FIRE-RESISTANT HEAT-INSULATION COMPOSITION, FIRE-RESISTANT HEAT-INSULATION COMPOSITION SLURRY, FIRE-RESISTANT HEAT-INSULATION BOARD, AND FIRE-RESISTANT HEAT-INSULATION STRUCTURE

Abstract

Provided is a structure having both fire resistance and heat insulation properties and capable of retaining its shape without being collapsed or deformed even when exposed to a flame. The present invention provides a fire-resistant heat-insulation composition comprising 70 to 250 parts by mass of gypsum based on 100 parts by mass of calcium aluminate having a CaO content of 34% or more, and 0.1 to 20 parts by mass of a fibrous inorganic clay mineral having a crystallization water ratio of 5% or more, based on 100 parts by mass of the total of the calcium aluminate and the gypsum.

Claims

1. A fire-resistant heat-insulation composition, comprising: 70 to 250 parts by mass of gypsum based on 100 parts by mass of calcium aluminate having a CaO content of 34% or more; and 0.1 to 20 parts by mass of a fibrous inorganic clay mineral having a water content of 5% or more, based on 100 parts by mass of the total of the calcium aluminate and the gypsum.

2. The fire-resistant heat-insulation composition according to claim 1, further comprising an inorganic powder having pores.

3. The fire-resistant heat-insulation composition according to claim 1, further comprising a setting retarder.

4. The fire-resistant heat-insulation composition according to claim 1, further comprising a hydration accelerator.

5. A fire-resistant heat-insulation composition slurry, obtained by mixing the fire-resistant heat-insulation composition according to claim 1 and water.

6. A fire-resistant heat-insulation board, comprising: a resin molded body having a continuous void ratio of 25 to 70 vol %; and the fire-resistant heat-insulation composition slurry according to claim 5 filled in the voids of the resin molded body and solidified.

7. A fire-resistant heat-insulation structure comprising the fire-resistant heat-insulation board according to claim 6.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0036] FIG. 1 is a schematic diagram of crystal structure of a fibrous inorganic clay mineral (sepiolite).

[0037] FIG. 2 is a side view showing construction of a fire-resistant structure.

[0038] FIG. 3 is a top view showing construction of a fire-resistant structure.

DESCRIPTION OF EMBODIMENTS

[0039] The present invention will be described in detail hereinafter. In the present specification, part and, are shown on the basis of mass unless otherwise specified. In the present specification, the numerical value range includes its upper limit and lower limit unless otherwise specified.

[0040] The fire-resistant heat-insulation composition according to the embodiment of the present invention (also referred to as “composition” simply hereinafter) is characterized by comprising predetermined calcium aluminate, gypsum and a fibrous inorganic clay mineral in predetermined ratios.

[0041] The calcium aluminate is a generic term for substances having hydration activity and containing, as main components, CaO and Al.sub.2O.sub.3, which can be obtained by mixing a calcia raw material, an alumina raw material, etc., then calcining the mixture in a kiln or melting the mixture by an electric furnace, and cooling it. The calcium aluminate is not particularly limited, but from the viewpoint of initial strength development after hardening, it is preferably amorphous calcium aluminate having been quenched after melting. The CaO content of the calcium aluminate is preferably 34% or more, and more preferably 40% or more, from the viewpoint of reaction activity. If the CaO content is less than 34%, sufficient fire resistance is not exhibited.

[0042] As the calcium aluminate, a compound wherein part of Cao or Al.sub.2O.sub.3 of calcium aluminate is substituted by an alkali metal oxide, an alkaline earth metal oxide, silicon oxide, titanium oxide, iron oxide, an alkali metal halide, an alkaline earth metal halide, an alkali metal sulfate, an alkaline earth metal sulfate, or the like may be used, or a compound containing CaO and Al.sub.2O.sub.3 as main components and containing any of the above substances in a small amount as a solid solution may be used.

[0043] The vitrification ratio of the calcium aluminate may preferably be 8% or more, more preferably 50% or more, and most preferably 90% or more. The vitrification ratio of the calcium aluminate can be calculated by the following method. Regarding a sample before heating, a main peak area S of the crystalline mineral is measured by powder X-ray diffractometry in advance, thereafter, the sample is heated at 1000° C. for 2 hours and then slowly cooled at a cooling rate of 1 to 10° C./min, then the main peak area S) of the crystalline mineral after heating is measured by powder X-ray diffractometry, and further, using these S.sub.0 and S values, the vitrification ratio χ is calculated from the following formula.

Vitrification ratio χ(%)=100×(1−S/S.sub.0)

[0044] Regarding the particle size of the calcium aluminate, a Blaine specific surface area thereof is preferably 3,000 cm.sup.2/g or more, and more preferably 5,000 cm.sup.2/g or more, from the viewpoint of initial strength development. When the Blaine specific surface area is 3,000 cm.sup.2/g or more, initial strength development is enhanced. Here, the Blaine specific surface area is a value measured in accordance with JIS R5201:2015, “Physical Testing Methods for Cement”.

[0045] As the gypsum contained in the composition, any of anhydrous gypsum, hemihydrate gypsum and dihydrate gypsum can be used without any restriction. Anhydrous gypsum is a generic term for a compound that is anhydrous calcium sulfate and is represented by a molecular formula of CaSO.sub.4, hemihydrate gypsum is a generic term for a compound represented by a molecular formula of CaSO.sub.4.1/2H.sub.2O, and dihydrate gypsum is a generic term for a compound represented by a molecular formula of CaSO.sub.4.2H.sub.2O.

[0046] Regarding the particle size of gypsum, an average particle size thereof may preferably be 1 to 30 μm, and more preferably 5 to 25 μm, from the viewpoint of obtaining incombustibility, initial strength development and appropriate working time. Here, the average particle size is a value measured using a measuring laser diffraction type particle size distribution meter in a state where gypsum has been dispersed using an ultrasonic device.

[0047] The amount of gypsum used in the composition may preferably be 70 to 250 parts by mass, and more preferably 100 to 200 parts by mass, based on 100 parts by mass of the calcium aluminate. If the amount of gypsum is less than 70 parts by mass or exceeds 300 parts by mass, sufficient fire resistance may not be imparted.

[0048] The fibrous inorganic clay mineral (also referred to as “fibrous mineral” simply hereinafter) contained in the composition needs to have a water content of at least 5% or more, from the viewpoint of obtaining heat insulation properties and fire resistance. The fibrous inorganic clay mineral not only imparts segregation reducing effect to the composition but also enhances fire resistance.

[0049] FIG. 1 is a schematic diagram of the crystal structure of the fibrous inorganic clay mineral which is sepiolite in FIG. 1. The diagram relies on to the structural model of Brauner and Preisinger; see also Japanese Patent Laid-Open No. 2004-59347, Japanese Patent Laid-Open No. 2002-338236. The fibrous mineral is a kind of a hydrous magnesium silicate mineral and is a fibrous clay mineral having such crystal structure as shown in FIG. 1 and being characterized in that pores are present inside the crystal, and in the pores, water of crystallization is present in the form of bound water or zeolite water.

[0050] According to FIG. 1, the two-dimensional crystal structure forms fibrous crystal structure wherein bricks are alternately stacked. In this unit crystal structure, four hydroxyl groups bonded to Mg atoms, four bound water bonded to Mg atoms, and eight zeolite water are present, as shown in FIG. 1. FIG. 1 indicates that the number of zeolite water in the unit structure is considered to be 8.

[0051] The fibrous mineral preferably has a specific surface area of 50 to 500 m.sup.2/g, a fiber length of 0.1 to 50 μm, and an aspect ratio, as represented by fiber length/fiber diameter, of 0.1 to 5000, though they vary depending upon the type of the fibrous mineral. Here, the specific surface area is a value measured in accordance with BET method and JIS Z8830:2013.

[0052] Typical examples of the fibrous minerals include, but are not limited to, sepiolite ((OH.sub.2).sub.4(OH).sub.4Mg.sub.8Si.sub.12O.sub.30.6-8H.sub.2O), palygorskite (attapulgite; (OH.sub.2).sub.4(OH).sub.2Mg.sub.5Si.sub.8O.sub.20.4H.sub.2O), wollastonite, and loglinite. Among these, one or more selected from sepiolite and palygorskite (or attapulgite) are preferable.

[0053] The water content of the fibrous mineral may preferably be 7% or more, and more preferably 9% or more. The upper limit of the water content is not particularly limited, but may preferably be, for example, 30% or less. A fibrous mineral is heated from 30° C. up to 200° C. by a thermogravimetric analyzer (TGA), and using mass X before heating and decreased mass X.sub.1, a water content W can be calculated from the following formula. Measurement was carried out under the conditions of a sample quantity of 10 mg, a temperature increasing rate of 5.0° C./min, and an atmosphere of air.

Water content W (mass %)=X.sub.1/X×100

[0054] The amount of the fibrous mineral used in the composition may preferably be 0.1 to 20 parts by mass, and more preferably 3 to 15 parts by mass, based on 100 parts by mass of the total of the calcium aluminate and the gypsum. If the amount of the fibrous mineral is less than 0.1 part by mass, there is a possibility that fire resistance and heat insulation properties may not be enhanced, and if the amount thereof exceeds 20 parts by mass, there is a possibility that fire resistance and heat insulation properties may be lowered. The fibrous mineral may be used by premixing it with calcium aluminate and gypsum, or may be used by dispersing it in water in advance.

[0055] In a preferred embodiment, the composition may further contain an inorganic powder having pores (also referred to as “inorganic powder” simply hereinafter). The inorganic powder is not particularly limited as long as it is a powder of an inorganic material having pores, and any of such powders is employable. Typical examples of the inorganic powders may include an inorganic powder obtained from a foam prepared by heating volcanic deposits at a high temperature, which is typified by Shirasu balloon, fly ash balloon generated from a thermal power plant, an inorganic powder obtained by calcining obsidian, perlite or shale, and a waste glass foam powder (recycled glass balloon) obtained by crushing a waste such as a glass bottle, then calcining the crushed waste and subjecting it to particle size adjustment, and one or more of these are employable. When fly ash balloon is used, one having an ignition loss of 5% or less is preferably used from the viewpoint of small amount of unburned carbon. In the present specification, the inorganic powder is an inorganic powder other than the aforesaid calcium aluminate, gypsum and fibrous inorganic clay mineral.

[0056] Regarding the particle size of the inorganic powder, an average particle size thereof may preferably be 1 to 150 μm, and more preferably 15 to 100 μm. Here, the average particle size is a value measured using a measuring laser diffraction type particle size distribution meter in a state where the powder has been dispersed by an ultrasonic device.

[0057] The amount of the inorganic powder used in the composition may preferably be 2 to 100 parts by mass, and more preferably 5 to 80 parts by mass, based on 100 parts by mass of the total of the calcium aluminate and the gypsum. When the amount of the inorganic powder is 2 parts by mass or more, heat insulation properties are enhanced, and when the amount thereof is 100 parts by mass or less, fire resistance is enhanced.

[0058] In a preferred embodiment, the composition may further contain a setting retarder. The setting retarder is a substance to adjust a usable time of the fire-resistant heat-insulation composition slurry. Examples of the setting retarders include inorganic setting retarders and organic setting retarders. Examples of the inorganic setting retarders include salts of phosphoric acid, silicofluoride, copper hydroxide, boric acid or its salt, zinc oxide, zinc chloride, and zinc carbonate. Examples of the organic setting retarders include oxycarboxylic acids (citric acid, gluconic acid, malic acid, tartaric acid, glucoheptonic acid, oxymalonic acid, lactic acid, etc.) or salts thereof (sodium salt, potassium salt, etc.), and saccharides typified by sugar. One or more of these are employable. Also, mixtures of combinations of the inorganic setting retarders, such as carbonate, bicarbonate, nitrate, hydroxide and silicate, and the above oxycarboxylic acids or their salts may be used. Among these, an oxycarboxylic acid or a salt thereof alone or a mixture of an inorganic setting retarder and an oxycarboxylic acid or a salt thereof is preferable. In the present specification, the setting retarder is a setting retarder other than the aforesaid calcium aluminate, gypsum, fibrous inorganic clay mineral and inorganic powder having pores.

[0059] The amount of the setting retarder used in the composition may preferably be 0.02 to 2.0 parts by mass, and more preferably 0.05 to 1.0 part by mass, based on 100 parts by mass of the total of the calcium aluminate and the gypsum. When the amount of the setting retarder is 0.02 part by mass or more, adjustment to a necessary usable time is facilitated, and when the amount thereof is 2.0 parts by mass or less, the hardening time does not become too long, and poor hardening does not easily occur.

[0060] In a preferred embodiment, the composition may further contain a hydration accelerator. The hydration accelerator is a substance that accelerates reaction of calcium aluminate with gypsum to increase the amount of water of crystallization, thereby enhancing fire resistance, and is not particularly limited. Examples of the hydration accelerators include a hydroxide such as calcium hydroxide, an alkali metal silicate, aluminum sulfate such as anhydrous aluminum sulfate, an alkali metal carbonate such as sodium carbonate, a nitrate, a nitrite, various Portland cement such as ordinary Portland cement, and various inorganic filler fine powders, and one or more of these are employable. In the present specification, the hydration accelerator is a hydration accelerator other than the aforesaid calcium aluminate, gypsum, fibrous inorganic clay mineral, inorganic powder having pores and setting retarder.

[0061] The amount of the hydration accelerator used in the composition is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total of the calcium aluminate and the gypsum. When the amount of the hydration accelerator is 0.1 part by mass or more, a sufficient hydration acceleration effect is obtained, and when the amount thereof is 15 parts by mass or less, an effect of securing a sufficient usable time is exerted.

[0062] By using water (tap water or the like) together with the fire-resistant heat-insulation composition according to the embodiment of the present invention, a fire-resistant heat-insulation composition slurry may be prepared. The amount of water for preparing the slurry is not particularly limited, but may preferably be 40 to 300 parts by mass, and more preferably 80 to 250 parts by mass, based on 100 parts by mass of the total of the calcium aluminate and the gypsum. When the amount of water is 40 parts by mass or more, the filling of voids becomes homogeneous, and the fire resistance is enhanced, and when the amount thereof is 300 parts by mass or less, the ettringite content in the hardened body in the void increases, and the fire resistance is enhanced.

[0063] By filling voids of a resin molded body having a continuous void ratio of 25 to 70 vol % (also referred to as “resin molded body” simply hereinafter) with the fire-resistant heat-insulation composition slurry according to an embodiment of the present invention and solidifying the slurry, a fire-resistant heat-insulation board may be produced. The resin molded body is a resin having continuous voids and refers to one having voids capable of being filled with the slurry. Examples of types of the resins include an expanded polyvinyl alcohol resin, an expanded polyurethane resin, an expanded polystyrene resin, an expanded polyolefin resin, and an expanded phenolic resin. By filling a mold with granular foams, which are formed of any of these resins, have closed cells and have a diameter of several millimeters, and subjecting the granular foams to heat-pressure molding to mold them in such a manner that continuous voids are formed among the granular foams, the resin molded body is obtained. The continuous void ratio of the resin molded body may be adjusted by the degree of pressurization during the production. Regarding the polystyrene resin, the resin molded body having continuous voids may be produced in accordance with a method for producing a bead method polystyrene foam. Among these, an expanded polystyrene resin molded body is preferable from the viewpoint of versatility. When the continuous void ratio is 25 vol % or more, sufficient fire resistance can be imparted to the resulting board, and when it is 70 vol % or less, board density is decreased and thermal conductivity is decreased, so that heat insulation properties are enhanced.

[0064] The continuous void ratio of the resin molded body can be determined by, for example, the following method. A rectangular parallelepiped sample is cut out from a thermoplastic resin foamed particle molded body having been allowed to stand for 24 hours or longer in an environment of the temperature of 23° C. and the relative humidity of 50%, and an apparent volume Va [cm.sup.3] is determined from external dimensions of the sample. Subsequently, the sample is sunk in a measuring cylinder containing ethanol of 23° C. using a tool such as a wire cloth, and slight vibration or the like is applied to the sample to remove air present in the voids of the molded body. Then, a true volume Vb [cm.sup.3] of the sample, which is read out from a water level rise taking into consideration a volume of the tool such as a wire cloth, is measured. Using the apparent volume Va [cm.sup.3] and the true volume Vb [cm.sup.3], the continuous void ratio V [%] can be determined from the following formula.

Continuous void ratio V[%]=[(Va−Vb)/Va]×100

[0065] The slurry filled in the continuous voids undergoes hydration reaction to produce a hydration product, and the product is hardened. The continuous voids in the resin molded body are filled with the hydration product. The hydration product is, for example, ettringite formed by the reaction of calcium aluminate with gypsum. Since ettringite has a large amount of water as water of crystallization in molecules, it is dehydrated by heating, exhibits fire extinguishing action, and imparts incombustibility to the resin molded body. In the embodiment of the present invention, ettringite is actively produced by using calcium aluminate having a CaO content of 34% or more, and enhances incombustibility of the resin molded body.

[0066] Examples of methods for filling the resin molded body with the fire-resistant heat-insulation composition slurry include, but are not limited to, a method of injecting the slurry with compressed air or sucking the slurry by reducing the pressure with a vacuum pump to perform filling, and a method of filling the voids while applying vibration of 30 to 60 Hz to the resin molded body set on a vibration table. Among these, a method of filling the voids while applying vibration is preferable from the viewpoint of quality stability.

[0067] A method for curing the fire-resistant heat-insulation board after filling of voids with the fire-resistant heat-insulation composition slurry is not particularly limited, but is, for example, a method of air-curing the board at ordinary temperature after filling or a method of coating the board surface with a plastic film and air-curing it at ordinary temperature. In order to shorten the curing time, the fire-resistant heat-insulation board may be cured at a temperature of 30 to 50° C.

[0068] In certain embodiments, the whole board may be further coated with a non-woven fabric, or a reinforcing material such as a lattice-like fiber sheet may be arranged on one or both surfaces of the board, or a non-woven fabric and a fiber sheet may be used in combination.

[0069] The shape of the fire-resistant heat-insulation board of the present invention is not particularly limited, but the board may preferably have a length of 500 to 1000 mm, a width of 1000 to 2000 mm, and a thickness of 10 to 100 mm. The thickness may more preferably be 50 to 100 mm. When the size is small, the fire-resistant heat-insulation board becomes lightweight, and workability during setting is improved.

[0070] In certain embodiments, in the preparation of the fire-resistant heat-insulation composition slurry, one or more of various additives may be used as long as they have no influence on performance. Examples of such additives include a surfactant, an air entraining agent, a carbonization accelerator, a flame retardant, a fire spread preventing agent, an inorganic substance, a rust preventive, an antifreezing agent, a shrinkage reducing agent, a clay mineral and an anion exchanger.

[0071] The density of the fire-resistant heat-insulation board according to the embodiment of the present invention is preferably 100 to 800 kg/m.sup.3, and more preferably 200 to 500 kg/m.sup.3, from the viewpoint that the fire resistance and the heat insulation properties are not impaired. When the density is 100 kg/m.sup.3 or more, sufficient fire resistance can be secured, and when the density is 800 kg/m.sup.3 or less, sufficient heat insulation properties are obtained.

[0072] In certain embodiments, by using the aforesaid fire-resistant heat-insulation board, a fire-resistant structure of a building can be constructed. Such a fire-resistant structure is, for example, a structure which consists of layers of a siding board, a moisture-permeable waterproof sheet, the fire-resistant heat-insulation board, structural plywood and a reinforced gypsum board arranged in this order when shown by layer construction from the exterior wall side and in which a space (i.e., space for placing therein a heat-insulation material such as glass wool) of about 100 mm is provided between the structural plywood and the reinforced gypsum board by means of studs.

[0073] According to an embodiment of the present invention, a fire-resistant heat-insulation structure including the fire-resistant heat-insulation board is obtained.

[0074] When the fire-resistant structure is constructed, a plurality of the fire-resistant heat-insulation boards may be piled up one upon another and bonded to one another, or the fire-resistant heat-insulation board may be used together with a reinforced gypsum board, depending upon the fireproof specifications required.

EXAMPLES

[0075] Hereinafter, the contents will be described in more detail with reference to Examples and Comparative Examples, but the present invention is in no way limited to these Examples.

Experimental Example 1

[0076] The lower part of a foamed resin molded body (size: length 20 cm×width 20 cm×thickness 5 cm) having continuous voids was reinforced with alkali-resistant glass fibers, and a polyester non-woven fabric was further superposed thereon. This was set in a vibration impregnation device, then a fire-resistant heat-insulation composition slurry of the compounding shown in Table 1 was poured onto the upper surface of the molded body, and vibration of 60 Hz was applied for 1 minute to impregnate the voids with the fire-resistant heat-insulation composition slurry, thereby producing a fire-resistant heat-insulation board. After filling, the fire-resistant heat-insulation board was taken out from the device and cured at ordinary temperature for 3 days. Regarding the cured fire-resistant heat-insulation board, the content of water of crystallization, fire resistance, shape retention, the shape retention ratio and the thermal conductivity were evaluated. The results are set forth in Table 1.

Materials Used

[0077] Foamed resin molded body A: The molded body was produced by filling a molding machine (manufactured by DAISEN INDUSTRY Co., Ltd., VS-500) with commercial polystyrene expanded beads (diameter: 1 to 5 mm) and heating the beads by steam to fusion-bond foamed particles to one another in a state where there were voids among the foamed particles. The continuous void ratio was controlled by adjusting the degree of pressurization. continuous void ratio: 36.8%, density of polystyrene expanded beads molded body: 10.5 kg/m.sup.3, thermal conductivity of polystyrene expanded beads molded body: 0.033 W/(m.Math.K)
Calcium aluminate 1 (CA1): amorphous calcium aluminate obtained by adjusting compounding ratios to CAO: 431 and Al.sub.2O.sub.3: 53% and subjecting them to melting and quenching by an electric furnace; vitrification ratio: 98% or more, Blaine specific surface area: 6050 cm.sup.2/g
Calcium aluminate 2 (CA2): Alumina Cement No. 1 manufactured by Denka Company Limited, CaO: 36%, vitrification ratio: 15%, Blaine specific surface area: 4570 cm.sup.2/g
Calcium aluminate 3 (CA3): Asahi Fondu manufactured by AGC Ceramics Co., Ltd., CaO: 37%, vitrification ratio: 12%, Blaine specific surface area: 3500 cm.sup.2/g
Calcium aluminate 4 (CA4): Denka High Alumina Cement manufactured by Denka Company Limited, CaO: 26%, vitrification ratio: 13%, Blaine specific surface area: 4660 cm.sup.2/g
Ettringite 1 (ET1): ettringite powder obtained by using slaked lime, aluminum sulfate and gypsum as staring raw materials, and by performing hydrothermal synthesis and subjecting the resulting product to filtration and drying; ratio of water of crystallization: 46%
Gypsum 1 (CS1): II type anhydrous gypsum manufactured by Noritake Co., Limited, trade name: D-101A, purity: 95%, average particle size 20 μm
Gypsum 2 (CS2): § type hemihydrate gypsum manufactured by Noritake Co., Limited, trade name: FT-2, purity: 95%, average particle size 20 μm
Gypsum 3 (CS3): dihydrate gypsum manufactured by Noritake Co., Limited, trade name: P52B, purity: 95%, average particle size: 20 μm
Fibrous mineral (F1): sepiolite manufactured by TOLSA, trade name: PANGEL AD, water content: 13.2%, fiber length: 5 μm, fiber diameter: 0.1 μm, specific surface area: 270 m.sup.2/g
Fibrous mineral (F2): palygorskite (attapulgite) manufactured by Active Minerals International, LLC, trade name: MIN-U-GEL 200, water content: 9.8%, fiber length: 5 μm, fiber diameter: 0.1 μm, specific surface area: 270 m.sup.2/g
Fibrous mineral (F3): wollastonite manufactured by KANSAI MATEC CO., LTD., trade name: KTP-H02, water content: 2.0%, fiber length: 75 μm, fiber diameter: 10 μm, specific surface area: 4200 cm.sup.2/g
Non-fibrous mineral (N1): bentonite manufactured by KUNIMINE INDUSTRIES CO. LTD., trade name: KUNIGEL V1, the ratio of water of crystallization: 3.5%, specific surface area: 60 m.sup.2/g
Water: tap water

Preparation of Fire-Resistant Heat-Insulation Composition Slurry and Amount of Charge

[0078] To 100 parts by mass of calcium aluminate, gypsum was added in the amount shown in Table 1 to prepare a mixture, then to 100 parts by mass of the mixture, a fibrous mineral of the type and the amount shown in Table 1 and 100 parts by mass of water were added, and they were stirred for 5 minutes to prepare a slurry. The prepared slurry was poured onto the upper surface of the foamed resin molded body in an amount of 810 cm.sup.3 (i.e., 1.1 times the void volume of the resin molded body). Regarding the synthetic ettringite, 100 parts by mass of the synthetic ettringite were mixed with a predetermined amount of a fibrous mineral to prepare a mixture, then to 100 parts by mass of the mixture, 100 parts by mass of water were added, and they were stirred for 5 minutes to prepare a slurry.

Measuring Methods

[0079] Continuous void ratio: A continuous void ratio of the foamed resin molded body was determined. A sample was cut out from the foamed resin molded body having been allowed to stand for 24 hours or more in an environment of the temperature of 23° C. and the relative humidity of 50%, then an apparent volume Va [cm.sup.3] was determined from external dimensions (length 10 cm×width 10 cm×thickness 5 cm) of the sample, the sample was sunk in a measuring cylinder containing ethanol of 23° C. using a wire cloth, and slight vibration or the like was applied to the sample to remove air present in the voids of the molded body. Then, taking into consideration a volume of the wire cloth, a water level rise was read out, and a true volume Vb of the sample was measured. Using the apparent volume Va and the true volume Vb, the continuous void ratio V [%] was determined from the following formula.

Continuous void ratio V[%]=[(Va−Vb)/Va]×100

Content of water of crystallization (amount of water of crystallization): A sample of 20 g was obtained from the fire-resistant heat-insulation board, then the free water in the hardened body and the foam were dissolved in acetone, the resulting solution was filtered, and thereafter, the residue was thoroughly washed with acetone and vacuum-dried for 48 hours in a desiccator in an environment of 25° C. A mass decrease of the dried hardened substance in the range of 50 to 200° C. was measured by a thermal analyzer (temperature increasing rate: 10° C./min, in the air), and the measured value was taken as the amount of water of crystallization. The water of crystallization in the present specification refers to water contained in the fire-resistant heat-insulation board and chemically or physically bonded thereto, except free water capable of being removed by drying of acetone or the like.
Fire resistance: Reaction-to-fire tests by a cone calorimeter shown in ISO-5660-1:2002 were carried out, and fire resistance was simply evaluated. It is preferable that the gross calorific value, as measured under the conditions of a heating time of 20 minutes using a specimen having length 10 cm×width 10 cm×thickness 5 cm, be 8 MJ/m.sup.2 or less because the specimen has fire resistance (incombustibility).
Thermal conductivity: Using a specimen having length 10 cm×width 5 cm×thickness 5 cm obtained from the fire-resistant heat-insulation board, a thermal conductivity was measured by a quick thermal conductivity meter (box type probe method).
Shape retention: A specimen was subjected to a combustion test by a cone calorimeter, then a case where the specimen was free from crack, breakage, collapse, defective part and shrinkage was evaluated as circle (OK), and a case where the specimen had been confirmed to have crack, breakage, collapse and defective part was evaluated as X-mark (NG).
Shape retention ratio: A shape retention ratio was measured by comparing a volume of a specimen after a combustion test by a cone calorimeter with a volume of the specimen before the test.

TABLE-US-00001 TABLE 1 Amount of CS water of Shape (part(s) F (part(s) crystal- Fire retention Thermal Experiment CA by by lization resistance Shape ratio conductivity No. type mass) mass) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 1-1 CA1 CS1 100 — 0 32.0 8.9 x unmea- 0.088 Comparative surable Example 1-2 CA1 CS1 100 F1 7 36.0 3.9 ○ 96.8 0.049 Example 1-3 CA1 CS2 100 F1 7 35.2 4.3 ○ 96.5 0.051 Example 1-4 CA1 CS3 100 F1 7 35.0 4.4 ○ 96.4 0.055 Example 1-5 CA2 CS1 100 F1 7 34.0 6.5 ○ 97.0 0.058 Example 1-6 CA3 CS1 100 F1 7 33.0 6.8 ○ 95.6 0.062 Example 1-7 CA4 CS1 100 F1 7 22.4 10.1 x 89.9 0.099 Comparative Example 1-8 CA1 CS1 70 F1 7 35.9 5.0 ○ 96.7 0.052 Example 1-9 CA1 CS1 120 F1 7 36.5 3.7 ○ 97.1 0.046 Example 1-10 CA1 CS1 150 F1 7 35.8 4.1 ○ 96.7 0.049 Example 1-11 CA1 CS1 200 F1 7 35.7 4.4 ○ 97.0 0.051 Example 1-12 CA1 CS1 250 F1 7 34.6 4.6 ○ 97.0 0.053 Example 1-13 CA1 CS1 100 F1 0.1 35.1 4.5 ○ 96.5 0.059 Example 1-14 CA1 CS1 100 F1 0.5 35.3 4.3 ○ 96.5 0.058 Example 1-15 CA1 CS1 100 F1 1 35.5 4.3 ○ 96.5 0.058 Example 1-16 CA1 CS1 100 F1 3 35.6 4.1 ○ 96.8 0.053 Example 1-17 CA1 CS1 100 F1 5 35.9 3.9 ○ 96.8 0.052 Example 1-18 CA1 CS1 100 F1 10 36.0 3.8 ○ 97.1 0.048 Example 1-19 CA1 CS1 100 F1 15 36.2 4.2 ○ 97.1 0.052 Example 1-20 CA1 CS1 100 F1 20 36.0 4.9 ○ 96.9 0.058 Example 1-21 CA1 CS1 100 F2 7 36.0 3.9 ○ 97.0 0.050 Example 1-22 CA1 CS1 100 F3 7 32.2 8.3 x 88.8 0.076 Comparative Example 1-23 CA1 CS1 100 F1/ F2 5/5 35.6 3.8 ○ 97.1 0.048 Example 1-24 CA1 CS1 100 N1 7 32.0 8.9 x 87.6 0.078 Comparative Example 1-25 ET1 — — F1 7 23.9 16.5 x unmea- 0.079 Comparative surable Example 1-26 ET1 — — F1 20 25.7 13.5 x unmea- 0.079 Comparative surable Example 1-27 ET1 — — F1 50 29.6 11.2 x 84.2 0.079 Comparative Example
The amount of gypsum (CS) is an amount in terms of part(s) by mass based on 100 parts by mass of calcium aluminate (CA).
The amount of the fibrous mineral (F) is an amount in terms of part(s) by mass based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS).
In Experiment No. 1-23, based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS), 5 parts by mass of the fibrous mineral (F1) and 5 parts by mass of the fibrous mineral (f2) were mixed and used.

[0080] From Table 1, it can be seen that by using calcium aluminate satisfying the predetermined conditions, gypsum and a fibrous mineral, the amount of water of crystallization in the hardened body having been filled, e.g., the amount of water of crystallization in ettringite, greatly increased. That is to say, since the fibrous mineral contributes to the reaction of calcium aluminate with gypsum, the ettringite content increases, and fire resistance, shape retention and thermal conductivity can be enhanced. By contrast, it can be seen that in the Comparative Example using synthetic ettringite, the amount of water of crystallization did not increase even by using a fibrous mineral. It is though that in the Comparative Example, most of water added in the preparation of the slurry exists as free water not as water of crystallization, so that the free water is easily lost when dried over time or heated, and such an effect as exerted by the Examples cannot be obtained.

Experimental Example 2

[0081] To 100 parts by mass of calcium aluminate (CA1), 120 parts by mass of gypsum (CS1) were added, then to 100 parts by mass of the mixture of calcium aluminate and gypsum, an inorganic powder of the type and the amount shown in Table 2, 7 parts by mass of the fibrous mineral (F1) and 100 parts by mass of water were added, and a fire-resistant heat-insulation composition slurry was prepared in the same manner as in Experimental Example 1, followed by evaluating performance. The results are set forth in Table 2.

Materials Used

[0082] Inorganic powder 1 (P1): Shirasu balloon manufactured by AXYZ Chemical Co. Ltd., trade name: MSB-301, average particle size: 50 μm
Inorganic powder 2 (P2): Shirasu balloon manufactured by AXYZ Chemical Co. Ltd., trade name: ISM-F015, average particle size: 22 μm
Inorganic powder 3 (P3): Shirasu balloon manufactured by AXYZ Chemical Co. Ltd., trade name: MSB-5011, average particle size: 96 μm
Inorganic powder 4 (P4): fly ash balloon manufactured by TOMOE Engineering Co., Ltd., trade name: Cenolite SA, average particle size: 80 μm
Inorganic powder 5 (P5): waste glass foam powder manufactured by DENNERT PORAVER GMBH, trade name: Poraver (0.04-0.125 mm particle size product, average particle size: 90 μm

TABLE-US-00002 TABLE 2 Amount of water of Shape P (part(s) crystal- Fire retention Thermal Experiment by lization resistance Shape ratio conductivity No. mass) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 1-9 — 0 36.5 3.7 ○ 97.1 0.046 Example 2-1 P1 15 35.0 4.7 ○ 99.1 0.042 Example 2-2 P2 15 35.2 4.8 ○ 99.2 0.042 Example 2-3 P3 15 35.1 5.0 ○ 98.9 0.043 Example 2-4 P4 15 35.0 4.9 ○ 98.9 0.042 Example 2-5 P5 15 35.1 4.9 ○ 99.2 0.043 Example 2-6 P1 2 36.2 4.4 ○ 97.8 0.045 Example 2-7 P1 5 35.9 3.9 ○ 98.5 0.044 Example 2-8 P1 10 35.4 3.9 ○ 98.9 0.043 Example 2-9 P1 30 32.5 4.0 ○ 99.1 0.041 Example 2-10 P1 50 29.6 4.1 ○ 99.1 0.040 Example 2-11 P1 70 27.4 4.2 ○ 99.2 0.039 Example 2-12 P1 100 23.5 4.4 ○ 99.3 0.038 Example 2-13 P1/P4 7/7 35.3 4.4 ○ 99.0 0.043 Example
The amount of the inorganic powder (P) is an amount in terms of part(s) by mass based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS). In Experiment No. 2-13, based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS), 7 parts by mass of an inorganic powder (P1) and 7 parts by mass of an inorganic powder (P4) were mixed and used.

[0083] From Table 2, it can be seen that since the fire-resistant heat-insulation composition further contained an inorganic powder, heat insulation properties were enhanced while maintaining excellent fire resistance and shape retention.

Experimental Example 3

[0084] To 100 parts by mass of calcium aluminate (CA1), 120 parts by mass of gypsum (CS1) were added, then to 100 parts by mass of the mixture of calcium aluminate and gypsum, a setting retarder of the type and the amount shown in Table 3, 7 parts by mass of the fibrous mineral (F1) and 100 parts by mass of water were added, and a fire-resistant heat-insulation composition slurry was prepared in the same manner as in Experimental Example 1, followed by evaluating performance. The results are set forth in Table 3.

Materials Used

[0085] Setting retarder (R2): first grade reagent sodium citrate
Setting retarder (R2): first grade reagent tartaric acid
Setting retarder (R3): first grade reagent sodium gluconate

Measuring Methods

[0086] Gelation time: In a plastic beaker, the fire-resistant heat-insulation composition slurry prepared was placed, then this was placed in a heat-insulation container, and a resistance thermometer bulb was put thereinto. A period of time in which owing to the generation of heat accompanying hardening of mortar, the temperature increased by 2° C. from the temperature measured immediately after completion of kneading by means of a thermograph was taken as a gelation time.

TABLE-US-00003 TABLE 3 Amount of water of Shape P (part(s) Gelation crystal- Fire retention Thermal Experiment by time lization resistance Shape ratio conductivity No. mass) (min) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 1-9 — 0 35 36.5 3.7 ○ 97.1 0.046 Example 3-1 R1 0.05 50 36.4 3.7 ○ 96.9 0.046 Example 3-1 R2 0.05 60 36.2 3.8 ○ 97.0 0.047 Example 3-2 R3 0.05 85 36.2 3.8 ○ 96.7 0.047 Example 3-3 R1 0.02 40 36.4 3.7 ○ 97.0 0.046 Example 3-4 R1 0.07 60 36.0 3.9 ○ 96.8 0.047 Example 3-5 R1 1.0 135 35.8 4.0 ○ 96.8 0.047 Example 3-6 R1 2.0 210 35.5 4.1 ○ 96.6 0.047 Example
The amount of the setting retarder (R) is an amount in terms of part(s) by mass based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS).

[0087] From Table 3, it can be seen that since the fire-resistant heat-insulation composition further contained a setting retarder, the usable time was able to be adjusted while maintaining excellent fire resistance, shape retention and heat insulation properties.

Experimental Example 4

[0088] To 100 parts by mass of calcium aluminate (CA1), 120 parts by mass of gypsum (CS1) were added, then to 100 parts by mass of the mixture of calcium aluminate and gypsum, 0.07 part by mass of a setting retarder, a hydration accelerator of the type and the amount shown in Table 4, 7 parts by mass of the fibrous mineral (F1) and 100 parts by mass of water were added, and a fire-resistant heat-insulation composition slurry was prepared in the same manner as in Experimental Example 1, followed by evaluating performance. The results are set forth in Table 4.

Materials Used

[0089] Hydration accelerator 1 (ACC1): first grade reagent potassium hydroxide
Hydration accelerator 2 (ACC2): ordinary Portland cement manufactured by Denka Company Limited
Hydration accelerator 3 (ACC3): first grade reagent sodium carbonate
Hydration accelerator 4 (ACC4): first grade reagent anhydrous aluminum sulfate

TABLE-US-00004 TABLE 4 Amount of ACC water of Shape (part(s) Gelation crystal- Fire retention Thermal Experiment by time lization resistance Shape ratio conductivity No. mass) (min) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 3-4 — 0 60 36.0 3.9 ○ 96.8 0.047 Example 4-1 ACC1 5 30 38.2 3.6 ○ 97.6 0.046 Example 4-2 ACC2 5 45 38.0 3.6 ○ 97.3 0.046 Example 4-3 ACC3 5 50 37.9 3.7 ○ 97.4 0.047 Example 4-4 ACC4 5 45 37.9 3.7 ○ 97.3 0.047 Example 4-5 ACC1 0.1 60 36.5 3.8 ○ 97.2 0.047 Example 4-6 ACC1 1 55 37.2 3.7 ○ 97.4 0.047 Example 4-7 ACC1 3 50 37.6 3.7 ○ 97.5 0.047 Example 4-8 ACC1 7 20 38.2 3.6 ○ 97.6 0.046 Example 4-9 ACC1 10 10 38.4 3.6 ○ 97.5 0.047 Example 4-10 ACC1 15 5 38.5 3.5 ○ 97.2 0.046 Example
The amount of the hydration accelerator (ACC) is an amount in terms of part(s) by mass based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS).

[0090] From Table 4, it can be seen that since the fire-resistant heat-insulation composition further contained a hydration accelerator, the amount of water of crystallization was able to be increased, and the fire resistance was able to be enhanced while maintaining excellent heat insulation properties and shape retention.

Experimental Example 5

[0091] To 100 parts by mass of calcium aluminate (CA1), 120 parts by mass of gypsum (CS1) were added to prepare a mixture, then to 100 parts by mass of the mixture of calcium aluminate and gypsum, 7 parts by mass of the fibrous mineral (F1) and water of the amount shown in Table 5 were added, and a fire-resistant heat-insulation composition slurry was prepared in the same manner as in Experimental Example 1, followed by evaluating performance. The results are set forth in Table 5.

TABLE-US-00005 TABLE 5 Amount of Water water of Shape (part(s) crystal- Fire retention Thermal Experiment by lization resistance Shape ratio conductivity No. mass) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 5-1 50 35.1 3.9 ○ 97.0 0.053 Example 5-2 70 36.3 3.8 ○ 97.0 0.052 Example 1-9 100 36.5 3.7 ○ 97.1 0.046 Example 5-3 150 36.2 4.0 ○ 97.7 0.046 Example 5-4 200 35.9 4.4 ○ 97.5 0.046 Example 5-5 250 35.5 4.8 ○ 96.2 0.047 Example 5-6 300 33.5 5.2 ○ 95.2 0.050 Example
The amount of water is an amount in terms of part(s) by mass based on 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS).

[0092] From Table 5, it can be seen that by preparing a fire-resistant heat-insulation composition slurry using an appropriate amount of water, excellent fire resistance, shape retention and heat insulation properties were exhibited.

Experimental Example 6

[0093] To 100 parts by mass of calcium aluminate (CA1), 120 parts by mass of gypsum (CS1) were added, then to 100 parts by mass of the mixture of calcium aluminate and gypsum, 7 parts by mass of the fibrous mineral (F1) and 100 parts by mass of water were added, and a fire-resistant heat-insulation composition slurry was prepared in the same manner as in Experimental Example 1 while the void ratio of the foamed resin molded body was changed as shown in Table 6, followed by evaluating performance. The results are set forth in Table 6.

Materials Used

[0094] Foamed resin molded body B: The molded body was produced by filling a molding machine (manufactured by DAISEN INDUSTRY Co., Ltd., VS-500) with commercial polystyrene expanded beads (diameter: 1 to 5 mm) and heating the beads by steam to fusion-bond foamed particles to one another in a state where there were voids among the foamed particles. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio: 25.3%, density of polystyrene expanded beads molded body: 10.5 kg/m.sup.3, thermal conductivity of polystyrene expanded beads molded body: 0.033 W/m.Math.K
Foamed resin molded body C: The molded body was produced by filling a molding machine (manufactured by DAISEN INDUSTRY Co., Ltd., VS-500) with commercial polystyrene expanded beads (diameter: 1 to 5 mm) and heating the beads by steam to fusion-bond foamed particles to one another in a state where there were voids among the foamed particles. The continuous void ratio was controlled by adjusting the degree of pressurization. continuous void ratio: 43.9%, density of polystyrene expanded beads molded body: 10.5 kg/m.sup.3, thermal conductivity of polystyrene expanded beads molded body: 0.033 W/m.Math.K
Foamed resin molded body D: The molded body was produced by filling a molding machine (manufactured by DAISEN INDUSTRY Co., Ltd., VS-500) with commercial polystyrene expanded beads (diameter: 1 to 5 mm) and heating the beads by steam to fusion-bond foamed particles to one another in a state where there were voids among the foamed particles. The continuous void ratio was controlled by adjusting the degree of pressurization. continuous void ratio: 58.7%, density of polystyrene expanded beads molded body: 10.5 kg/m.sup.3, thermal conductivity of polystyrene expanded beads molded body: 0.033 W/m.Math.K
Foamed resin molded body E: The molded body was produced by filling a molding machine (manufactured by DAISEN INDUSTRY Co., Ltd., VS-500) with commercial polystyrene expanded beads (diameter: 1 to 5 mm) and heating the beads by steam to fusion-bond foamed particles to one another in a state where there were voids among the foamed particles. The continuous void ratio was controlled by adjusting the degree of pressurization. continuous void ratio: 69.4%, density of polystyrene expanded beads molded body: 10.5 kg/m.sup.3, thermal conductivity of polystyrene expanded beads molded body: 0.033 W/m.Math.K

TABLE-US-00006 TABLE 6 Amount of Foamed Continuous water of Shape resin void crystal- Fire retention Thermal Experiment molded ratio lization resistance Shape ratio conductivity No. body (%) (%) (MJ/m.sup.2) retention (%) (W/mK) Remarks 1-9 A 36.8 36.5 3.7 ○ 97.1 0.046 Example 6-1 B 25.3 36.4 6.9 ○ 95.5 0.041 Example 6-2 C 43.9 36.5 3.5 ○ 98.0 0.047 Example 6-3 D 58.7 36.5 3.3 ○ 99.1 0.049 Example 6-4 E 69.4 36.2 3.3 ○ 99.8 0.052 Example

[0095] From Table 6, it can be seen that by using a foamed resin molded body having appropriate continuous voids, excellent incombustibility, shape retention and heat-insulation properties were exhibited.

Experimental Example 7

[0096] Fire-resistant heat-insulation boards (length 1000 mm×width 1000 mm×thickness 25 mm) were prepared from fire-resistant heat-insulation compositions of Experiments No. 1-7, 1-9 and 4-1, and they were each assembled so as to form a fire-resistant structure shown in FIGS. 2 and 3, and the fire-resistant structure was set in a refractory furnace. The size of the fire-resistant structure was adjusted to width 2200 mm×length 1200 mm. The test was carried out by changing the type and the thickness of the fire-resistant heat-insulation composition of the fire-resistant heat-insulation board, and the state of combustion of the fire-resistant structure after the test was confirmed. Change of the thickness was carried out by changing the number of boards set. The results are set forth in Table 7.

Fire Resistance Test Methods

[0097] As shown in the side view of FIG. 2 and the top view of FIG. 3, the fire-resistant structure was set in a refractory furnace, and heating was carried out on the side of the siding board simulating an exterior wall, that is, flames from gas burners (five in total) were applied to heat the fire-resistant structure for 1 hour in accordance with a standard heating curve based on ISO 834. Thereafter, heating was terminated, and the state where the fire-resistant structure had been set in the refractory furnace was kept for 3 hours. The structure was removed from the refractory furnace, and the siding board on the heating side was peeled off to confirm the combustion state.

TABLE-US-00007 TABLE 7 Material Thickness composition of of fire-resistant Combustion state of fire-resistant Experiment fire-resistant heat- heat-insulation heat-insulation board at No. insulation board board (mm) the time of removing siding board Remarks 7-1 Experiment 25 Shape of fire-resistant heat-insulation board Comparative No. 1-7 was retained, but 80% or more of structural Example plywood and 80% or more of studs inside burned and were carbonized. 7-2 50 Shapes of two fire-resistant heat-insulation Comparative boards were retained, but 30% of structural Example plywood and 20% of studs inside burned and were carbonized. 7-3 Experiment 25 Shape of fire-resistant heat-insulation board Example No. 1-9 was retained, and studs did not burn, but 10% of structural plywood inside burned and was carbonized. 7-4 50 Shapes of two fire-resistant heat-insulation Example boards were retained, and structural plywood and studs inside did not burn at all. 7-5 Experiment 25 Shapes of two fire-resistant heat-insulation Example No. 4-1 boards were retained, and structural plywood and studs inside did not burn at all. 7-6 50 Shapes of two fire-resistant heat-insulation Example boards were retained, and structural plywood and studs inside did not burn at all.
The thickness of the fire-resistant heat-insulation board corresponds to the thickness X in FIG. 3.

[0098] From Table 7, it can be seen that as a result of evaluation of fire resistance of the fire-resistant structure constructed by using the fire-resistant heat-insulation board of the present invention, the fire resistance was enhanced. Particularly by laminating two fire-resistant heat-insulation boards together, the fire-resistant structure exhibited excellent fire resistance without burning of wood portion at all.

INDUSTRIAL APPLICABILITY

[0099] By using the fire-resistant heat-insulation composition according to the embodiment of the present invention and its slurry, a fire-resistant heat-insulation board having fire resistance and heat insulation properties can be obtained. When a structure such as a wall or a pillar is constructed by using the board, the structure can retain its shape even if it is exposed to a flame, so that the structure has an effect of inhibiting spread of fire in case of fire. Accordingly, the embodiment of the present invention can contribute to construction of buildings, vehicles, aircrafts, ships, freezing facilities and refrigerating facilities having high fire safety.