WO2022004749A1

WO2022004749A1 - Fire-resistant heat insulation composition, fire-resistant heat insulation composition slurry, fire-resistant heat insulation board, and fire-resistant heat insulation structure

Info

Publication number: WO2022004749A1
Application number: PCT/JP2021/024628
Authority: WO
Inventors: 和人田原; 浩徳長崎; 航平水田; 正憲三本; 芳範下條; 博伸吉川
Original assignee: 株式会社ジェイエスピー; デンカ株式会社
Priority date: 2020-07-01
Filing date: 2021-06-29
Publication date: 2022-01-06
Also published as: JPWO2022004749A1

Abstract

Provided is a fire-resistant heat insulation composition whereby it is possible to achieve suitable heat insulation properties and fire resistance.　The fire-resistant heat insulation composition includes: 5-100 parts by mass of gypsum with respect to 100 parts by mass of calcium sulfoaluminate including at least 40-70 mass% of hauyne and 5-30 mass% of belite; and 0.1-20 parts by mass of a fibrous inorganic clay mineral with a moisture content of at least 5% with respect to a total of 100 parts by mass of the calcium sulfoaluminate and the gypsum.

Description

Fireproof insulation composition, fireproof insulation composition slurry, fireproof insulation board and fireproof insulation structure

The present invention relates to a fire-resistant heat insulating composition, a fire-resistant heat insulating composition slurry, a fire-resistant heat insulating board, and a fire-resistant heat insulating structure for constructing a fire-resistant heat insulating structure of a building.

Various heat insulating materials and fireproof materials are used in buildings, and polyurethane foam, polystyrene foam, phenol foam, etc., which are resin foams with high heat insulating effect, light weight, and good workability, are used as heat insulating materials. We also use inorganic fiber aggregates such as glass wool and rock wool, which are inexpensive in terms of cost.

Since the resin foam is an organic substance, it burns in the event of a fire and often causes the damage to spread due to the spread of fire, so countermeasures are desired.

On the other hand, inorganic fiber aggregates such as glass wool and rock wool are mainly composed of non-combustible materials, but they tend to have higher thermal conductivity than resin foams and are inferior in heat insulation, and fibers. There was also a problem that the workability was inferior due to the piercing feeling due to the shape. Furthermore, conventionally, the method of packing the fiber aggregate in a plastic bag at the time of construction and fitting it between the pillar and the outer wall of the house has been adopted, but a gap may occur or it may fall off over time. There was a problem such as.

On the other hand, a heat insulating material that imparts nonflammability to a resin foam is already on the market. For example, a non-combustible heat insulating board having a structure in which one side or both sides of a phenolic foam board is laminated with aluminum foil, aluminum hydroxide paper, a sekko-based plate material or the like which is a non-combustible material can be mentioned. However, although these conventional non-combustible heat insulating boards do not burn on the surface facing the flame in the event of a fire, the heat melts the phenolic foam inside and creates cavities, and the problem that the board itself falls off and spreads the fire can be solved. However, it is not a material that satisfies the fireproof structural specifications stipulated by the Building Standards Law.

To exemplify the existing techniques for improving the burn resistance of resin foams, for example, as a technique for improving the burn resistance of polyurethane foams, foams are formed with alkali metal carbonates, isocyanates, water and reaction catalysts. Technology related to heat insulating materials (Patent Document 1) and hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, hoe, which are selected from the group consisting of lithium, sodium, potassium, boron, and aluminum. A curable composition consisting of one or more kinds of inorganic compounds selected from the group consisting of salts and phosphates, water and isocyanates, and a technique mainly for an injection material for improving the ground of a tunnel (Patent Document). 2) is known.

However, the prior art of Patent Document 2 was developed for ground improvement and is not intended to obtain heat insulating properties. In particular, as in Patent Document 1, in the conventional method of reacting an aqueous solution of alkali metal carbonate of 30% or more with isocyanates, a large amount of unreacted water remains due to the use of a large amount of water, so that a heat insulating material is used. It is considered that the heat insulating property is not large because it needs to be dried in order to be used as an aqueous solution and the bubble size of the obtained foam is large.

As a technique for coating a synthetic resin foam to improve combustion resistance, foam particles of a synthetic resin formed a coating composed of sepiolite and an aqueous organic binder containing a water-soluble resin as a main component and subjected to surface treatment. In addition, a technique relating to a heat-insulating coated granule that is further coated with a coating material consisting of an aqueous inorganic binder containing an inorganic powder and water glass containing an alkali metal silicate as a main component and dried and cured (Patent Document 3). The bubble structure on the surface of at least a part of the synthetic resin foam was filled with a silica-based inorganic substance consisting of one or a mixture of calcium silicate, magnesium silicate, aluminum silicate, and aluminosilicate. A technique relating to an inorganic-containing synthetic resin foam (Patent Document 4) is disclosed.

However, in the conventional technique using these silicates, it is considered difficult to maintain the shape as a heat insulating board because the resin foam melts and the filling force of the silicate itself is lost and powdered by combustion. ..

Bead method In a foamed resin formed of polystyrene foam, a technique relating to a foamed resin composite structure in which a packing material made of an organic substance having an oxygen index of greater than 21 is filled in communication voids formed between the foamed beads (Patent Document 5). ), And a technique for a composite molded body in which the voids of a thermoplastic resin foamed particle molded article having communicating voids and a void ratio of 5 to 60% are filled with a cured product of cement or gypsum containing smectite. (Patent Document 6) is known.

However, in Patent Document 5, since the communication void is filled with a filling material which is an organic substance, improvement in combustion resistance at a non-combustible level cannot be expected. Patent Document 5 is intended for expanded polystyrene foam having a very solid void in the foam having a void ratio of about 3%, and it cannot be said that the void can be effectively used. Patent Document 6 preferably contains ettringite in the cured product as a cement, and exemplifies the cement containing ettringite by a trade name, and describes that it contains smectite, which is considered to be one of the material separation reducing materials. However, there is no description about the calcium sulfate of the present invention as a cement for producing ettringite.

Patent Document 7 contains calcium aluminate having a CaO content of 40% by mass or more, sucrose, an inorganic powder having a hollow structure with an average particle size of 20 to 60 μm, and a waste glass foam powder having an average particle size of 20 to 130 μm. Although the composition is described, it is different from the present invention because it contains calcium aluminate as a main component. It is considered that the material described in Patent Document 8 is used for the purpose of covering the surface of the steel frame and protecting it from a fire, and does not have a large heat insulating property.

Further, it is a heat insulating material containing isocyanate, an active hydrogen-containing compound, water, a reaction catalyst, and Auin hydrate and having a density of 350 kg / m ³ or less, and Auin hydrate is (1) cement and (2) cement. ) A hydrate obtained by mixing an Auin-containing substance and (3) water, and (2) a heat insulating material in which the Auin-containing substance contains free lime, anhydrous sucrose, Auin, and calcium aluminoferrite. (Patent Document 9), but it differs from the present invention in that the produced Auin hydrate is used.

It is a fire-resistant coating composition characterized by containing ettringite as a main component, and further contains an inorganic compound powder or granular material or titanium oxide powder or granular material that releases nonflammable gas at 100 to 1000 ° C. Compositions for use (Patent Document 10) are also known.

Technologies related to non-firing fireproof heat insulating materials consisting of heat-resistant aggregates, lightweight aggregates, alumina-based binders, silicon carbide, and reinforcing fibers have been disclosed. It is described (Patent Document 11).

Japanese Unexamined Patent Publication No. 10-67576 Japanese Unexamined Patent Publication No. 8-92555 Japanese Unexamined Patent Publication No. 2001-329629 Japanese Unexamined Patent Publication No. 2012-102305 Japanese Patent No. 4983967 JP-A-2015-199945 JP-A-2017-77994 Japanese Unexamined Patent Publication No. 7-48153 Japanese Unexamined Patent Publication No. 2016-160145 Japanese Unexamined Patent Publication No. 7-61841 Japanese Unexamined Patent Publication No. 62-417774

However, even the above-mentioned prior arts of Patent Documents 10 and 11 are premised on being used as a refractory heat insulating material in a high temperature region used in steelmaking and steelmaking, and the heat insulating property under normal environment and the fire resistance at the time of fire are insufficient. Met. Therefore, there has been a demand for a method capable of achieving both good heat insulation and fire resistance.
From the above, it is an object of the present invention to provide a refractory heat insulating composition capable of achieving both good heat insulating properties and fire resistance.

As a result of various studies, the present inventors have obtained the finding that a refractory heat insulating composition capable of solving the above-mentioned problems and achieving both good heat insulating property and fire resistance can be obtained by using a specific composition. This has led to the completion of the present invention. That is, the present invention is as follows.

[1] With respect to 100 parts by mass of calcium sulfate containing at least 40 to 70% by mass of Auin and 5 to 30% by mass of belite, 5 to 100 parts by mass of sekkou is contained, and the calcium sulfoluminate and the above. A fireproof heat insulating composition containing 0.1 to 20 parts by mass of a fibrous inorganic clay mineral having a water content of 5% by mass or more with respect to a total of 100 parts by mass of calcium.
[2] The refractory heat insulating composition according to [1], which comprises an inorganic powder having pores.
[3] The refractory heat insulating composition according to [1] or [2], which comprises a setting retarder.
[4] The refractory heat insulating composition according to any one of [1] to [3], which comprises a hydration accelerator.
[5] A refractory heat insulating composition slurry obtained by mixing water with the refractory heat insulating composition according to any one of [1] to [4].
[6] A refractory heat insulating board formed by filling the voids of a resin molded body having a continuous void ratio of 25 to 70% by volume with the refractory heat insulating composition slurry according to [5] and solidifying the slurry.
[7] A refractory insulation structure including the refractory insulation board according to [6].

According to the present invention, it is possible to provide a refractory heat insulating composition capable of achieving both good heat insulating properties and fire resistance.
Therefore, by using the refractory heat insulating composition of the present invention and its slurry, a refractory heat insulating board having both good fire resistance and heat insulating property can be obtained.

It is a schematic diagram of the crystal structure of a fibrous inorganic clay mineral (sepiolite). It is a side view which shows the structure of a fireproof structure. It is a top view which shows the structure of a fireproof structure.

Hereinafter, the present invention will be described in detail. Unless otherwise specified, parts and% in the present specification are shown on a mass basis. Unless otherwise specified, the numerical range in the present specification shall include the upper limit value and the lower limit value.

[Fireproof insulation composition]
The refractory heat insulating composition according to the embodiment of the present invention (hereinafter, may be simply referred to as “composition”) is a calcium sulfate containing at least 40 to 70% by mass of Auin and 5 to 30% by mass of Belite. A fibrous inorganic clay mineral having a water content of 5% or more is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass, and a fibrous inorganic clay mineral having a water content of 5% or more is contained in an amount of 0.1 to 100 parts by mass with respect to a total of 100 parts by mass of calcium sulfoluminate and sekko. Contains 20 parts by mass.

(Calcium sulfoluminate)
_{The calcium sulfoluminate is CaO, Al 2} O ₃ and SO ₃ obtained by mixing a calcia raw material, an alumina raw material, a sulfer raw material and the like, firing in a kiln, or melting and cooling in an electric furnace. It is a general term for substances having hydration activity whose main component is.

The calcium sulfoluminate is not particularly limited, but is different from the calcium sulfoluminate used for the expansion material defined in JIS A 6202. It is similar in that it contains Auin and that ettringite is a hydration product, but the calcium sulfoluminate contains belite, is used in combination with gypsum, and is an admixture for cement. It is different from the expansion material defined in JIS A6202 in that it is used as the main component.

The content of hauyne in calcium sulfoluminate is 40 to 70%, preferably 45 to 70%, more preferably 50 to 70%. If the content of hauyne is less than 40%, the fire resistance is inferior, and if it exceeds 70%, further improvement in fire resistance cannot be expected.
The content of belite in calcium sulfoluminate is 5 to 30%, preferably 5 to 20%, and more preferably 5 to 15%. If the content of belite is less than 5%, it becomes difficult to secure the pot life and the long-term strength development becomes low, resulting in poor fire resistance, and if it exceeds 30%, the fire resistance is poor. Will end up.

Furthermore as the calcium monkeys follower aluminate, part of the calcium monkeys follower aluminate CaO, Al ₂ O _3, or the can, alkali metal oxides, alkaline earth metal oxides, silicon oxide, titanium oxide, iron oxide, an alkali metal halide Compounds substituted with compounds, alkaline earth metal halides, alkali metal sulfates, alkaline earth metal sulfates and the like can also be used.

Furthermore as the calcium monkeys follower aluminate, as minerals other than Auin and belite, CaO 25% upper _{_{limit, 12CaO · 7Al 2 O 3,}} 2CaO · Al 2 O 3 · SiO 2, 3CaO · Al 2 O 3, 4CaO -Al ₂ O ₃ , Fe ₂ O ₃ and CaSO _{4 and the} like can be contained. If it is 25% or less, it does not adversely affect the fire resistance and pot life.

The particle size of calcium sulfoluminate is preferably a brain specific surface area of 3,000 cm ² / g or more, and more preferably 4,000 cm ² / g or more, in terms of initial strength development. When it is 3,000 cm ² / g or more, the initial strength development is improved. Here, the brain specific surface area is a value measured in accordance with JIS R5201: 2015 (physical test method for cement).

(Gypsum)
As the gypsum contained in the present composition, any of anhydrous gypsum, semi-water gypsum, and dihydrate gypsum can be used, and the gypsum is not particularly limited. The anhydrous gypsum is a generic name of the compound represented by the molecular formula comprising CaSO ₄ with calcium sulfate anhydrite, the hemihydrate gypsum is a general term for CaSO 4 · 1 _/ 2H 2 _O comprising molecular compound represented by the formula, gypsum and _is a generic name of the compound represented by CaSO 4 · _2H 2 O made molecular formula.

The particle size of gypsum is preferably 1 to 30 μm, more preferably 5 to 25 μm, in terms of nonflammability, initial strength development, and appropriate working time. Here, the average particle size is a value measured in a dispersed state using a measuring laser diffraction type particle size distribution meter and an ultrasonic device.

The content of gypsum in this composition is 5 to 100 parts by mass, preferably 15 to 50 parts by mass with respect to 100 parts by mass of calcium sulfoluminate. If the amount of gypsum is less than 5 parts by mass or more than 100 parts by mass, sufficient fire resistance cannot be imparted.

(Fibrous inorganic clay mineral)
The fibrous inorganic clay mineral contained in this composition (hereinafter, also referred to simply as "fibrous mineral") needs to have a water content of at least 5% or more in order to obtain heat insulating properties and fire resistance. .. The fibrous inorganic clay mineral gives the composition a material separation reducing effect and also improves the fire resistance.

FIG. 1 shows a schematic diagram of the crystal structure of a fibrous inorganic clay mineral (sepiolite in FIG. 1) (according to the structural models of Brauner and Pressinger. See JP-A-2004-59347 and JP-A-2002-338236). The fibrous mineral is a kind of hydrous magnesium silicate mineral, and is a fibrous clay mineral characterized by having a crystal structure as shown in FIG. 1 and having pores inside the crystal. , Water of crystallization exists in the pores in the form of bound water or silicate water.

According to FIG. 1, two-dimensional crystal structures form fibrous crystal structures that are alternately stacked like bricks. As shown in FIG. 1, this unit crystal structure contains four hydroxyl groups bonded to Mg atoms, four bound water bonded to Mg atoms, and eight zeolite waters. FIG. 1 shows that there are eight zeolite waters in the unit structure.

The fibrous mineral has a specific surface area of 50 to 500 m ² / g, an average fiber length of 0.1 to 50 μm, and an aspect ratio indicated by an average fiber length / average fiber diameter of 5, although it varies depending on the type. It is preferably about 5000. Here, the specific surface area is a value measured according to the BET method, JIS Z8830: 2013. The average fiber length and the average fiber diameter are the values obtained by image analysis of the SEM photograph taken.

The fibrous minerals are not particularly limited, but typical ones are sepiolite ((OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ / 6-8H ₂ O) and parigolite (atapaljite) ((OH). ₂ ) ₄ (OH) ₂ Mg ₅ Si ₈ O ₂₀・ 4H ₂ O), wollastonite, loglinite and the like. Among these, one or more selected from sepiolite and parigolite (atapaljite) are preferable.

From the viewpoint of good fire resistance and heat insulating properties, the water content of the fibrous mineral is 5% or more, preferably 7% or more, and more preferably 9% or more. The upper limit of the water content is not particularly limited, but is preferably 30% or less, for example. The fibrous mineral was heated from 30 ° C to 200 ° C by a thermogravimetric analyzer (TGA), and the mass X before the temperature rise and the reduced mass (mass decreased when the temperature was raised from 30 ° C to 200 ° C) X1 were used. The water content W can be calculated from the following formula. The sample amount was measured under the conditions of 10 mg, a heating rate of 5.0 ° C./min, and an air atmosphere.
Moisture content W (mass%) = (X1 / X) x 100

The content of the fibrous mineral in this composition is 0.1 to 20 parts, preferably 3 to 15 parts, relative to 100 parts in total of calcium sulfoluminate and gypsum. If the amount of the fibrous mineral is less than 0.1 part, the fire resistance and heat insulating property may not be improved, and if it exceeds 20 parts, the fire resistance and heat insulating property may be lowered. The fibrous mineral may be premixed with calcium sulfoluminate or gypsum in advance, or may be dispersed in water in advance for use.

(Inorganic powder with pores)
In a preferred embodiment, the composition may further contain an inorganic powder having pores (hereinafter, may be simply referred to as “inorganic powder”). The inorganic powder is not particularly limited as long as it is a powder of an inorganic material having pores, and any powder can be used.

Typical examples of inorganic powder having pores are inorganic powder obtained from foam formed by heating volcanic deposits such as silas balloon at high temperature, and fly ash balloon generated from thermal power plant. Examples thereof include inorganic powder obtained by firing black stone, pearl rock, or shale, and waste glass foam powder (recycled glass balloon) whose grain size is adjusted by firing after crushing waste such as glass bottles. One or more of these can be used. When using a fly ash balloon, it is preferable to use one having a loss on ignition of 5% or less because the amount of unburned carbon is small. In the present specification, the inorganic powder excludes the above-mentioned calcium sulfate, gypsum, and fibrous inorganic clay minerals.

Among these, one or more of the group consisting of Shirasu balloon, fly ash balloon, and waste glass foam powder is preferable because the heat insulating property is not easily impaired when the open cells of the foamed resin molded product are filled.

The particle size of the inorganic powder is preferably an average particle diameter of 1 to 150 μm, more preferably 15 to 100 μm. Here, the average particle size is a value measured in a dispersed state using a measuring laser diffraction type particle size distribution meter and an ultrasonic device.

The content of the inorganic powder in the present composition is preferably 2 to 100 parts, more preferably 5 to 80 parts, based on 100 parts in total of calcium sulfoluminate and gypsum. When the amount of the inorganic powder is 2 parts or more, the heat insulating property is improved, and when the amount is 100 parts or less, the fire resistance is improved.

(Condensation retarder)
In a preferred embodiment, the composition may further contain a condensation retarder. The condensation retarder is a substance that adjusts the pot life of the refractory heat insulating composition slurry. Examples of the condensation retarder include an inorganic condensation retarder and an organic condensation retarder. Examples of the inorganic setting retarder include phosphate, silicate, copper hydroxide, boric acid or a salt thereof, zinc oxide, zinc chloride, zinc carbonate and the like. Examples of the organic setting retarder 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 sugar. Examples include sugars and the like. One or more of these can be used. Further, a mixture of an inorganic setting retarder such as carbonate, bicarbonate, nitrate, hydroxide, silicate and the like and the above oxycarboxylic acids or salts thereof can also be used. Among these, oxycarboxylic acids or salts thereof alone or a mixture of an inorganic condensation retarder and oxycarboxylic acids or salts thereof is preferable. In the present specification, the setting retarder excludes the above-mentioned calcium sulfate, gypsum, fibrous inorganic clay mineral, and inorganic powder having pores.

The content of the setting retarder in the present composition is preferably 0.02 to 2.0 parts, more preferably 0.05 to 1.0 parts, based on 100 parts in total of calcium sulfoluminate and gypsum. When the amount of the setting retarder is 0.02 part or more, it becomes easy to adjust to the required pot life, and when it is 2.0 parts or less, the curing time does not become too long and curing failure is unlikely to occur.

In a preferred embodiment, the composition may further contain a hydration accelerator. The hydration accelerator is a substance that promotes the reaction between calcium sulfoluminate and gypsum to increase the amount of crystalline water and improve the fire resistance, and is not particularly limited. Examples of the hydration accelerator include hydroxides such as calcium hydroxide, alkali metal silicates, aluminum sulfate such as anhydrous aluminum sulfate, alkali metal carbonates such as sodium carbonate, nitrates, nitrites, and ordinary Portland cement. Various Portland cements, various inorganic filler fine powders and the like can be mentioned, and one or more of these can be used. In the present specification, the hydration accelerator excludes the above-mentioned calcium sulfate, gypsum, fibrous inorganic clay mineral, inorganic powder having pores, and a setting retarder.

The content of the hydration accelerator in the present composition is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts with respect to 100 parts in total of calcium sulfoluminate and gypsum. When the amount of the hydration promoter is 0.1 part or more, a sufficient hydration promoting effect can be obtained, and when the amount is 15 parts or less, a sufficient pot life can be secured.

The content of calcium sulfate in the refractory heat insulating composition according to the embodiment of the present invention is preferably 50 to 95%, more preferably 60 to 90% from the viewpoint of fire resistance.

[Refractory Insulation Composition Slurry]
The refractory heat insulating composition slurry according to the embodiment of the present invention is made by mixing the above-mentioned refractory heat insulating composition and water. That is, the refractory heat insulating composition slurry can be prepared by using the above-mentioned fire resistant heat insulating composition and water (tap water or the like). The amount of water when preparing the slurry is not particularly limited, but is preferably 40 to 300 parts by mass, more preferably 80 to 250 parts by mass with respect to 100 parts by mass of the total of calcium sulfoluminate and gypsum. preferable. When the amount of water is 40 parts by mass or more, the filling into the void becomes uniform and the fire resistance is improved, and when it is 300 parts by mass or less, the ettringite content in the cured body in the void increases and the fire resistance is improved. Sex improves.

[Fireproof insulation board]
The refractory heat insulating board according to the embodiment of the present invention is solidified by filling the voids of the resin molded body having a continuous void ratio of 25 to 70% by volume with the refractory heat insulating composition slurry according to the embodiment of the present invention. ..

The refractory heat insulating composition slurry according to the embodiment of the present invention is filled in the voids of a resin molded product having a continuous void ratio of 25 to 70% by volume (hereinafter, may be simply referred to as “resin molded product”) and solidified. Therefore, the fireproof heat insulating board according to the embodiment of the present invention can be manufactured.

The resin molded product is a resin having continuous voids and has voids that can be filled with the slurry. Examples of the type of resin include foamed polyvinyl alcohol resin, foamed polyurethane resin, foamed polystyrene resin, foamed polyolefin resin, foamed phenol resin and the like. Granular foams having closed cells and having a diameter of several mm, which are made of these resins, are packed in a mold and heat-pressed to form a resin molded body so that continuous voids are formed between the granular foams. can get. The continuous void ratio of the resin molded product can be adjusted by the degree of pressurization during manufacturing. As for polystyrene resin, a resin molded body having continuous voids can be manufactured according to the method for manufacturing polystyrene foam by the bead method. Among these, expanded polystyrene resin molded products are preferable from the viewpoint of versatility. When the continuous void ratio is 25% by volume or more, sufficient fire resistance can be imparted to the obtained board, and when it is 70% by volume or less, the board density becomes small, the thermal conductivity becomes small, and the heat insulating property is improved. ..
The continuous void ratio V of the resin molded product can be obtained by, for example, the following method.
First, a rectangular parallelepiped sample is cut out from a resin molded body left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more, and an apparent volume (Va) is obtained from the external dimensions of the sample. The sample is then submerged in a graduated cylinder containing ethanol at a temperature of 23 ° C. using a wire mesh tool, and light vibration is applied to degas the air present in the voids in the molded product. Then, the water level rise is read in consideration of the volume of the wire mesh tool, and the true volume (Vb) of the sample is measured. From the obtained apparent volume (Va) and true volume (Vb) of the sample, the continuous void ratio (V) can be obtained by the following equation.
Continuous void ratio V (%) = [(Va-Vb) / Va] × 100

The slurry filled in the continuous voids produces a hydration product due to the hydration reaction and solidifies (cures). The continuous voids in the resin molding are filled with the hydration product. Examples of the hydration product include ettringite produced by the reaction of calcium sulfoluminate with gypsum. Since ettringite has a large amount of water in the molecule as water of crystallization, it dehydrates by heating, exhibits a fire extinguishing effect, and imparts nonflammability to the resin molded product.

The method for filling the resin molded product with the fire-resistant heat insulating composition slurry is not particularly limited, but the method is to press-fit with compressed air, depressurize with a vacuum pump and fill by suction, or install the resin molded product on a vibration table. Examples thereof include a method of filling the voids while applying a vibration of 30 to 60 hertz. Among these, from the viewpoint of quality stability, a method of filling the voids while applying vibration is preferable.

The method for curing the refractory heat insulating board after filling the voids with the refractory heat insulating composition slurry is not particularly limited, but after filling, the refractory heat insulating board can be cured in the air at room temperature, or the board surface can be covered with a plastic film at room temperature. Examples include a method of curing in the air. The refractory insulation board may be cured at a temperature of 30 to 50 ° C. in order to shorten the curing time.

In some embodiments, the entire board may be further covered with a non-woven fabric, a reinforcing material such as a lattice-shaped fiber sheet may be arranged on one side or both sides of the board, or the non-woven fabric and the fiber sheet may be used in combination.

The shape of the refractory heat insulating board of the present invention is not particularly limited, but is preferably 500 to 1000 mm in length, 1000 to 2000 mm in width, and 10 to 100 mm in thickness. The thickness is more preferably 50 to 100 mm. The smaller the size, the lighter the fireproof insulation board and the better the workability during installation.

In a certain embodiment, one or more of various additives can be used in the preparation of the present refractory heat insulating composition slurry as long as the performance is not affected. Examples of such additives include surfactants, air entrainers, carbonization accelerators, flame retardant-imparting agents, fire spread inhibitors, inorganic substances, rust inhibitors, antifreeze agents, shrinkage reducing agents, clay minerals, anion exchangers and the like. Can be mentioned.

The density of the refractory heat insulating board according to the embodiment of the present invention ^{is preferably 100 to 800 kg / m 3 and} more preferably 200 to 500 kg / m ^{3 in} that the fire resistance and the heat insulating property are not impaired. When it is 100 kg / m ³ or more, sufficient fire resistance can be ensured, ^{and when it is 800 kg / m 3} or less, sufficient heat insulating property can be obtained.

[Fireproof insulation structure]
The fireproof heat insulating structure according to the embodiment of the present invention includes a fireproof heat insulating board. That is, the fireproof structure of the building can be constructed by using the fireproof heat insulating board described above. Such a fireproof structure includes, for example, a siding board, a moisture permeable waterproof sheet, a fireproof heat insulating board, a structural plywood, and a fireproof heat insulating board in the order of the layer structure from the outer wall side, and the structural plywood and the fireproof structure. An example is a structure in which a space of about 100 mm (a space in which a heat insulating material such as glass wool can be accommodated) is provided between studs (studs in FIG. 3) between the heat insulating boards. A furring strip may be provided between the siding board and the breathable waterproof sheet (see FIG. 3).

According to the embodiment of the present invention, a fireproof heat insulating structure including a fireproof heat insulating board can be obtained. When constructing a fireproof structure, depending on the required fireproof specifications, a plurality of the fireproof heat insulating boards may be stacked and attached, or the fireproof heat insulating board may be used in combination with the reinforced gypsum board.

Hereinafter, the contents will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

"Experimental Example 1"
The foamed resin molded body A (size: length 20 cm × width 20 cm × thickness 5 cm) having continuous voids was reinforced with alkali-resistant glass fiber at the lower portion in the thickness direction, and a polyester non-woven fabric was further layered. This is set in a vibration impregnation device, a refractory heat insulating composition slurry having the composition shown in Table 1 is poured onto the upper surface of the molded body, vibration of 60 hertz is applied for 1 minute, and the void is impregnated with the refractory heat insulating composition slurry to impregnate the fire resistant heat insulating composition board. Manufactured. After filling, the refractory heat insulating board was taken out from the apparatus and cured at room temperature for 3 days. The cured fireproof heat insulating board was evaluated for water of crystallization content, fire resistance, shape retention, shape retention and thermal conductivity. The results are shown in Table 1.

(Material used)
Foamed resin molded body A: Commercially available polystyrene foam beads (diameter 1 to 5 mm) are filled in a molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) and heated by steam to have voids between the foamed particles. It was manufactured by fusing the foamed particles together in this state. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio 36.8%, density of polystyrene foam beads 10.5 kg / m ³ , thermal conductivity of polystyrene foam bead molded body 0.033 W / (m · K)

Calcium monkey follower aluminate 1 (CSA1): CaO raw material, blended with _Al 2 _{O 3} raw material, and CaSO ₄ material, after mixing and grinding, using an electric furnace, to synthesize clinker was heat-treated for 3 hours at 1300 ° C., Prepared by grinding with a ball mill. Hauyne: 69%, Beelite: 10%, Other minerals: 12%, Brain specific surface area 4800 cm ² / g

Calcium monkey follower aluminate 2 (CSA2): CaO raw material, blended with _Al 2 _{O 3} raw material, and CaSO ₄ material, after mixing and grinding, using an electric furnace, to synthesize clinker was heat-treated for 3 hours at 1300 ° C., Prepared by grinding with a ball mill. Hauyne: 55%, Beelite: 24%, Other minerals: 16%, Brain specific surface area 4900 cm ² / g

Calcium monkey follower aluminate 3 (CSA3): CaO raw material, blended with _Al 2 _{O 3} raw material, and CaSO ₄ material, after mixing and grinding, using an electric furnace, to synthesize clinker was heat-treated for 3 hours at 1300 ° C., Prepared by grinding with a ball mill. Hauyne: 42%, Beelite: 29%, Other minerals: 25%, Brain specific surface area 4950 cm ² / g

Ethringite 1 (ET1): Ethringite powder obtained by filtering and drying hydrothermally synthesized slaked lime, aluminum sulfate and gypsum as starting materials, water of crystallization: 46%

Gypsum 1 (CS1): Type II anhydrous gypsum manufactured by Noritake Company, trade name D-101A, purity 95%, average particle diameter 20 μm

Gypsum 2 (CS2): β-type half-water gypsum manufactured by Noritake Company, trade name FT-2, purity 95%, average particle diameter 20 μm

Gypsum 3 (CS3): Nisui Gypsum manufactured by Noritake Company, trade name P52B, purity 95%, average particle diameter 20 μm

Fibrous mineral (F1): Sepiolite manufactured by TORSA, trade name: PANGEL AD, water content: 13.2%, average fiber length 5 μm, average fiber diameter 0.1 μm, specific surface area 320 m ² / g

Fibrous mineral (F2): Parisolskite (Attapulsite) manufactured by Active Military International, trade name: MIN-U-GEL 200, water content: 9.8%, average fiber length 5 μm, average fiber diameter 0.1 μm, specific surface area 270 m. ² / g

Fibrous mineral (F3): Wollastonite manufactured by Kansai Matek Co., Ltd., trade name: KTP-H02, water content: 2.0%, average fiber length 75 μm, average fiber diameter 10 μm, specific surface area 4200 cm ² / g

Non-fibrous mineral (N1): Bentonite manufactured by Kunimine Kogyo Co., Ltd., trade name: Kunigel V1, water of crystallization: 3.5%, specific surface area 60 m ² / g, layered

Water: Tap water

(Preparation and preparation amount of refractory heat insulating composition slurry)
(1) When calcium sulfate is used A mixture is prepared by adding gypsum in an amount shown in Table 1 to 100 parts by mass of calcium sulfate (CSA1 to 3), and the mixture is prepared with respect to 100 parts by mass of the mixture. Then, fibrous minerals (F1 to F3) or non-fibrous minerals (N1) were added in the type and amount shown in Table 1 and 100 parts by mass of water, and stirred for 5 minutes to prepare a slurry (fireproof heat insulating composition slurry). .. The prepared slurry was poured onto the upper surface of the foamed resin molded body so as to have a size ^{of 810 cm 3 (1.1 times the amount of voids in the resin molded body).}

(2) When synthetic ettringite is used In the case of using synthetic ettringite (ET1), a mixture of fibrous minerals (F1) in a predetermined ratio shown in Table 1 with respect to 100 parts by mass of the synthetic ettringite. Was prepared, water was added so as to be 100 parts by mass with respect to 100 parts by mass of the mixture, and the mixture was stirred for 5 minutes to prepare a slurry (fireproof heat insulating composition slurry). The prepared slurry was poured onto the upper surface of the foamed resin molded body so as to have a size ^{of 810 cm 3 (1.1 times the amount of voids in the resin molded body).}

(Measuring method)
Continuous void ratio: The continuous void ratio of the foamed resin molded product was determined as follows. First, the apparent volume (Va) was obtained from the external dimensions (length 10 cm × width 10 cm × thickness 5 cm) of the foamed resin molded body left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and the sample was subjected to a temperature of 23. It was submerged in a graduated cylinder containing ethanol at ° C using a wire mesh tool, and the air existing in the voids in the molded body was degassed by applying a light vibration. Then, the water level rise is read in consideration of the volume of the wire mesh tool, and the true volume (Vb) of the sample is measured. From the obtained apparent volume (Va) and true volume (Vb) of the sample, the continuous void ratio (V) was obtained by the following equation.

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

Content of water of crystallization (water of crystallization): 20 g was sampled from a fire-resistant heat insulating board, free water and foam in the cured product were dissolved with acetone, filtered, and the residue was thoroughly washed with acetone to create an environment of 25 ° C. Below, vacuum dried in a desiccator for 48 hours. The amount of crystalline water was determined by measuring the mass reduction rate (%) of the dried cured product (residue) in the range of 50 to 200 ° C. with a thermal analyzer (heating rate: 10 ° C./min, in air).
The water of crystallization in the present specification refers to chemically or physically bonded water contained in the fireproof heat insulating board, excluding free water that can be removed by drying such as acetone.

Fire resistance: A heat generation test using a cone calorie meter shown in ISO-5660-1: 2002 was carried out, and the fire resistance was simply evaluated. Using a test piece of 10 cm in length × 10 cm in width × 5 cm in thickness obtained from a refractory heat insulating board, the total calorific value when the heating time is 20 minutes is 8 MJ / m ² or less, which is fire resistance (non-combustible). ) Is preferable.

Thermal conductivity: Measured with a rapid thermal conductivity meter (box type probe method) using a test piece having a length of 10 cm, a width of 5 cm, and a thickness of 5 cm obtained from a refractory heat insulating board.
It can be said that the lower the thermal conductivity, the higher the heat insulating property. The thermal conductivity is preferably 0.070 W / mK or less.

Shape retention: If there are no cracks, cracks, collapses, defects, or shrinkage in the test piece after the combustion test (fire resistance test) using a cone calorie meter, ○, if cracks, cracks, collapses, or defects are confirmed. It was marked as x.

Shape retention: By comparing the volume of the test piece after the combustion test (fire resistance test) with the cone calorimeter with the volume of the test piece before the test, the shape retention ((volume of the test piece after the test / volume before the test) The volume of the test piece) × 100 (%)) was measured.

The amount of gypsum (CS) in Table 1 above is a mass portion with respect to 100 parts by mass of calcium sulfoluminate (CSA). The amount of the fibrous mineral (F) is parts by mass with respect to 100 parts by mass of the mixture of calcium sulfoluminate (CSA) and gypsum (CS). In addition, Experiment No. In 1-22, 5 parts by mass of fibrous mineral (F1) and 5 parts by mass of fibrous mineral (F2) are mixed with 100 parts by mass of a mixture of calcium aluminate (CA) and sekkou (CS). used.

From Table 1, the amount of crystalline water in the packed cured product, for example, the amount of crystalline water in ettringite, is greatly increased by using calcium sulfate, gypsum, and fibrous minerals that satisfy the predetermined conditions. That is, since fibrous minerals contribute to the reaction between calcium sulfate and gypsum, the ettringite content ratio can be increased, and fire resistance, shape retention, and thermal conductivity can be improved. On the other hand, in the comparative example using synthetic ettringite, it can be seen that the amount of crystalline water does not increase due to the use of fibrous minerals. In the comparative example, most of the water added when preparing the slurry exists as free water instead of water of crystallization, so that the free water is easily lost when it is dried or heated over time, and the example plays a role. It is considered that the effect cannot be obtained.

"Experimental Example 2"
The types and amounts of inorganic powder shown in Table 2 are as shown in Table 2 for 100 parts by mass of calcium sulfoluminate (CSA1), 50 parts by mass of gypsum (CS1), and 100 parts by mass of a mixture of calcium sulfoluminate and gypsum. , 7 parts by mass of fibrous mineral (F1) and 100 parts by mass of water were added to prepare a fire-resistant heat insulating composition slurry in the same manner as in Experimental Example 1, and the performance was evaluated. The results are shown in Table 2.

(Material used)
Inorganic powder 1 (P1): Shirasu balloon manufactured by AXYZ Chemical Co., Ltd., trade name: MSB-301, average particle diameter 50 μm
Inorganic powder 2 (P2): Shirasu balloon manufactured by AXYZ Chemical Co., Ltd., trade name: ISM-F015, average particle diameter 22 μm
Inorganic powder 3 (P3): Shirasu balloon manufactured by AXYZ Chemical Co., Ltd., trade name: MSB-5011, average particle diameter 96 μm
Inorganic powder 4 (P4): Fly ash balloon manufactured by Tomoe Engineering Co., Ltd., trade name: Senolite SA, average particle diameter 80 μm
Inorganic powder 5 (P5): Waste glass foam powder manufactured by DENNERT PORAVER GMBH, trade name: Traveler (0.04-0.125 mm particle size product), average particle diameter 90 μm

In Table 2 above, the amount of the inorganic powder (P) is a mass part with respect to 100 parts by mass of a mixture of calcium sulfoluminate (CA) and gypsum (CS). Experiment No. In 2-13, 7 parts by mass of the inorganic powder (P1) and 7 parts by mass of the inorganic powder (P4) are mixed with 100 parts by mass of the mixture of calcium sulfate (CA) and gypsum (CS). used.

From Table 2, it can be seen that the refractory heat insulating composition further contains the inorganic powder to improve the heat insulating property while maintaining excellent fire resistance and shape retention.

"Experimental Example 3"
The types and amounts of the setting retarder are shown in Table 3 for 100 parts by mass of calcium sulfate (CSA1), 50 parts by mass of gypsum (SC1), and 100 parts by mass of the mixture of calcium aluminate and gypsum. 7 parts by mass of fibrous mineral (F1) and 100 parts by mass of water were added to prepare a fire-resistant heat insulating composition slurry in the same manner as in Experimental Example 1, and the performance was evaluated. The gelation time was also evaluated. The results are shown in Table 3.

(Material used)
Condensation retarder (R1): Reagent 1st grade sodium citrate Coagulation retarder (R2): Reagent 1st grade tartrate Coagulation retarder (R3): Reagent 1st grade sodium gluconate

(Measuring method)
Gelling time: The prepared refractory heat insulating composition slurry was placed in a polybeaker, placed in a heat insulating container, and a resistance temperature detector was inserted. The time at which the temperature rose by 2 ° C. due to the heat generated by the curing of the mortar with respect to the temperature immediately after the kneading was completed by the recorder was defined as the gelling time.

In Table 3 above, the amount of the setting retarder (R) is a mass portion with respect to 100 parts by mass of the mixture of calcium sulfoluminate (CSA) and gypsum (CS).

From Table 3, it can be seen that the pot life can be adjusted while maintaining excellent fire resistance, shape retention, and heat insulation by further containing the condensation retarder in the fire resistance heat insulating composition.

"Experimental Example 4"
For 100 parts by mass of calcium sulfate (CSA1), 50 parts by mass of gypsum (SC1), for 100 parts by mass of a mixture of calcium sulfate and gypsum, 0.07 parts by mass of a setting retarder and water. Add 7 parts by mass of fibrous mineral (F1) and 100 parts by mass of water as the type and amount of sum accelerator shown in Table 4, and prepare a fire-resistant heat insulating composition slurry in the same manner as in Experimental Example 1 to improve the performance. evaluated. The gelation time was also evaluated. The results are shown in Table 4.

(Material used)
Hydration accelerator 1 (ACC1): Reagent 1st grade Calcium hydroxide hydration accelerator 2 (ACC2): Denka ordinary Portland cement hydration accelerator 3 (ACC3): Reagent 1st grade sodium carbonate hydration accelerator 4 ( ACC4): Reagent grade 1 anhydrous aluminum sulfate

In Table 4 above, the amount of the hydration accelerator (ACC) is the mass part with respect to 100 parts by mass of the mixture of calcium sulfoluminate (CSA) and gypsum (CS).

From Table 4, it can be seen that the amount of crystalline water can be improved and the refractory resistance can be improved while maintaining excellent heat insulating properties and shape retention by further containing the hydration accelerator in the refractory heat insulating composition.

"Experimental Example 5"
A mixture was prepared by adding 50 parts by mass of gypsum (CS1) to 100 parts by mass of calcium sulfoluminate (CSA1), and fibrous minerals were prepared with respect to 100 parts by mass of the mixture of calcium sulfoluminate and gypsum. 7 parts by mass of (F1) and the amount of water shown in Table 5 were added to prepare a fire-resistant heat insulating composition slurry in the same manner as in Experimental Example 1, and the performance was evaluated. The results are shown in Table 5.

In Table 5 above, the amount of water is the mass part with respect to 100 parts by mass of the mixture of calcium aluminate (CA) and gypsum (CS).

From Table 5, it can be seen that by preparing the refractory heat insulating composition slurry with an appropriate amount of water used, excellent fire resistance, shape retention, and heat insulating property are exhibited.

"Experimental Example 6"
50 parts by mass of gypsum (CS1) with respect to 100 parts by mass of calcium sulfoluminate (CSA1), and 7 parts by mass of fibrous mineral (F1) with respect to 100 parts by mass of the mixture of calcium sulfoluminate and gypsum. And 100 parts by mass of water were added, and the void ratio of the foamed resin molded body was changed as shown in Table 6, and a fireproof heat insulating composition slurry was prepared in the same manner as in Experimental Example 1 and its performance was evaluated. The results are shown in Table 6.
The void ratio was changed by using foamed resin molded bodies B to E having different void ratios.

(Material used)
Foamed resin molded body B: Commercially available polystyrene foam beads (diameter 1 to 5 mm) are filled in a molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) and heated by steam to have voids between the foamed particles. It was manufactured by fusing the foamed particles together in this state. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio 25.3%, density of polystyrene foam beads 10.5 kg / m ³ , thermal conductivity of polystyrene foam bead molded body 0.033 W / m · K

Foamed resin molded body C: Commercially available polystyrene foam beads (diameter 1 to 5 mm) are filled in a molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) and heated by steam to have voids between the foamed particles. It was manufactured by fusing the foamed particles together in this state. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio 43.9%, density of polystyrene foam beads 10.5 kg / m ³ , thermal conductivity of polystyrene foam bead molded body 0.033 W / m · K

Foamed resin molded body D: Commercially available polystyrene foam beads (diameter 1 to 5 mm) are filled in a molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) and heated by steam to have voids between the foamed particles. It was manufactured by fusing the foamed particles together in this state. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio 58.7%, density of polystyrene foam beads 10.5 kg / m ³ , thermal conductivity of polystyrene foam bead molded body 0.033 W / m · K

Foamed resin molded body E: Commercially available polystyrene foam beads (diameter 1 to 5 mm) are filled in a molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) and heated by steam to have voids between the foamed particles. It was manufactured by fusing the foamed particles together in this state. The continuous void ratio was controlled by adjusting the degree of pressurization. Continuous void ratio 69.4%, density of polystyrene foam beads 10.5 kg / m ³ , thermal conductivity of polystyrene foam beads molded body 0.033 W / m · K

From Table 6, it can be seen that by using a foamed resin molded product having appropriate continuous voids, excellent nonflammability, shape retention, and heat insulating properties are exhibited.

"Experimental Example 7"
Experiment No. Using the refractory heat insulating composition slurry 1-1, 1-2, 2-5 and 4-1 in the same manner as in Experimental Example 1, a refractory heat insulating board (length 1000 mm × width 1000 mm × thickness 25 mm) was produced.
Using the prepared refractory heat insulating board, it was assembled into the refractory structure shown in FIGS. 2 and 3 and installed in the refractory furnace.
As shown in FIG. 3, in the fireproof structure, a ceramic siding board is fixed to a laminated board composed of a moisture permeable waterproof sheet, a fireproof heat insulating board, and a structural plywood via a furring strip, and is used for the structure of the laminated board. It has a structure in which the plywood is fixed to the fireproof insulation board via columns. Then, this refractory structure was installed in a refractory furnace so that the ceramic siding board side was the heating surface.

The size of the fireproof structure was 2200 mm in width × 1200 mm in length. In the test, the combustion state of the refractory structure after the test was confirmed by changing the type and thickness of the refractory heat insulating composition of the refractory heat insulating board. When installing the board with different thickness, the number of installed boards was changed. The results are shown in Table 7.
The details of the materials used are as follows.

(Material used)
Ceramic siding board: Nichiha, Moen siding, thickness 16 mm
Breathable waterproof sheet: Super Airtex KD manufactured by Fukubi Chemical Co., Ltd.
Structural plywood: Polyethylene type, JAS standard product, special type, thickness 9 mm
Pillars (studs): wood (sugi), length 15 mm
Furnace: wood (sugi), length 105 mm

(Fire resistance test method)
As shown in the side view of FIG. 2 and the top view of FIG. 3, which show the internal structure, heating is performed on the ceramic siding board side simulating the outer wall with the refractory structure installed in the refractory furnace, and the gas burner (total). The fire-resistant structure was heated for 1 hour with a standard overheating curve conforming to ISO 834 by inflaming from 5 units). After that, the heating was stopped and the state of being installed in the refractory furnace was maintained for 3 hours. The structure was removed from the refractory furnace, the refractory insulation board was peeled off, and the combustion state of the columns was confirmed.

From Table 7, it can be seen that the fire resistance is improved when the fire resistant structure is made of the fire resistant heat insulating board according to the embodiment of the present invention.

By using the refractory heat insulating composition and the slurry thereof according to the embodiment of the present invention, a refractory heat insulating board having fire resistance and heat insulating properties can be obtained. Further, when a structure such as a wall or a pillar is constructed using the board, the shape can be maintained even if it receives a flame, so that it has an effect of preventing the spread of fire in the event of a fire. Therefore, the embodiment of the present invention can contribute to the construction of buildings, vehicles, aircraft, ships, refrigeration equipment, and refrigeration equipment having high fire prevention safety.

Claims

It contains 5 to 100 parts by mass of gypsum with respect to 100 parts by mass of calcium sulfoluminate containing at least 40 to 70% by mass of hauyne and 5 to 30% by mass of belite.
A fire-resistant heat insulating composition containing 0.1 to 20 parts by mass of a fibrous inorganic clay mineral having a water content of 5% by mass or more with respect to a total of 100 parts by mass of the calcium sulfoluminate and the gypsum.
The refractory heat insulating composition according to claim 1, which contains an inorganic powder having pores.
The refractory heat insulating composition according to claim 1 or 2, which comprises a setting retarder.
The refractory heat insulating composition according to any one of claims 1 to 3, which contains a hydration accelerator.
A refractory heat insulating composition slurry obtained by mixing water with the refractory heat insulating composition according to any one of claims 1 to 4.
A refractory heat insulating board formed by filling the gap portion of a resin molded body having a continuous void ratio of 25 to 70% by volume with the refractory heat insulating composition slurry according to claim 5 and solidifying it.
A fireproof heat insulating structure including the fireproof heat insulating board according to claim 6.