JP3790332B2 - Foam refractory paint and coated structure - Google Patents

Description

【００２７】
【表２】

【００２８】
【表３】

【００２９】
［試験方法］
ＪＩＳ Ａ １３０４に規定する標準曲線に基づいて、１時間の間、電気炉で試験体片面を加熱昇温し熱間圧延鋼板の裏面温度が３５０℃に達した時点での経過時間を耐火性能（時間）とし、１時間加熱後の試験体についてその他の性能評価を行った。
［評価方法］
耐火性能（時間）、気泡の均一性、鉄板との付着、発泡層の剥離、作業性について表３のような基準にて評価した。このようにして評価した結果を表１，２に示した。
【００３０】
【発明の効果】
本発明で得られる発泡性耐火塗料は、断熱性の高い多孔質層の形成温度速めることと、塗膜成分の燃焼熱を抑えることにより、従来の耐火塗料を大きく上回る耐火性能を基材に付与することができる。この特徴から▲１▼高層ビル下層部の鉄骨構造材の耐火塗装、▲２▼住宅での鉄骨構造材の耐火塗装、▲３▼プラント設備の鉄骨構造材の耐火塗装などの分野での使用が見込まれる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel foamable fire-resistant paint exhibiting high fire resistance and a structure coated therewith.
[0002]
[Prior art]
Conventionally, various refractory materials have been used for the purpose of coating on structures such as steel frames and concrete, delaying the temperature rise of the base material when the temperature rises due to a fire, and preventing a sudden drop in mechanical strength. Yes. One of the refractory materials is a foamable refractory paint. This is to prevent the temperature of the base material from rising by forming a heat insulating layer by foaming the coating film when the temperature of the fire rises. The paint contains a component that decomposes due to temperature rise to generate nonflammable gas, and a component that carbonizes to form a porous carbonized layer, and extinguishes fire by generating nonflammable gas. An effect is exhibited by the formation of a porous carbonized layer by a carbonized component (for example, JP-A-05-86310). Since this foamable fire-resistant paint is applied with a thickness of several millimeters, it is lighter than a wet fire-resistant coating material that is thickened with an inorganic binder such as cement. The above problems are also solved.
[0003]
[Problems to be solved by the invention]
However, in the above-mentioned foam fire-resistant paint, (1) since the component forming the coating film is flammable, the temperature of the substrate rises due to combustion of the coating film itself, and (2) foams to form a heat insulating layer. Since the temperature to perform is 250 degreeC or more, there exists a problem that the heat insulation effect to this temperature is low.
[0004]
[Means for Solving the Problems]
As a result of intensive studies on a paint imparting high fire resistance that solves these problems, the present inventors have achieved a foaming property having a high fire resistance performance by using a specific resin and a foaming agent as components of the foaming fire resistant paint. I found fireproof paint.
[0005]
That is, the present invention is coated with a foamable refractory paint comprising an α, β-unsaturated carboxylic acid (co) polymer metal crosslinked product-forming composition containing a foaming agent; and a coating film formed from the paint. Structure.
The present invention further delays the temperature rise of the base material due to a fire and imparts high fire resistance performance to the base material as compared with the conventional foamable fireproof paint. The reason for this is as follows: (1) The porous layer forming temperature having high heat insulating properties was conventionally 250 ° C. or higher, while the present invention forms a porous layer from 100 ° C. (2) The heat of combustion of the components constituting the coating film is less than in the prior art, and the temperature rise of the substrate due to the combustion of the coating film itself is small.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the α, β-unsaturated carboxylic acid (co) polymer metal cross-linked product comprises (1) α, β-unsaturated carboxylic acid and, if necessary, other vinyl monomers as constituent units (co). It is formed by a method of reacting a polymer with a metal hydroxide or an oxide, or a method of (2) (co) polymerizing an α, β-unsaturated carboxylic acid metal salt with another vinyl monomer as required.
Examples of the α, β-unsaturated carboxylic acid (co) polymer metal crosslinked product-forming composition containing a foaming agent include the following two-component compositions.
[1] An A, β-unsaturated carboxylic acid metal salt and, if necessary, a liquid A composed of another vinyl monomer and a liquid B composed of a polymerization initiator, and the foaming agent is either liquid A or liquid B Contained in one or both.
[2] A liquid consisting of an α, β-unsaturated carboxylic acid and optionally another vinyl monomer, and a liquid B consisting of a polymerization initiator and a metal hydroxide or oxide. And one contained in either or both of the B liquid.
[3] A foaming agent comprising a liquid A composed of a (co) polymer of an α, β-unsaturated carboxylic acid and optionally another vinyl monomer, and a liquid B composed of a metal hydroxide or an oxide. Is contained in one or both of liquid A and liquid B.
[0007]
In the present invention, examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. Salts include alkali metals (eg, sodium, potassium, rubidium), alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, Zinc) and the like.
Among these, acrylic acid, methacrylic acid and salts thereof are preferable from the viewpoint of cost.
[0008]
Examples of the α, β-unsaturated carboxylic acid metal salt include the above metal salt of α, β-unsaturated carboxylic acid. Metals include alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc, silver, titanium). Among these, at least one polyvalent metal selected from the group consisting of calcium, magnesium, barium, zinc, aluminum, iron, copper, nickel, titanium and cobalt is preferable. Preferable α, β-unsaturated carboxylic acid metal salts are acrylic acid metal salts and methacrylic acid metal salts.
[0009]
The (co) polymer comprising α, β-unsaturated carboxylic acid and, if necessary, other vinyl monomers as constituent units is one or more of the above monomers or optionally other vinyl monomers ( The polymerization method and conditions of the (co) polymer can be known methods. For example, methods for initiating polymerization and examples of catalysts are described in JP-B 63-221843 and JP-B 63-. It is illustrated by No. 445 gazette etc.
[0010]
As other vinyl monomers constituting the (co) polymer, known ones can be used. For example, (meth) acrylamide, vinylpyrrolidone, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkylene oxide addition , Sodium (meth) acrylate, potassium (meth) acrylate, rubidium (meth) acrylate, (meth) acryloyl polyoxyethylene methyl ether, 2- (meth) acryloylamino-2-methylpropanesulfonic acid (salt) Water-soluble monovinyl monomers such as vinyl sulfonic acid (salt), styrene sulfonic acid (salt), itaconic acid (salt), maleic acid (salt), styrene, alpha methyl styrene, methyl (meth) acrylate, acrylonitrile, vinyl acetate, And oil-soluble monovinyl monomers.
[0011]
The proportion of the other vinyl monomer used may be arbitrarily selected according to the purpose, but is usually 70% by weight or less based on the total weight of the vinyl monomer, and the quality and cost of the resulting fire-resistant fire-resistant coating material are low. From the viewpoint, it is preferably 50% by weight or less, more preferably 30% by weight or less.
[0012]
A polyfunctional vinyl monomer may be used as a part of other vinyl monomers used in the present invention. Polyfunctional vinyl monomers include divinylbenzene, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane poly (meth) acrylate, and glycerin poly ( And (meth) acrylate, poly (meth) acrylate of pentaerythritol, diallyl phthalate, diallyl ether of (poly) ethylene glycol, and the like. Of these, poly (meth) acrylate is preferable from the viewpoint of the quality of the obtained fire-resistant fire-resistant paint.
[0013]
The use ratio of the polyfunctional vinyl monomer may be arbitrarily selected according to the purpose, but is usually 70% by weight or less with respect to the total weight of the vinyl monomer. From the viewpoint, it is preferably 50% by weight or less, more preferably 30% by weight or less.
[0014]
Metal hydroxides and metal oxides include alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc, Silver, titanium). Among these, at least one polyvalent metal selected from the group consisting of calcium, magnesium, barium, zinc, aluminum, iron, copper, nickel, titanium and cobalt is preferable. The ratio of the metal hydroxide and the metal oxide used may be arbitrarily selected according to the purpose, but is usually 30 with respect to the total number of moles of the α, β-unsaturated carboxylic acid polymer as the carboxylic acid metal salt. It is at least mol%, preferably at least 50 mol%, more preferably at least 70 mol%.
[0015]
As the polymerization initiator, known radical polymerization initiators, for example, oil-soluble radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide; azobiscyanovaleric acid, azobisamidinopropane salt, ascorbic acid and hydrogen peroxide solution Water-soluble radical polymerization initiators such as a combination of (redox), potassium persulfate or sodium persulfate and sodium bisulfate sulfate (redox), and the like, preferably a water-soluble radical polymerization initiator.
In these methods, the temperature for cross-linking polymerization is usually from 0 to 100 ° C, preferably from room temperature to 70 ° C.
[0016]
The foaming agent is a known organic or inorganic substance that decomposes by heating and generates, for example, non-combustible gases such as carbon dioxide, nitrogen, and ammonia and crystal water release. From the viewpoint of the performance of the resulting foamable fireproof paint, an inorganic substance having a decomposition temperature of preferably 100 to 250 ° C., such as aluminum chloride hexahydrate, ammonium aluminum sulfate 12 hydrate, iron (III) sulfate 9 hydrate, Iron (III) nitrate nonahydrate, magnesium sulfate heptahydrate, magnesium phosphate octahydrate, sodium sulfite heptahydrate, sodium sulfate decahydrate, sodium phosphate dodecahydrate, nickel sulfate ( II) Hexahydrate, zinc nitrate hexahydrate and the like.
[0017]
The foamable fire-resistant paint of the present invention can contain inorganic powder or inorganic fiber as necessary. Examples of inorganic powders include silicates, clay, clay, shirasu, mica, pigments, and nitric acid, and examples of inorganic fibers include metal whiskers, carbon fibers, ceramic fibers, glass fibers, asbestos, rock wool, and silica alumina fibers. It is done. The use ratio of these components may be arbitrarily selected according to the purpose, but is usually 50% by weight or less, preferably 20% by weight or less, based on the quality of the foamable fireproof paint. is there.
[0018]
Moreover, a diluent can be used if necessary. Examples of the diluent include water, methanol, toluene and the like, preferably water. In this case, it may be in a state dissolved in a diluent or in a slurry state.
[0019]
The mixing ratio of the A liquid and the B liquid in the above embodiment is usually [1] A liquid composed of an α, β-unsaturated carboxylic acid metal salt and, if necessary, another vinyl monomer, and B liquid composed of a polymerization initiator. When the foaming agent is contained in one or both of the liquid A and liquid B, the amount of the polymerization initiator relative to the vinyl monomer is determined as a standard, and the liquid A is obtained as a solid content excluding the diluent. B is 0.001-10 with respect to 100.
[2] A liquid consisting of an α, β-unsaturated carboxylic acid and optionally another vinyl monomer, and a liquid B consisting of a polymerization initiator and a metal hydroxide or oxide. And liquid B, if it is contained in one or both of them, it is determined based on the amount of polymerization initiator and metal hydroxide or oxide with respect to the vinyl monomer, and liquid A is obtained as a solid content excluding the diluent. 100 liquids are 5-100.
[3] A foaming agent comprising a liquid A composed of a (co) polymer of an α, β-unsaturated carboxylic acid and optionally another vinyl monomer, and a liquid B composed of a metal hydroxide or an oxide. Is contained in one or both of liquid A and liquid B, and is determined based on the amount of metal hydroxide or oxide with respect to the (co) polymer, and liquid A as a solid content excluding the diluent 100 liquids are 5-100.
[0020]
As a general construction method of the present invention, a method of spraying the steel structure material while mixing the two liquids of the above-described aspects by spraying is desirable. The formation speed of the coating film of the present invention is extremely fast and is not suitable for application with a trowel, a brush, or a roller. Moreover, undercoating for the purpose of rust prevention or the like can be appropriately applied to the steel frame material before construction of the present invention, or for the purpose of improving weather resistance and coloring after construction.
The weight of the (co) polymer metal salt crosslinked product in the coating film obtained from the paint of the present invention is usually 10% or more, preferably 20% or more.
[0021]
Examples of the structure in the present invention include metal structures or inorganic structures used for building columns, beams, floors, walls, roof structures, and the like.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not a thing limited to this. In the following, “parts” and “%” are based on weight.
[0023]
The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
AAc-Zn: zinc diacrylate 40% aqueous solution AAc-Ca: calcium diacrylate 20% aqueous solution AAc-Ba: barium diacrylate 40% aqueous solution AAc: acrylic acid PAAc: polyacrylic acid 50% aqueous solution with an average molecular weight of about 10,000 ZnO: oxidation Zinc CaO: Calcium oxide Ca (OH) 2: Calcium hydroxide foaming agent A: Magnesium sulfate heptahydrate foaming agent B: Magnesium phosphate octahydrate foaming agent C: Aluminum chloride hexahydrate DHA: Dipentaerythritol Hexaacrylate epoxy resin: "Epicoat 1001" manufactured by Yuka Shell Epoxy Co., Ltd. made of 2 parts by weight of m-xylylenediamine reacted with 1000 parts by weight PPA: ammonium pyrophosphate melamine: melamine powder PE: penta Erythritol pigment: Titanium oxide Diluent: Toluene [0024]
Examples 1-6
The raw material A liquid and B liquid shown in Table 1 were mixed at a predetermined ratio, and sprayed onto a hot-rolled steel sheet (300 × 300 × 9 mm) by spraying. Polymerization and crosslinking occurred almost instantaneously, and a coated steel plate with a thickness of 2 mm was obtained within a few minutes. This specimen was cured for 2 weeks or more and fire resistance was measured. The measurement results are shown in Table 1.
[0025]
Comparative Examples 1-2
The mixture shown in Table 2 was applied to a hot-rolled steel plate (300 × 300 × 9 mm) with a trowel. A coating-coated steel sheet having a thickness of 2 mm was obtained within a few hours after application. This specimen was cured for 2 weeks or more and fire resistance was measured. The measurement results are shown in Table 2.
[0026]
[Table 1]

[0027]
[Table 2]

[0028]
[Table 3]

[0029]
[Test method]
Based on the standard curve prescribed in JIS A 1304, the elapsed time at the time when the back surface temperature of the hot-rolled steel sheet reaches 350 ° C. by heating and heating the one side of the specimen in an electric furnace for 1 hour is shown as fire resistance ( Time), and other performance evaluations were performed on the test specimen after heating for 1 hour.
[Evaluation methods]
The fire resistance (time), bubble uniformity, adhesion to the iron plate, exfoliation of the foam layer, and workability were evaluated according to the criteria shown in Table 3. The results evaluated in this way are shown in Tables 1 and 2.
[0030]
【The invention's effect】
The foamable fire-resistant paint obtained by the present invention gives the base material fire resistance that greatly exceeds the conventional fire-resistant paint by accelerating the formation temperature of the porous layer with high heat insulation and suppressing the heat of combustion of the coating component. can do. Because of this feature, it can be used in fields such as (1) fireproof coating of steel structure materials in the lower part of high-rise buildings, (2) fireproof coating of steel structure materials in houses, and (3) fireproof coating of steel structure materials in plant facilities. Expected.

Claims (10)

A foamable refractory paint comprising an α, β-unsaturated carboxylic acid (co) polymer metal crosslinked product-forming composition containing a foaming agent. It consists of liquid A consisting of an α, β-unsaturated carboxylic acid metal salt and, if necessary, other vinyl monomers, and liquid B consisting of a polymerization initiator. The two-component foamable fireproof paint according to claim 1, which is contained in the composition. The liquid A is composed of an α, β-unsaturated carboxylic acid and, if necessary, another vinyl monomer, and the liquid B is composed of a polymerization initiator and a metal hydroxide or oxide. The two-component foamable fireproof paint according to claim 1, which is contained in one or both of the above. It consists of A liquid consisting of (co) polymer of α, β-unsaturated carboxylic acid and, if necessary, other vinyl monomer, and B liquid consisting of metal hydroxide or oxide. The two-component foamable fire-resistant paint according to claim 1, which is contained in one or both of the liquid B and the liquid B. The two-component foamable fireproof paint according to any one of claims 1 to 4, further comprising inorganic powder and / or inorganic fiber in one or both of the liquid A and liquid B.   The foaming fireproof paint according to any one of claims 1 to 5, wherein a decomposition temperature of the foaming agent is 100 to 250 ° C. Foaming agent is aluminum chloride hexahydrate, ammonium aluminum sulfate 12 hydrate, iron (III) sulfate 9 hydrate, iron nitrate (III) 9 hydrate, magnesium sulfate heptahydrate, magnesium phosphate octahydrate At least one selected from the group consisting of sodium sulfite heptahydrate, sodium sulfate decahydrate, sodium phosphate dodecahydrate, nickel (II) sulfate hexahydrate and zinc nitrate hexahydrate The foamable fire-resistant paint according to any one of claims 1 to 6. The foamable fire-resistant paint according to any one of claims 1 to 7, wherein the metal of the metal cross-linked product is a polyvalent metal. The foamable fire-resistant paint according to claim 8, wherein the polyvalent metal is at least one polyvalent metal selected from the group consisting of calcium, magnesium, zinc, barium, aluminum, iron, copper, nickel, titanium and cobalt. A structure coated with a coating film formed from the foamable fire-resistant paint according to claim 1.