JP7288379B2 - Repair material and repair method - Google Patents

Description

The present invention relates to a novel repair material and repair method.

BACKGROUND ART Conventionally, various coating materials have been proposed that foam and form a carbonized heat insulating layer due to a temperature rise in the event of a fire for the purpose of protecting base materials such as steel, concrete, wood and synthetic resin from fire. As such a coating material, a synthetic resin compounded with a heat-resistant powder or the like is known. Such coatings are applied to the surface of the substrate to be protected to form a thermally protective coating. Furthermore, the surface of such a coating may be provided with a decorative coating or the like for the purpose of improving aesthetic appearance.

However, in the above-mentioned coating, if defects such as swelling, peeling, cracking, chipping, etc. occur due to various conditions during or after coating formation (construction conditions, environmental conditions, etc.), or physical damage, etc. In some cases, the coating needs to be repaired. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-136288) describes a specific repair method using an undercoat paint, a thermally foamable paint, or the like.

JP 2011-136288 A

However, in the repair method such as the above-mentioned patent document, it is necessary to apply the foaming paint to the concave part of the film to be repaired multiple times, and it takes a certain amount of labor and time to complete the repair, and the finish is poor. Sometimes it was worse.

The present invention has been made in view of the above points, and an object of the present invention is to provide a repair material that is excellent in thick coating properties and finish properties.

In order to solve such problems, the present inventors, as a result of intensive studies, have found a repairing agent containing a resin component (A) containing a polyol component and a polyisocyanate component, a powder component (B), and a high boiling point compound (C). I came up with the material and completed the present invention.

That is, the present invention has the following features.
1. A repair material for a film having heat-resistant protection,
The repair material has a coating that forms a carbonized heat insulating layer when the temperature rises,
The repair material contains a resin component (A), a powder component (B), and a high boiling point compound (C), and has a heating residue of 90% by weight or more,
The resin component (A) contains a polyol component and a polyisocyanate component,
The polyol component contains a polyether polyol having a molecular weight of 1000 or more,
The repair material , wherein the high boiling point compound (C) has a boiling point of 150° C. or higher .
2. 1. To the part to be repaired of the film having heat-resistant protective properties, 1. A method for repairing a film having heat-resistant protective properties, characterized by applying the repair material according to 1.

The repairing material of the present invention contains a specific resin component (A), a powder component (B), and a high boiling point compound (C), and has a heating residue of 90% by weight or more, so that thick coating and finish are obtained. Excellent for In addition, the formed film has excellent foamability and heat-resistant protection performance when the temperature rises due to fire or the like. Such a repair material can be suitably used as a repair material (filler, putty material, sealing material, etc.) used for repairing a film having heat-resistant protective properties (hereinafter also referred to as "heat-resistant protective film"). .

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

(repair material)
The repair material of the present invention contains a resin component (A), a powder component (B), and a high boiling point compound (C), and the coating thereof forms a carbonized heat insulating layer when the temperature is raised (heated) by a fire or the like. . The present invention is characterized in that the heating residue of the repair material is 90% by weight or more (preferably 90 to 100% by weight, more preferably 92 to 98% by weight). When the heat residue of the repair material satisfies the above range, it is excellent in thick coating properties and finishing properties, and can be efficiently applied to the portion to be repaired with a heat-resistant protective film. If the thickness is less than the above lower limit, excessive recoating or the like is required to obtain a desired film thickness, which is troublesome. In addition, there is a possibility that a sufficient film thickness cannot be secured.
The heating residue of the repair material is the value measured by the method of JIS K 5601-1-2, the heating temperature is 105° C., and the heating time is 60 minutes). In the present invention, "α to β" has the same meaning as "more than or equal to α and less than or equal to β".

In the present invention, by applying a repair material that satisfies the range of the heating residue to the portion to be repaired of the heat-resistant protective coating, the repair can be performed efficiently. In addition, the coating formed from the repair material exhibits excellent foaming properties similar to the heat-resistant protective coating when the temperature rises due to a fire or the like, and can form a carbonized heat insulating layer. Thereby, the heat-resistant protective performance of the substrate can be maintained without impairing the performance of the heat-resistant protective film.

Furthermore, the viscosity of the repair material is preferably 30 to 200 Pa·s (more preferably 40 to 180 Pa·s, still more preferably 50 to 150 Pa·s). When the viscosity of the repair material satisfies the above range, sagging can be suppressed, the thick coating property and finish property can be excellent, and the above effects can be enhanced. The viscosity of the repair material is the viscosity at 20 rpm measured with a BH viscometer at a temperature of 23 ° C immediately after preparing the repair material (in the case of a two-component type, after mixing the main agent and the curing agent) guideline value).

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

The polyol component (A1) of the present invention contains a polyether polyol (a1) and has a molecular weight of 1000 or more (preferably 3000 or more and 20000 or less, more preferably 5000 or more and 18000 or less, still more preferably 6000 or more and 15000 or less, most preferably is 6500 or more and 12000 or less). By using such a polyol component (A1), the temperature rise of the film (preferably, the surface temperature of the film is 200°C or higher, more preferably 250°C or higher) provides excellent foamability and heat resistance of the substrate. Protection performance can be improved. In the present invention, the molecular weight of the polyol component is the number average molecular weight (Mn), which is the so-called polystyrene equivalent molecular weight determined by gel permeation chromatography using a polystyrene polymer as a reference.

The polyether polyol (a1) is, for example, addition polymerization of polyhydric alcohols such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol derivatives, sorbitol, neopentyl glycol, and alkylene oxides such as ethylene oxide and propylene oxide. It is obtained by In the present invention, polymers obtained by addition polymerization of the above polyhydric alcohols and ethylene oxide and/or propylene oxide are preferred, and polymers having ethylene oxide and/or propylene oxide added to the ends are more preferred. be. Furthermore, it is preferable that the above polyether polyol contains a polyether polyol having 3 or more functional groups having active hydrogen atoms (3 or more functional groups). In this case, the effect of the present invention can be easily obtained because the curability is excellent and the film can be stably formed. A hydroxyl group is suitable as the functional group having an active hydrogen atom.

Such a polyether polyol (a1) preferably has a hydroxyl value of 3 to 150 mgKOH/g (more preferably 5 to 100 mgKOH/g, still more preferably 7 to 40 mgKOH/g, most preferably 10 to 30 mgKOH/g). is. By using such a polyol component (a1), even better foamability can be exhibited, and the heat-resistant protection performance of the substrate can be enhanced.

In addition, the content of the polyether polyol (a1) is 50% by weight or more (more preferably 60 to 99% by weight, still more preferably 70 to 98% by weight) relative to the total amount of the polyol component (A1). is preferred.

In the present invention, the polyol component (A1) preferably contains a fluorine-containing polyol (a2). As a result, the temperature rise of the coating (preferably the coating surface temperature is 200 ° C. or higher, more preferably 250 ° C. or higher) provides excellent foamability and suppresses ashing, shrinkage, etc. of the carbonized heat insulating layer to stabilize it. A carbonized heat-insulating layer can be formed to enhance the heat-resistant protection of the substrate.

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

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

Such a fluorine-containing polyol (a2) has a fluorine content of 10 to 50% by weight (more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight) in the solid content of the fluorine-containing polyol (a2). ) is preferred. Also, the hydroxyl value is preferably 5 to 100 mgKOH/g (more preferably 10 to 80 mgKOH/g). Furthermore, the molecular weight [number average molecular weight (Mn)] is preferably 5,000 to 100,000 (more preferably 8,000 to 60,000). By including such a fluorine-containing polyol (a2), when the temperature rises due to a fire, etc., the coating exhibits excellent foamability and forms a carbonized heat insulating layer, suppressing ashing and shrinkage even in a high-temperature atmosphere. can be used, and the heat-resistant protective performance of the base material can be enhanced.

The content of the fluorine-containing polyol (a2) is preferably 0.1 to 30% by weight (more preferably 0.5 to 20% by weight, more preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight). By satisfying this range, the effects of the present invention can be sufficiently exhibited.

（式１）
例えば、イソシアヌル酸トリス（ヒドロキシアルキル）エステル等が使用できる。イソシアヌル酸トリス（ヒドロキシアルキル）エステルとしては、例えば、イソシアヌル酸トリス（２ヒドロキシエチル）、イソシアヌル酸トリス（２ヒドロキシプロピル）、イソシアヌル酸トリス（２ヒドロキシブチル）、イソシアヌル酸トリス（２,３ジヒドロキシプロピル）等のイソシアヌレート環と水酸基を有するアルキルエステルが挙げられる。 Furthermore, in the present invention, it is preferable that the polyol compound (a3) having an isocyanurate ring is included as the 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 and the like can be used. Examples of tris(hydroxyalkyl) isocyanurate include tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxypropyl) isocyanurate, tris(2-hydroxybutyl) isocyanurate, and tris(2,3-dihydroxypropyl) isocyanurate. and alkyl esters having an isocyanurate ring and a hydroxyl group.

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, etc. is reacted during the production of an acrylic polyol. can be obtained by For the reaction here, for example, a combination of a polymerizable unsaturated double bond and a vinyl group, an acryloyl group, a thiol group, an alkoxysilyl group, a glycidyl group and a carboxyl group, an amino group and a glycidyl group, or the like may be used.

The polyol compound (a3) having an isocyanurate ring preferably accounts for 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 resin component (A) can be further enhanced, and a stable carbonized heat insulating layer can be formed when the temperature rises due to fire or the like. Especially at high temperatures, it has excellent adhesion to the heat-resistant protective film and the substrate, and can suppress detachment of the carbonized heat-insulating layer.

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

As the polyol component (A1), for example, one that is liquid at 20° C. can be used. ) is preferred. This makes it easier to obtain the effects of the present invention. The viscosity of the polyol component is the viscosity at 20 rpm (point value at 5th rotation) measured with a BH type viscometer at a temperature of 23°C.

Examples of the polyisocyanate component (A2) that forms a film by reacting with the polyol composition include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, and xylylene diisocyanate (XDI). , hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc., or allophanate, biuret, dimerization (uretdione formation), trimerization (isocyanurate formation), adduct formation, Carbodiimidated derivatives, etc.; can be used. The component (a3) described above is a different component from the component (A2) described above.

In the present invention, the polyisocyanate component (A2) preferably contains hexamethylene diisocyanate (HMDI) and/or derivatives 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) relative to the total amount of the polyisocyanate component (A2). Moreover, the aspect from which a polyisocyanate component (A2) consists only of HMDIs is also suitable. Moreover, as the derivative, biuret and/or isocyanurate are preferable. 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.

In mixing the polyol component (A1) and the polyisocyanate component (A2), the NCO/OH equivalent ratio of the polyol component (A1) and the polyisocyanate component (A2) is preferably 0.6 to 3.5 (more preferably 1 to 3.0, more preferably 1.1 to 2.5). In such a case, it has excellent curability and can form a uniform coating with a desired thickness, and has excellent foamability in the event of a temperature rise due to a fire, etc., and forms a stable carbonized heat insulating layer. can enhance the heat-resistant protection performance of the base material. Furthermore, the formed film has excellent durability (for example, waterproofness, water permeability resistance, crack resistance, substrate conformability, etc.), and can maintain the initial appearance (aesthetics) for a long period of time. The effects of the present invention can be sufficiently exhibited for temperature rise and the like.

In the present invention, a curing catalyst that accelerates the reaction between the polyol component (A1) and the polyisocyanate component (A2) can be used in combination. A curing catalyst is a substance that has the effect of accelerating curing by reacting isocyanate groups. Examples of curing catalysts include various types such as amine catalysts, organometallic catalysts, and inorganic catalysts. For example, amine-based catalysts include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, and hexamethylenediamine or their derivatives or mixtures with solvents. Examples of organometallic catalysts include organometallic compounds such as dibutyltin dilaurate and dibutyltin diacetate; and organometallic salts such as potassium acetate, zinc stearate, calcium stearate, lead stearate, aluminum stearate and tin octylate. Tin chloride etc. are mentioned as an inorganic system catalyst. These can be used alone or in combination of two or more, and can also be used by mixing with a solvent. In the present invention, it is particularly preferred to contain an organometallic catalyst. In this case, curing can be accelerated and the curability of the resin component (A) can be enhanced, thereby enhancing the effects of the present invention.

Further, the repair material of the present invention is characterized by containing a powder component (B) as a component different from the resin component (A). The powder component (B) preferably contains, for example, a foaming agent (b1), a carbonizing agent (b2), a flame retardant (b3), a filler (b4), and the like. As a result, when the temperature rises due to a fire or the like, it exhibits excellent foamability, forms a good carbonized heat insulating layer, exhibits heat protection performance, and can enhance the heat protection performance of the base material.

The foaming agent (b1) imparts a foaming effect to the coating when the temperature rises in the event of a fire or the like. It is. Examples of such foaming agents (b1) include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, thiourea, expandable graphite and the like. These can be used singly or in combination of two or more. The content of the foaming agent (b1) is preferably 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) per 100 parts by weight of the solid content of the resin component (A).

The carbonizing agent (b2) of the present invention imparts an effect of forming a carbonized heat insulating layer by carbonizing the resin component (A) and dehydrating and carbonizing the resin component (A) when the temperature rises in the event of a fire or the like. Examples of such carbonizing agents (b3) include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein. These can be used singly or in combination of two or more. In the present invention, pentaerythritol and dipentaerythritol are particularly preferred because they are excellent in dehydration cooling effect and carbonization heat insulating layer forming effect. The content of the carbonizing agent (b2) is preferably 10 to 200 parts by weight (more preferably 20 to 120 parts by weight) per 100 parts by weight of the solid content of the resin component (A).

Flame retardants (b3) include, for example, organic phosphorus compounds such as tricresyl phosphate and diphenyl cresyl phosphate; Chlorine compounds such as esters, perchloropentacyclodecane, chlorinated naphthalene, 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, and aluminum polyphosphate; and inorganic compounds such as zinc borate and sodium borate. be done. These can be used singly or in combination of two or more. In the present invention, examples of the flame retardant (b4) include melamine polyphosphate, melam polyphosphate, melamine/melam/melem polyphosphate double salt, or a composite compound of melamine/melam/melem polyphosphate and dimeram pyrosulfate. It is preferable to contain at least one or more phosphorus compounds selected from, and more preferably to contain these in combination with ammonium polyphosphate. The content of the flame retardant (b3) is preferably 100 to 1000 parts by weight (more preferably 200 to 800 parts by weight) with respect to 100 parts by weight of the solid content of the resin component (A).

Examples of the filler (b4) include talc, calcium carbonate, sodium carbonate, aluminum oxide (alumina), titanium oxide, zinc oxide, magnesium oxide, silica, clay, clay, shirasu, zeolite, mica, silica sand, silica powder, Quartz powder, barium sulfate, glass balloons, silica balloons, alumina balloons, shirasu balloons, resin balloons, and the like. These can be used singly or in combination of two or more. The content of the filler (b4) is preferably 3-200 parts by weight (more preferably 5-150 parts by weight) per 100 parts by weight of the solid content of the resin component (A).

Furthermore, in the present invention, metal hydrate (b5) and fiber (b6) can be included as the powder component (B).
The metal hydrate (b5) exhibits endothermic properties due to dehydration reaction or the like when the temperature rises, and is different from the filler (b4). Examples of such metal hydrates (b5) include aluminum hydroxide and magnesium hydroxide. These can be used alone or in combination of two or more. Also, the average particle size of the metal hydrate (b5) 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). is. The content of the metal hydrate (b5) is preferably 1 to 200 parts by weight (more preferably 5 to 100 parts by weight, still more preferably 8 to 80 parts by weight).

In the present invention, it is preferable to use the filler (b4) and the metal hydrate (b5) together. In this case, the weight ratio of the filler (b4) and the metal hydrate (b5) is 1:9 to 9:1. (more preferably 2:8 to 8:2). In this case, foamability, especially shrinkage of the carbonized heat insulating layer at high temperatures can be suppressed, and a stable carbonized heat insulating layer can be formed, so that the effects of the present invention can be enhanced. The average particle size is measured by a laser diffraction particle size distribution analyzer.

The fibers (b6) can improve thick coating properties (suppress thinning) and suppress cracking of the coating. In addition, the fibers (b6) can make it difficult for the coating to sag when the temperature rises due to a fire or the like, and can increase the thermal conductivity inside the coating. As a result, excellent foamability can be exhibited, a uniform carbonized heat insulating layer can be formed, and heat protection performance can be enhanced. Examples of such fibers (b6) include acrylic fiber, acetate fiber, aramid fiber, cuprammonium fiber (cupra), nylon fiber, novoloid fiber, pulp fiber, viscose rayon, vinylidene fiber, polyester fiber, polyethylene fiber, Organic fibers such as polyvinyl chloride fiber, polyclar fiber, vorinosic 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 Fibers, inorganic fibers such as silicon carbide fibers, and the like. These can be used singly or in combination of two or more.

In the present invention, the fibers (b6) preferably contain inorganic fibers, and among them, artificial mineral fibers such as rock wool fibers, slag wool fibers, glass fibers and ceramic fibers are preferable. As a result, cracking of the coating can be further suppressed, and when the temperature rises due to a fire or the like, it is possible to make it difficult for the coating to sag, etc., and further increase the thermal conductivity inside the coating. can. As a result, even the inside (core part) of the film exhibits excellent foamability, a more uniform carbonized heat insulating layer can be formed, and the heat-resistant protective performance of the substrate can be further enhanced.

In addition, the size (fiber length and fiber diameter) of the fiber (b6) may be set according to the performance of the repair material, the applicable base material, the specifications of the applicator, etc. The average fiber length is preferably 10 to 10. 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). Also, 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, cracking of the formed coating is less likely to occur, and when the temperature rises due to fire, etc., the coating is less likely to sag, etc., and a stable carbonized heat insulating layer can be formed. can be formed. The content of the fiber (b6) is preferably 0.5 to 30 parts by weight (more preferably 1 to 25 parts by weight, still more preferably 2 to 20 parts by weight) with respect to 100 parts by weight of the solid content of the resin component (A). parts by weight).

The repair material of the present invention is characterized by further containing a high boiling point compound (C). The high boiling point compound (C) is a high boiling point liquid compound that is liquid at 20° C. and has 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 (C), the heating residue and viscosity of the repair material can be optimized, and the dispersion stability of the powder component (B) can be enhanced. In addition, by mixing and reacting with the polyisocyanate component, a good coating with excellent adhesion can be formed, and in particular, the elasticity of the coating can be improved to prevent cracking of the coating. Furthermore, when the coating is exposed to high temperatures due to fire or the like, it contributes to moderate softening of the coating, further enhancing foamability, suppressing the falling off (peeling) of the formed carbonized heat insulating layer, etc. It can improve heat resistance protection performance.

The high boiling point compound (C) is not particularly limited as long as it satisfies the above conditions. Examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dihexyl phthalate, and di-2-ethylhexyl phthalate. , diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, butyl benzyl phthalate, and other phthalate compounds; diethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, adipic acid Aliphatic dibasic acid ester compounds such as dioctyl, diisononyl adipate, diisodecyl adipate, bis(butyl diglycol) adipate, diethyl sebacate, dibutyl sebacate, dihexyl sebacate, di-2-ethylhexyl sebacate; adipic acid Adipic acid-based polyesters such as -1,3-butylene glycol-based polyesters and adipate-1,2-propylene glycol-based polyesters; dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di-2-ethylhexyl maleate, Maleic acid ester compounds such as diisononyl maleate and diisodecyl maleate; Phosphate ester compounds such as;

trimetate ester compounds such as tris-2-ethylhexyl trimellitate; ricinoleate ester compounds such as methylacetyl ricinoleate; di-2-ethylhexyl epoxyhexahydrophthalate, diepoxystearyl epoxyhexahydrophthalate, epoxidized fatty acid butyl, Epoxy ester compounds such as epoxidized fatty acid 2-ethylhexyl, epoxidized soybean oil, and epoxidized linseed oil; Benzoic acid ester compounds such as benzoic acid glycol ester; 1-phenyl-1-xylylethane, 1-phenyl-1-ethyl Examples include aromatic hydrocarbon compounds such as phenylethane, lactones such as γ-butyrolactone, and mixtures of petroleum resin (aromatic hydrocarbon fraction polymer having 8 to 10 carbon atoms) and styrylxylene. These can be used singly or in combination of two or more.

In the present invention, the high boiling point compound (C) preferably contains one or more selected from phthalate compounds, aliphatic dibasic acid ester compounds, and phosphate ester compounds. It preferably contains one or more selected from 4 to 11 (more preferably 5 to 10, still more preferably 6 to 9) phthalate compounds and aliphatic dibasic acid ester compounds. Specific examples thereof include diisononyl phthalate, diisononyl adipate, di-2-ethylhexyl phthalate, and the like.

The content of the high boiling point compound (C) is preferably 5 to 200 parts by weight (more preferably 10 to 150 parts by weight, more preferably 15 to 100 parts by weight) with respect to 100 parts by weight of the solid content of the resin component (A). parts by weight). When such a range is satisfied, it is excellent in thick coating properties, has excellent foaming properties when the temperature rises due to a fire, etc., and can sufficiently exhibit the effect of maintaining the heat-resistant protective performance of the substrate. . Furthermore, in the case of such a range, not only the adhesion between the heat-resistant protective film and the repair material, but also sufficient adhesion (adhesion ) can be ensured, it is possible to form a coating excellent in finish.

In addition, any additive may be used as long as it does not significantly inhibit the effects of the present invention. Viscous agents, leveling agents, dispersants, antifoaming agents, water absorbing agents, dehydrating agents, cross-linking agents, silane coupling agents, ultraviolet absorbers, antioxidants, halogen scavengers, dilution solvents and the like.

Among these antioxidants, for example, phosphorus-based, sulfur-based or hindered-type phenol-based antioxidants can be used. These can be used alone or in combination of two or more. By containing such an antioxidant, it is possible to suppress the deterioration of the film not only in normal times but also in the event of 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 present invention is preferably used as a two-liquid type repair material containing the polyol composition containing the polyol component (A1) and the powder component (B) as a main component and the polyisocyanate component (A2) as a curing agent. That is, during distribution, the main agent and curing agent are stored in separate packages, and these are mixed during use (during application, that is, during film formation). The powder component (B) can also be mixed with the polyisocyanate component (A2) (curing agent side).

(Repair method)
The repair material of the present invention is suitable as a repair material (filler, putty material, sealing material, etc.) used for repairing or surface finishing heat-resistant protective coatings. It is characterized by applying a repair material.

In the present invention, the heat-resistant protective film specifically has the ability to protect the base material from high heat such as fire. Such a heat-resistant protective coating foams to form a carbonized heat insulating layer due to a temperature rise in the event of a fire (preferably when the surface temperature of the coating reaches 200° C. or higher, more preferably 250° C. or higher). protect from high heat.

Examples of base materials include various base materials that constitute various parts such as walls, pillars, floors, beams, roofs, stairs, ceilings, and doors. Examples of materials that constitute such base materials include steel materials, metals, concrete, mortar, siding boards, tiles, bricks, glass, wood, synthetic resins, plastics, and rubbers. These substrates are those on which a coating (anticorrosive coating, undercoat, topcoat, etc.) has already been formed, or to which some kind of surface treatment (antirust treatment, flame retardant treatment, etc.) has been applied. may

The heat-resistant protective film is formed of a coating material (thermally foamable paint, thermally foamable sheet, etc.) containing, for example, a resin and a heat-resistant powder such as a foaming agent, a carbonizing agent, a flame retardant, and a filler. and the like.

Examples of resins include acrylic resins, vinyl acetate resins, vinyl acetate-acrylic copolymer resins, polyethylene resins, acrylic-styrene copolymer resins, vinyl acetate-ethylene copolymer resins, polyester resins, vinyl acetate-vinyl versatate copolymers. Polymeric resin, vinyl acetate-vinyl versatate-acrylic copolymer resin, phenolic resin, petroleum resin, vinyl chloride resin, epoxy resin, urethane resin, polybutadiene resin, alkyd resin, melamine resin, fluorine resin, propylene rubber, chloroprene rubber, Butyl rubber, isobutylene rubber and the like can be mentioned. These can be used singly or in combination of two or more. As the foaming agent, carbonizing agent, flame retardant, and filler, the same ones as those used in the repair material of the present invention can be used.

In addition to the above ingredients, the coating material that forms the heat-resistant protective film includes, for example, pigments, fibers, wetting agents, plasticizers, lubricants, preservatives, antifungal agents, anti-algae agents, antibacterial agents, thickeners, and leveling agents. , a dispersant, an antifoaming agent, a cross-linking agent, an ultraviolet absorber, an antioxidant, a dilution solvent, and the like.

The thickness of the heat-resistant protective film formed by such a coating material may be appropriately set depending on the desired functionality, application site, etc., but is preferably about 0.4 to 5 mm.

Further, the heat-resistant protective film may be provided with a decorative film or the like on its surface for the purpose of improving aesthetic appearance, improving durability, or the like. Such a decorative film can be formed by applying a known topcoat material. Examples of topcoat materials include acrylic resin-based, urethane resin-based, acrylic silicone resin-based, and fluororesin-based coating materials.

Examples of the portion to be repaired of the heat-resistant protective film include:
(1) defective part of the heat-resistant protective film,
(2) the interface between the base material and the heat-resistant protective film, the seams between the heat-resistant protective films,
(3) surface irregularities of the heat-resistant protective coating (such as orange skin),
etc. By applying the aforementioned repair material to such a repaired portion, it is possible to repair efficiently and to obtain a finish excellent in aesthetics. Specific repair methods for the parts to be repaired in (1) to (3) are shown below.

As a method for repairing defective portions of the heat-resistant protective film in (1) above, if a defective portion (for example, swelling, floating, cracking, cracking, chipping, etc.) occurs in the heat-resistant protective film, It repairs the heat-resistant protective film. Prior to repairing a defective portion such as a bulge or a float, it is desirable to partially remove the coating film on the defective portion and its vicinity. As a result, a concave portion to be repaired (repaired portion) is formed. In many cases, recesses are formed in defective areas such as cracks, cracks, chips, etc. at the time of occurrence of defects, but by partially removing the film near the defective areas, repair is possible. It is also possible to arrange the shape of the recess to be formed.

The shape of the recess to be repaired (the shape when the coating is viewed from the front) is not particularly limited, and may be irregular, such as circular, elliptical, triangular, quadrangular, rectangular, and the like. , or if it is arranged in a shape similar to these, work efficiency can be improved. The size of such recesses (length in the lateral direction when the coating is viewed from the front) is preferably 5 to 300 mm, more preferably 10 to 100 mm. The depth of the recess is preferably 0.3-10 mm, more preferably 0.5-6 mm.

As a method for repairing the interface between the base material and the heat-resistant protective coating of (2) above, or the joint between the heat-resistant protective coatings, a repair material is applied (filled) to the interface and the joint, and the base material and the It uniformly finishes the boundaries between heat-resistant protective films or the boundaries between heat-resistant protective films. Thereby, the heat resistance can be sufficiently improved.

The above method (3) for repairing uneven portions of the surface of the heat-resistant protective coating is carried out when the heat-resistant protective coating is finished smoothly (for example, by mirror finishing). If the heat-resistant protective film has fine irregularities such as citrus peel, a smooth film can be formed by applying a repair material to the surface and, if necessary, polishing the surface.

The method of applying the repair material to the repaired part of (1) to (3) above is not particularly limited, but for example, a roller, brush, spatula, trowel, caulking gun, or other applicator may be used. is preferred. In the present invention, since the repairing material satisfies the above-mentioned condition of the residue after heating, it is possible to form a thick film and form a uniform coating. The repair material of the present invention can be diluted at the time of painting. In this case, the viscosity of the repair material preferably satisfies 20 to 180 Pa·s (preferably 30 to 150 Pa·s).

In addition, a repair material coating can be formed by drying the coating after applying the repair material. The drying temperature is preferably 0° C. or higher and 40° C. or lower (normal temperature), and can be heated as necessary. The drying time is preferably 4 hours or longer, more preferably 24 hours or longer.

In the present invention, in order to protect the film formed by the repair material, a topcoat material may be applied as necessary. Such a topcoat material can be formed by applying a known coating material. Coating materials such as acrylic resin, urethane resin, acrylic silicon resin, fluororesin, epoxy resin, and vinyl acetate resin can be used as the overcoat material. These can be used alone or in combination of two or more, and two or more topcoat materials can be laminated and applied. The topcoat material may be applied by a known application method, and for example, a spray, roller, brush or other coating tool can be used.

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

The following were used as each raw material.
・Resin component (A)
- Polyether polyol (a1)
(a1-1): Polyether polyol (addition polymer of ethylene oxide and propylene oxide with glycerin as an initiator, number average molecular weight of 10000, number of functional groups of 3, hydroxyl value of 17 mgKOH/g, terminal ethylene oxide addition)
(a1-2): Polyether polyol (addition polymer of ethylene oxide and propylene oxide using glycerin as an initiator, number average molecular weight of 7000, number of functional groups of 3, hydroxyl value of 24 mgKOH/g, terminal ethylene oxide addition)
(a1-3) Polyether polyol (addition polymer of ethylene oxide and propylene oxide with glycerin as an initiator, number average molecular weight of 6000, number of functional groups of 3, hydroxyl value of 28 mgKOH/g, terminal ethylene oxide addition)
(a1-4): Polyether polyol (ethylene oxide and propylene oxide addition polymer starting with propylene glycol, number average molecular weight 5100, number of functional groups 3, hydroxyl value 33 mgKOH/g, terminal ethylene oxide addition)
(a1-5): Polyether polyol (addition polymer with propylene oxide using glycerin as an initiator, number average molecular weight 4000, number of functional groups 3, hydroxyl value 43 mgKOH/g, terminal propylene oxide addition)
(a1-6): Polyether polyol (addition polymer with propylene oxide using glycerin as an initiator, number average molecular weight 700, number of functional groups 3, hydroxyl value 225 mgKOH/g, terminal propylene oxide addition)

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

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

<Powder component (B)>
・Blowing agent (b1): melamine ・Carbonizing agent (b2): pentaerythritol ・Flame retardant (b3): ammonium polyphosphate ・Filler (b4): titanium oxide ・Metal hydrate (b5): aluminum hydroxide (average particle diameter 1 μm)
- Fiber (b6): rock wool fiber (average fiber length 125 µm, average fiber diameter 4.5 µm)

<High boiling point compound (C)>
- High boiling point compound (c1): diisononyl phthalate (boiling point 420°C)
- High boiling point compound (c2): diisononyl adipate (boiling point 227°C)
- High boiling point compound (c3): di-2-ethylhexyl phthalate (boiling point 386 ° C.)
- High boiling point compound (c4): diisodecyl phthalate (boiling point 420°C)
- High boiling point compound (c5): diundecyl phthalate (boiling point 523°C)
- High boiling point compound (c6): dibutyl phthalate (boiling point 340 ° C.)

<Others>
・Curing catalyst: organometallic catalyst ・Additive 1: dispersant, antifoaming agent, etc. ・Additive 2: Diluent solvent (aromatic hydrocarbon)

(Repair materials 1 to 15)
Repair materials 1 to 15 were produced according to the formulations shown in Table 1. The resin component (A) is obtained by mixing the polyol component (A1) and the polyisocyanate component (A2) at a mixing ratio of NCO/OH equivalent ratio of 1.2.
As a method for preparing the repair material, the components (A1), (B), (C), catalyst, and additives are mixed in a conventional manner to prepare a polyol composition (main agent), and then (A2). A restorative material was prepared by mixing the components.

(Examples 1-13, Comparative Examples 1-2)
The following evaluations were performed for each of the repair materials 1 to 15. Results are shown in Table 1.

<Thickness Evaluation 1>
Coat the entire surface of a steel plate (length 150mm x width 70mm x thickness 1.6mm) with a 2mm wet film thickness using a trowel, and then at room temperature (25°C) for 24 hours, then at 50°C. After aging for 24 hours, the dry film thickness was measured to confirm changes in the film thickness. Evaluation criteria are as follows. Moreover, the results are shown in Table 1.
A: The thickness reduction rate is less than 15% B: The thickness reduction rate is 15% or more and less than 30% C: The thickness reduction rate is 30% or more and less than 45% D: The thickness reduction rate is 45% or more

Then, the entire surface of a steel plate (length 150 mm x width 70 mm x thickness 1.6 mm) that has been pre-painted to prevent rust is coated with a repair material (dry film thickness: 1.5 mm) with a trowel and cured at room temperature (25°C) for 7 days. The test sample [I] was prepared and subjected to the following evaluations.

<Heat resistance evaluation 1>
Based on the ISO 5660-1 cone calorimeter method, an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.) was used to radiate 50 kW / m ² of radiant heat to the surface of the specimen [I] for 15 minutes. The temperature of the back surface of the steel plate was measured. Each evaluation criterion is as follows. Moreover, the results are shown in Table 1.
(effervescent)
AA: More than 35 times expansion ratio A: More than 25 times more than 35 times less than 35 times B: More than 20 times more than 25 times less than 25 times expansion ratio C: More than 15 times more than 20 times less than 20 times expansion ratio D: More than 15 times expansion ratio (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: 550°C or more (denseness)
The test piece 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-grade evaluation (excellent: A>B>C>D: inferior) with "A" for high density and "D" for low density.

Furthermore, as a specimen [II], a steel plate (length 150 mm × width 70 mm × thickness 1.6 mm) was coated with an epoxy resin-based anti-rust undercoat material, a urethane resin-based thermally foaming paint, and an acrylic emulsion paint (white). A laminate was prepared, and a part of the film of this test piece was cut to form a circular concave portion (40 mm in diameter and 3 mm in depth). Next, each of the repair materials 1 to 15 was filled in the concave portion of the specimen and cured at room temperature (25° C.) for 7 days. Furthermore, acrylic emulsion paint (white) was applied to the concave portion and its vicinity to repair the concave portion.

<Finishing evaluation>
The finish of the repaired portion of the specimen [II] was evaluated. The evaluation criteria were a four-grade evaluation (excellent: A>B>C>D: inferior), with "A" indicating excellent aesthetic appearance with inconspicuous repaired areas and "D" indicating conspicuous repaired areas. Moreover, the results are shown in Table 1.

<Heat resistance evaluation after repair>
The surface of the test specimen [II] after repair was heated with a burner to evaluate the foamability of the entire coating including the repaired portion. The evaluation criteria are 4-grade evaluation with "A" when the entire coating including the repaired part foams and a uniform carbonized heat insulating layer is formed, and "D" when the foaming is uneven at the repaired part (excellent: A >B>C>D: inferior). Moreover, the results are shown in Table 1.

Examples 1 to 13 were excellent in film thickness (thickness of coating) and exhibited excellent heat-resistant protective properties. In addition, the portion to be repaired of the heat-resistant film could be repaired efficiently, and the finish was excellent in appearance. On the other hand, in Comparative Example 1, it was difficult to increase the film thickness, repairing the heat-resistant film was troublesome, and the finish was poor. Moreover, in Comparative Examples 1 and 2, sufficient heat protection was not obtained.

(Repair material 16-27)
Repair materials 16 to 27 were produced according to the formulations shown in Table 2. The resin component (A) is obtained by mixing the polyol component (A1) and the polyisocyanate component (A2) at a mixing ratio of NCO/OH equivalent ratio of 1.2.
As a method for preparing the repair material, the components (A1), (B), (C), catalyst, and additives are mixed in a conventional manner to prepare a polyol composition (main agent), and then (A2). A restorative material was prepared by mixing the components.

(Examples 14-26)
Furthermore, repair material 2 and repair materials 16 to 27 were subjected to the following evaluations in addition to the film thickness evaluation 1, heat resistance evaluation 1, finish evaluation, and heat resistance evaluation after repair.
<Thickness Evaluation 2>
Evaluation was performed in the same manner as in Thick Film Evaluation 1, except that the coating material was applied with a wet film thickness of 3 mm. Results are shown in Table 2.
<Thickness evaluation 3>
In film thickness evaluation 2, the state of the formed film was visually confirmed. Evaluation criteria were 4-grade evaluation (excellent: A>B>C>D: inferior) with "A" for a uniform coating and "D" for a cracked coating. Results are shown in Table 2.

<Heat resistance evaluation 2>
Based on the ISO 5660-1 cone calorimeter method, an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.) was used to radiate 50 kW / m ² of radiant heat to the surface of the specimen [I] for 30 minutes. The temperature of the back surface of the steel sheet was measured, and the denseness and ashing property were also evaluated. The foaming ratio, the temperature on the back surface of the steel sheet, and the evaluation criteria for denseness are the same as those for heat resistance evaluation 1 above. The evaluation criteria for ashing property are as follows. Moreover, the results are shown in Table 2.

(Ashes 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 checked, and the ratio of the ashed (white) portion was calculated. The evaluation criteria were 4 grades (excellent: A>B>C>D: poor), with "A" for little incineration and "D" for advanced incineration. Moreover, the results are shown in Table 2.

Claims (2)

A repair material for a film having heat-resistant protection,
The repair material has a coating that forms a carbonized heat insulating layer when the temperature rises,
The repair material contains a resin component (A), a powder component (B), and a high boiling point compound (C), and has a heating residue of 90% by weight or more,
The resin component (A) contains a polyol component and a polyisocyanate component,
The polyol component contains a polyether polyol having a molecular weight of 1000 or more,
The repair material , wherein the high boiling point compound (C) has a boiling point of 150° C. or higher . A method for repairing a film having heat-resistant protection, comprising applying the repair material according to claim 1 to a portion of the film having heat-resistant protection to be repaired.