JP2019065259A - Covering material - Google Patents

Abstract

A coating material having excellent foamability and capable of maintaining the heat-resistant protective performance of a substrate is provided. The present invention relates to a covering material whose coating forms a carbonized heat insulating layer upon temperature rise, wherein the covering material contains a polyol component (a1) and a polyisocyanate component (a2) as binders (A). and the fluorine content of the film is 10-150 mg/kg. [Selection figure] None

Description

  The present invention relates to a novel coating material.

  For the purpose of protecting a base material such as steel, concrete, wood, synthetic resin and the like from fires, various coating materials are proposed which are foamed by temperature rise at the time of fire etc. to form a carbonized heat insulating layer. As such a covering material, what mixed a foaming agent, a carbonization agent, a flame retardant, etc. with synthetic resin is known. Such a coating material is often determined by the film thickness to be heat resistant protective performance, and in order to obtain the desired heat resistant protective performance, it is important to apply a uniform coating thickness. Among them, the choice 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 blended in a composition comprising a polyol component and a polyisocyanate component has been developed (for example, Patent Document 1).

Unexamined-Japanese-Patent No. 5-70540

However, in the case of Patent Document 1 above, the expansion ratio of the film at a 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 or shrinkage of the carbonized heat insulating layer (foamed layer) And the like, and there is still room for improvement to obtain the desired heat protection performance.
The present invention has been made in view of such problems, and it is an object of the present invention to provide a covering material capable of forming a stable carbonized heat insulation layer at the time of temperature rise and ensuring excellent heat protection performance. I assume.

  In order to solve such problems, the present inventors have included a polyol component and a polyisocyanate component for a coating material whose coating forms a carbonized heat insulating layer due to a temperature rise during a fire, etc., and the fluorine content of the coating By finding that the amount is a specific amount, it is found that the above problems can be solved and the heat resistance protective performance of the substrate can be enhanced, and the present invention has been accomplished.

That is, the present invention has the following features.
1. The coating is a coating material which forms a carbonized heat insulating layer by temperature rise,
The coating material contains a polyol component (a1) and a polyisocyanate component (a2) as a binder (A),
Coating material characterized in that the fluorine content of the film is 10 to 150 mg / kg.
2. A fluorine-containing polyol is included as the polyol component (a1). Coating material as described in.
3. Characterized by including a fluorine compound (B) (excluding a fluorine-containing polyol). Or 2. Coating material as described in.
4. 2. The fluorine compound (B) is a fluorine-containing resin. Coating material as described in.

The present invention is a coating material whose coating film forms a carbonized heat insulating layer by temperature rise, and the coating material contains a polyol component (a1) and a polyisocyanate component (a2) as a binder (A), and the film Since the fluorine content of is a specific range, it has excellent foamability when temperature rises due to fire etc., and suppresses carbonization and shrinkage of carbonized heat insulation layer to form a stable carbonized heat insulation layer, The heat protection of the substrate can be enhanced.

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

In the coating material of the present invention, the coating film forms a carbonized heat insulating layer by temperature rise (heating) due to a fire or the like, and the coating material contains a polyol component (a1) and a polyisocyanate component (a2) as a binder (A). ) As an essential component, and the fluorine content of the film is 10 to 150 mg / kg.

The polyol component (a1) and the polyisocyanate component (a2) of the present invention are components that react to form a film. The coating material of the present invention contains a polyol component (a1) and a polyisocyanate component (a2) as a binder (A), and the fluorine content of the film is 10 to 150 mg / kg (preferably 15 to 130 mg / kg, more preferably) Form a fluorine-containing coating of 20 to 110 mg / kg).

When the fluorine content in the film satisfies the above range, the temperature of the film increases (preferably, the film surface temperature is 200 ° C. or more, more preferably 250 ° C. or more) to have excellent foamability and the carbonized heat insulating layer By suppressing ashing, shrinkage and the like, a stable carbonized heat insulating layer can be formed, and the heat protection properties of the substrate can be enhanced. In addition, when the fluorine content in the film does not satisfy the lower limit, ashing of the carbonized heat insulating layer is accompanied by temperature increase of the carbonized heat insulating layer (specifically, when the surface temperature of the carbonized heat insulating layer exceeds 400 ° C.) There is a risk that the carbonized heat insulating layer formed may progress or shrink. On the other hand, when the fluorine content exceeds the upper limit, the foamability may be insufficient.

In the present invention, the fluorine content is a value measured by combustion ion chromatography. Specifically, the coating material of the present invention is coated on a release paper, and the coating dried in a standard state (air temperature 23 ° C., relative humidity 50%) is pulverized to collect 20 mg of the coating to obtain a sample. Then, using an automatic sample combustion apparatus ("AQF-100" manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the sample is heated under conditions of 1000 ° C. and 10 minutes under argon and oxygen atmosphere, and the amount of generated fluorine is It can obtain | require by quantifying using an ion chromatograph ("ICS-1600" Thermo Fisher Scientific Co., Ltd. product made).

The coating material which forms such a fluorine-containing film is obtained by the aspect of the following (1) and / or (2), for example.
(1) A fluorine-containing polyol is included as a polyol component (a1).
(2) The fluorine compound (B) (excluding the fluorine-containing polyol) is included.

As an aspect of the polyol component (a1) of said (1), a liquid is preferable and any aspect of a non-solvent type or a solvent type may be sufficient. The fluorine-containing polyol contained as such a polyol component (a1) is not particularly limited. For example, a fluorine-containing monomer such as a fluoroolefin monomer or a fluoroalkyl group-containing acrylic monomer, and a hydroxyl group-containing vinyl monomer It is obtained by copolymerizing with other polymerizable monomers as needed. Examples of the fluoroolefin monomer include perfluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like, vinyl fluoride, vinylidene fluoride and the like. Examples of the fluoroalkyl group-containing acrylic monomer include perfluoromethyl methacrylate, perfluoroisononyl methyl methacrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl 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 at least one selected from tetrafluoroethylene and chlorotrifluoroethylene, more preferably chlorotrifluoroethylene.

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

As other polymerizable monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic acid alkyl esters such as acrylates; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylamino (meth) acrylate, aminoethyl (meth) acrylate ) 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 vinyl toluene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate; and olefin monomers such as ethylene and propylene Etc., and one or two or more of these can be used if necessary.

The fluorine-containing polyol preferably has a hydroxyl value of 5 to 100 mg KOH / g (more preferably 10 to 80 mg KOH / g). By containing such a fluorine-containing polyol, the film can exhibit excellent foamability by temperature rise to form a carbonized heat insulating layer, and ashing and shrinkage can be sufficiently suppressed even in a high temperature atmosphere. The heat protection performance of the

  The content of the fluorine-containing polyol is such that the fluorine content in the film formed by the coating material is 10 to 150 mg / kg (preferably 15 to 130 mg / kg, more preferably 20 to 110 mg / kg). Just do it. Specifically, it is preferably 0.1 to 30 parts by weight (more preferably 1 to 10 parts by weight) in terms of solid content with respect to the total amount of the polyol component (a1).

The fluorine compound (B) (excluding the fluorine-containing polyol) in the above (2) is not particularly limited as long as it is a fluorine-containing component, and, for example, a fluorine-containing resin, various fluorine-containing additives and the like can be used. In the present invention, a fluorine-containing resin is preferred.

As the fluorine-containing resin, for example, homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and the like; fluorine-containing monomers; And copolymers thereof with, for example, (meth) acrylic acid alkyl esters, olefin monomers and the like.

As such fluorine-containing resin, specifically, homopolymers such as polyvinyl fluoride (PVF), polyvinylidene fluoride, polytrifluoroethylene, polychlorotrifluoroethylene, polytetrafluoroethylene and the like; tetrafluoroethylene -Copolymers such as hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and the like can be exemplified. The fluorine-containing resins can be used alone or in combination of two or more. The fluorine-containing resin may be a solvent-soluble resin, a solvent-based resin such as a non-aqueous dispersion resin, or a powder resin, but in the present invention, the solvent-soluble resin and / or powder resin Is preferred.

Furthermore, as a fluorine compound (B) of this invention, acrylic compound fluorine-containing resin is suitable. When the fluorine compound (B) has an acrylic (composite) portion, the compatibility and dispersibility with the binder (A) can be enhanced, and the effect of the present invention can be enhanced. As such an acrylic compound fluorine-containing resin, for example, a mixture and / or a reaction product of an acrylic resin and a fluorine-containing resin can be used, and in particular, the powdery acrylic compound polytetrafluoroethylene is dispersed in a film. And the effects of the invention can be further enhanced.

The above acrylic resin is a resin containing a (meth) acrylic acid alkyl ester as a constituent component (except for a fluorine-containing resin), for example, a (meth) acrylic acid alkyl ester and the above-mentioned other polymerizable monomers as necessary. A copolymer obtained by polymerizing (except for (meth) acrylic acid alkyl ester, for example, an aromatic vinyl monomer such as styrene, a vinyl ester such as vinyl acetate monomer, etc.) can be used. The content of the acrylic resin in the acrylic compound fluorine-containing resin is preferably 10 to 90% by weight (more preferably 20 to 80% by weight). In such a case, excellent dispersibility can be exhibited, and the effects of the present invention can be sufficiently exhibited.

  The method for producing the acrylic composite polytetrafluoroethylene is not particularly limited as long as it is a known method, and for example, a method of mixing a polytetrafluoroethylene particle dispersion and an acrylic resin dispersion and obtaining them by coagulation or spray drying, A method of polymerizing the above (meth) acrylic acid alkyl ester or the like in the presence of a polytetrafluoroethylene particle dispersion, and coagulating or spray-drying it, a polytetrafluoroethylene particle dispersion and a latex mixed with an acrylic resin dispersion The method etc. which are obtained by polymerizing the said (meth) acrylic-acid alkylester etc. below, and coagulating or spray-drying are mentioned.

The content of the fluorine compound (B) is such that the fluorine content in the film formed by the coating material is 10 to 150 mg / kg (preferably 15 to 130 mg / kg, more preferably 20 to 110 mg / kg) It should just be mix | blended. Specifically, it is preferably 0.1 to 30 parts by weight (more preferably 0.3 to 20 parts by weight, still more preferably 1 to 10 parts by weight) based on 100 parts by weight of the solid content of the binder (A). ). Thereby, the effects of the present invention can be sufficiently exhibited.

  The coating material which forms the fluorine-containing film of the present invention is preferably an embodiment including only the above (1), an embodiment including only the above (2), or an embodiment including the above (1) and the above (2). Thereby, the film exhibits excellent foamability by temperature rise to form a carbonized heat insulation layer, and it is possible to suppress ashing and shrinkage of the carbonized heat insulation layer even in a high temperature atmosphere, and improve the heat protection property of the substrate. be able to.

As the polyol component (a1) of the present invention, in addition to the above-mentioned fluorine-containing polyol, for example, polyether polyol, polyester polyol, acrylic polyol, epoxy-containing polyol, silicone-containing polyol, castor oil, castor oil modified polyol, polycarbonate polyol, polylactone A polyol, a polybutadiene polyol, a polypentadiene polyol etc. are mentioned, 1 type (s) or 2 or more types selected from these can be used.

In the present invention, it is preferable to include a polyether polyol as the polyol component (a1). The molecular weight of the polyether polyol is preferably 1000 or more (more preferably 3000 to 20000, still more preferably 5000 to 18000, particularly preferably 6000 to 15000, and most preferably 6500 to 12000). By including such a polyol component, it is possible to enhance the foamability and form an excellent carbonized heat insulating layer by raising the temperature of the film (preferably the upper surface temperature of the film is 200 ° C. or more, more preferably 250 ° C.) The heat resistance protection performance of the substrate can be further 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 polyether polyol is obtained, for example, by addition polymerization of polyhydric alcohol such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol derivative, sorbitol, neopentyl glycol and the like and alkylene oxide such as ethylene oxide and propylene oxide. It is a thing. In the present invention, a polymer obtained by the addition polymerization of the above-mentioned polyhydric alcohol and ethylene oxide and / or propylene oxide is preferred, and one having ethylene oxide and / or propylene oxide added at its terminal is more preferred. is there. Furthermore, it is preferable that the functional group which has an active hydrogen atom contains 3 or more (3 or more functional group) polyether polyol as said polyether polyol. In this case, the effect of the present invention can be easily obtained because the film can be stably formed with excellent curability. As a functional group having an active hydrogen atom, a hydroxyl group is preferred.

The polyether polyol preferably has a hydroxyl value of 3 to 150 mg KOH / g (more preferably 5 to 100 mg KOH / g, still more preferably 7 to 40 mg KOH / g, most preferably 10 to 30 mg KOH / g). . By using such a polyol component, it is possible to exhibit a further excellent foamability and to improve the heat protection performance of the substrate.

The content of the polyether polyol is preferably 70% by weight or more (more preferably 90% by weight or more, still more preferably 95% by weight or more) with respect to the total amount of the polyol component (a1). The aspect which a polyol component (a1) consists only of said polyether polyol is also suitable, and, in this case, this invention coating material is suitably obtained by the aspect containing the fluorine compound (B) of said (2).

Examples of the polyisocyanate component (a2) of the present invention include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone Diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc., or allophanatized, biuretized, dimerized (uretdioned), trimerized (isocyanurated), adducted, carbodiimidated derivatives, etc .; Blocked isocyanates etc. which are blocked with alcohols, phenols, ε-caprolactam, oximes, active methylene compounds etc., and one or more selected from these may be used Kill.

In the present invention, as the polyisocyanate component (a2), it is preferable to contain hexamethylene diisocyanate (HMDI) and / or a derivative thereof (hereinafter also referred to as “HMDIs”). The content of the above 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 which a polyisocyanate component (a2) consists only of HMDIs is also suitable. Moreover, as a derivative, a biuret body and / or an isocyanurate body is suitable. In such a case, the curability of the formed film is excellent, and when the temperature rises, the foamability can be further enhanced, and the heat resistance protection 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 6) as the NCO / OH equivalent ratio of the polyol component (a1) and the polyisocyanate component (a2). The ratio is preferably 2.5, more preferably 1.1 to 1.9). In such a case, it is possible to form a uniform film with a desired thickness and excellent curability, and to form a stable carbonized heat insulation layer having more excellent foamability for temperature rise due to fire etc. Thus, the heat resistance protection performance of the substrate can be enhanced.

In the present invention, a curing catalyst that promotes the reaction of the polyol component (a1) and the polyisocyanate component (a2) can be used in combination. The curing catalyst is a substance having an action to accelerate the reaction and curing of the isocyanate group. Examples of the curing catalyst include various catalysts such as amine catalysts, organometallic catalysts, and inorganic catalysts. For example, as the amine catalyst, ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, and hexamethylenediamine or a derivative thereof or a mixture thereof with a solvent, and the like can be mentioned. Examples of the organic metal catalyst include organic metal compounds such as dibutyltin dilaurate and dibutyltin diacetate; and organic metal salts such as potassium acetate, zinc stearate, lead stearate, aluminum stearate and tin octylate. As an inorganic type catalyst, a tin chloride etc. are mentioned, for example. These may be used alone or in combination of two or more, and may be used in combination with a solvent. In the present invention, it is particularly preferable to include an organometallic catalyst. In this case, the curing can be promoted and the curability of the film-forming component (A) can be enhanced, and the effects of the present invention can be enhanced.

Furthermore, the covering material of the present invention can contain, for example, a foaming agent (C), a carbonizing agent (D), a flame retardant (E), a filler (F) and the like.

Examples of the foaming agent (C) include melamine and derivatives thereof, dicyandiamide and derivatives thereof, azobistetrasome and derivatives thereof, azodicarbonamide, urea, thiourea and the like. These can be used alone or in combination of two or more. The content of the foaming agent (C) 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 binder (A). Incidentally, the foaming agent (C) of the present invention imparts a foaming action to the film by temperature rise at the time of fire etc. Specifically, when the temperature of the film surface is preferably 200 ° C. or more It imparts an effervescent action.

Examples of the carbonizing agent (D) 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, in particular, pentaerythritol and dipentaerythritol are preferable in that they are excellent in the dehydration cooling effect and the carbonized heat insulating layer forming action. The content of the carbonizing agent (D) 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 binder (A). In addition, the carbonization agent (D) of this invention provides the effect | action which forms a carbonization heat insulation layer by dewatering-carbonizing with the carbonization of the said binder (A) by temperature rise at the time of a fire etc.

Examples of the flame retardant (E) include organophosphorus compounds such as tricresyl phosphate and diphenyl cresyl phosphate; chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin and fatty acid pentachloride Chlorinated compounds such as ester, perchloropentacyclodecane, chlorinated naphthalene and tetrachlorophthalic anhydride; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, phosphorus Phosphoric compounds such as melamine acid phosphate, melamine polyphosphate, melamine polyphosphate, melem polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, aluminum polyphosphate, etc .; and other inorganic compounds such as zinc borate and sodium borate Be These can be used alone or in combination of two or more. In the present invention, it is preferable to contain a phosphorus compound as the flame retardant (E). The content of the flame retardant (E) 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 binder (A).

As the filler (F), for example, talc, calcium carbonate, sodium carbonate, aluminum oxide (alumina), titanium oxide, zinc oxide, silica, clay, clay, clay, shirasu, mica, silica sand, silica powder, quartz powder, barium sulfate Etc. These can be used alone or in combination of two or more. The content of the filler (F) 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 binder (A).

Furthermore, in the present invention, metal hydrate (G) can be included in addition to the above components. The metal hydrate (G) exhibits endothermic property due to dehydration reaction or the like when the temperature rises, and is different from the filler (F). As such metal hydrate (G), aluminum hydroxide, magnesium hydroxide etc. are mentioned, for example. These can be used alone or in combination of two or more. The average particle size of the metal hydrate (G) 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 (G) is preferably 1 to 200 parts by weight (more preferably 10 to 100 parts by weight, still more preferably 25 to 5 parts by weight) with respect to 100 parts by weight of the solid content of the binder (A). 80 parts by weight).

In the present invention, the filler (F) and the metal hydrate (G) are preferably used in combination, and in this case, the filler (F) and the metal hydrate (G) have a weight ratio of 1: 9 to 9: 1. It is preferable to set (more preferably 2: 8 to 8: 2). In this case, the foamability, in particular, the shrinkage and the like of the carbonized heat insulating layer under high temperature can be suppressed, and a stable carbonized heat insulating layer can be formed, so the effect of the present invention can be enhanced. The average particle size is measured by a laser diffraction type particle size distribution measuring apparatus.

  In addition, any additive may be used as long as it does not significantly inhibit the effects of the present invention. Examples include pigments, fibers, wetting agents, plasticizers, lubricants, preservatives, fungicides, algaecides, antibacterial agents, and the like. There may be mentioned tackifiers, leveling agents, dispersants, antifoaming agents, crosslinking agents, silane coupling agents, UV absorbers, antioxidants, halogen scavengers, dilution solvents and the like.

Among them, 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, deterioration of the 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 enhanced. .

  The coating material of the present invention is preferably a two-component coating material having a main agent containing the above-mentioned polyol component (a1) and a curing agent containing the above-mentioned polyisocyanate component (a2). That is, at the time of distribution, the main agent and the curing agent may be stored in separate packages, and they may be mixed at the time of use (at the time of application). In this case, the fluorine compound (B), the blowing agent (C), the carbonization agent (D), the flame retardant (E), and the filler (F) (further, the metal hydrate (G)) 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 preferable to mix with the main agent. Moreover, each component can also be added at the time of mixing of a main ingredient and a hardening agent.

  The covering material of the present invention is suitable as a foamable fireproof covering material applied to the surface covering of structures such as buildings and civil engineering structures. Specifically, it can be applied to various substrates such as walls, columns, floors, beams, roofs, stairs, ceilings, and doors. Examples of applicable substrates include concrete, mortar, siding board, extruded plate, gypsum board, perlite plate, brick, plastic, wood, metal, steel frame (steel material), glass, porcelain tile and the like. These substrates may be those on which a film has already been formed, those on which some surface treatment (anticorrosion treatment, flame retardant treatment, etc.) has been applied, those on which wallpaper has been affixed, etc.

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

  In the present invention, in order to protect the film formed by the above-mentioned coating material, an overcoating material can also be applied if necessary. Such a top coat material can be formed by applying a known coating material. As an upper-coating material, coating materials, such as an acrylic resin type, a urethane resin type, an acrylic silicone resin type, a fluorine resin type, can be used, for example. The application of the top coat material may be performed according to a known application method, and for example, a paint, such as a spray, a roller, or a brush can be used.

  The following examples illustrate the features of the present invention more clearly. However, the present invention is not limited to this range.

(Covering materials 1 to 27)
According to the composition shown in Tables 1 and 2, the main agent was prepared by mixing the (a1) component, the (B) component to the (G) component, the catalyst and the additive by a conventional method. Subsequently, the (a2) component was mixed to obtain covering materials 1 to 27. In addition, the following were used as a raw material.

・ Binder (A)
Polyol component (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 mg KOH / 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 mg KOH / 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 mg KOH / g, addition of terminal ethylene oxide)
(A1-4): Polyether polyol (Polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight 5100, functional group number 3, hydroxyl value 33 mg KOH / 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 mg KOH / g, addition of terminal propylene oxide)
(A1-6): Polyether polyol (polymer with propylene oxide using propylene glycol as an initiator, number average molecular weight 4000, functional group number 2, hydroxyl value 28 mg KOH / g, terminal ethylene oxide addition)
(A1-7): Polyether polyol (polymer with propylene oxide using glycerin as an initiator, number average molecular weight 700, functional group number 3, hydroxyl value 225 mg KOH / g, terminal propylene oxide addition)
(A1-8): Fluorine-containing polyol (chlorotrifluoroethylene-vinyl ether-hydroxyalkyl vinyl ether, hydroxyl value 52 mg KOH / g, solid content 60 wt%, xylene solvent content)

Polyisocyanate component (a2)
(A2-1) biuret type hexamethylene diisocyanate (a2-2) isocyanurate type hexamethylene diisocyanate

-Fluorine compound (B): Fluorine-containing resin (acrylic composite polytetrafluoroethylene)

-Blowing agent (C): Melamine-Carbonization agent (D): Dipentaerythritol-Flame retardant (E): Ammonium polyphosphate-Filler (F): Titanium oxide-Metal hydrate (G): Aluminum hydroxide (A) Average particle size: 1 μm)
-Curing catalyst: Organometallic catalyst-Additive 1: Dispersant, antifoaming agent, etc.-Additive 2: Plasticizer, dilution solvent

(Test Examples 1 to 27)
A coating material was applied by spray (dry film thickness 1.5 mm) to the entire surface of a steel plate (150 mm long × 70 mm wide × 1.6 mm thick) which had been previously anticorrosion coated and dried for 7 days at normal temperature (25 ° C.) The following evaluations were carried out using the sample as a test body.
<Curable evaluation>
The curability (presence or absence of tack) of the formed film was evaluated by a finger touch test. Evaluation criteria are as follows.
A: There is no tack, good curing B: Some tack remains C: Some tack remains D: Poor curing

<Heat resistance evaluation 1>
Based on the ISO 5660-1 corn calorimeter method, using an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.), the expansion ratio when the radiant heat of 50 kW / m ² is radiated for 15 minutes on the surface of the test body, and the steel plate back surface temperature Was measured. Each evaluation standard is as follows. Also, the results are shown in Table 1.
(Expansion ratio)
AA: Foaming ratio of 35 or more A: Foaming ratio of 25 or more and 35 or less B: Foaming ratio of 20 or more and 25 or less C: Foaming ratio of 10 or more and 20 or less D: Foaming ratio of 10 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 corn calorimeter method, using an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.), the expansion ratio when radiating heat of 50 kW / m ² for 30 minutes to the surface of the test body, and the back surface temperature of the steel sheet Were measured, and the compactness and ashability were further evaluated. Evaluation criteria for the expansion ratio and the back surface temperature of the steel sheet are the same as in the above heat resistance evaluation 1. The compactness evaluation and the ashing evaluation criteria are as follows. Also, the results are shown in Table 1

(Evaluation of density)
The test body for which the expansion ratio was measured was cut, and the compactness of the carbonized heat insulating layer in the cross section was visually confirmed. The evaluation criteria were a four-step evaluation (A: B> C: D: inferior) in which those with high density are “A” and those with low density are “D”.
(Incineration evaluation)
In the heat resistance evaluation 2 above, 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 four-stage evaluations (A: B>C> D: inferior) in which those with low ashing were "A" and those in which ashing progressed were "D".

Test Examples 1 to 25 are excellent in foamability and stably form a carbonized heat insulating layer in any of heat resistance evaluation 1 and heat resistance evaluation 2 (under high temperature extended heating test), and further a carbonized heat insulation layer It was possible to suppress the shrinkage of the rubber and to exhibit sufficient heat resistance protection performance. In particular, in the test examples 10 and 25, when the heating test was extended, the shrinkage of the carbonized heat insulating layer was sufficiently suppressed (the change in the expansion ratio was small), and it was possible to exhibit further excellent heat protection performance. . On the other hand, in Test Example 26, in the heat resistance evaluation 2 (under the high temperature where the heating test was extended), the incineration of the carbonized layer proceeded, and the compactness was low and insufficient. Furthermore, in Test Example 27, the foamability was insufficient, and furthermore, when the heating test was extended, the shrinkage of the carbonized heat insulating layer was remarkable.

Claims (4)

The coating is a coating material which forms a carbonized heat insulating layer by temperature rise,
The coating material contains a polyol component (a1) and a polyisocyanate component (a2) as a binder (A),
Coating material characterized in that the fluorine content of the film is 10 to 150 mg / kg.   The coating material according to claim 1, comprising a fluorine-containing polyol as the polyol component (a1). The coating material according to claim 1 or 2, comprising a fluorine compound (B) (excluding a fluorine-containing polyol). The coating material according to claim 3, wherein the fluorine compound (B) is a fluorine-containing resin.