation criteria were set to a four-step evaluation (excellent: A>B>C> D: inferior), with “A” indicating less ashing and “D” indicating ashing progressed.

The covering materials 1 to 10 and 14 to 22 (Examples 1 to 10 and 14 to 22) are excellent in foamability in any of the heat resistance evaluation 1 and the heat resistance evaluation 2 (under a high temperature obtained by extending the heating test). It was possible to stably form a carbonized heat insulating layer, and further to suppress shrinkage of the carbonized heat insulating layer, and to exhibit sufficient heat protection performance. In particular, in the covering materials 14 to 22 (Examples 14 to 22), when the heating test is extended, the shrinkage of the carbonized heat insulation layer is sufficiently suppressed (the change in the expansion ratio is small), and the heat protection performance is further improved. 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 significant.

Next, in the heat resistance evaluations 1 and 2, in the coating materials 1 to 4, 7, 8, and 14 to 22 (Examples 1 to 4, 7, 8, and 14 to 22) that showed excellent foamability, the following evaluations were made. Carried out.
<Heat resistance evaluation 3>
(Evaluation of dropout prevention)
Install the test body horizontally so that the coating material is on the lower side, install a heater (heater temperature 680 ° C.) at a position 25 mm above the test body, and heat the test body with the heater. The steel plate temperature when it dropped out was measured. Evaluation was performed in the following four stages. The results are shown in Tables 2 and 3.
A: Drop-off temperature 250 ° C. or higher B: Drop-off temperature 220 ° C. or higher and lower than 250 ° C. C: Drop-off temperature 200 ° C. or higher and lower than 220 ° C. D: Drop-off temperature 200 ° C. or lower

Furthermore, the following evaluation was implemented in coating | covering materials 14-22 (Examples 14-22).
<Thickening evaluation 1>
A coating material is applied on the entire surface of a steel plate (150 mm long × 70 mm wide × 1.6 mm thick) coated in advance with a rust preventive film with a wet film thickness of 3 mm using a film applicator, 24 hours at room temperature (25 ° C.), and then 50 ° C. For 24 hours, the dry film thickness was measured, and the change in the 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-step evaluation (excellent: A>B>C> D: inferior), in which “A” was formed with a uniform film and “D” was cracked in the film. The results are shown in Table 4.

Claims (2)

The coating is a coating material that forms a carbonized thermal insulation layer by increasing the temperature,
The coating material includes a polyol component (A1) and a polyisocyanate component (A2) as a film forming component (A),
A coating material comprising a polyether polyol (a1) and a fluorine-containing polyol (a2) as the polyol component (A1). The covering material according to claim 1, comprising 0.1 to 30% by weight of the fluorine-containing polyol (a2) in terms of solid content with respect to the total amount of the polyol component (A1).