JPH07232971A - Formable inorganic composition - Google Patents

Abstract

PURPOSE:To produce the composition with which a foamed body having uniform cells, water resistance, high strength, low specific gravity and a low heat- shrinkage factor can be obtained by adding an alkali metal silicate, a peroxide and water to a prescribed powder and blending them together. CONSTITUTION:In the producing method of this composition, firstly, at least one reactive inorganic powder is selected from: (1) a powder that contains >=80wt.% particles having <=10mum particle size and is selected from fly ash (FA); (2) a powder that contains >=80wt.% particles having <=10mum particle size and is selected from FA fired at 400 to 1000 deg.C; (3) a powder obtained by atomizing molten FA in a gas; (4) a powder obtained by applying 0.1 to 30kwh/ kg mechanical energy to FA; (5) a powder obtained by further heating the powder obtained in (4) at 100 to 750 deg.C; (6) a powder obtained by atomizing molten clay in a gas; etc. Then, 100 pts.wt. of this inorganic powder, 0.2 to 450 pts.wt. of an alkali metal silicate, 0.01 to 10 pts.wt. of a peroxide and 35 to 1500 pts.wt. of water are blended together to produce the objective foamable inorganic composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a foamable inorganic composition.

[0002]

2. Description of the Related Art Heretofore, there have been proposed some inorganic compositions which are cured and foamed by heat in the presence of an alkali. For example, (a) a method of obtaining a foam by generating steam under heating without using a foaming agent, or (b) a method of adding a metal powder to generate a gas to obtain a foam has been known. For example, as a method of (b), JP-A-57-77062 discloses that (A) water-soluble alkali silicate, (B) metal-based foaming agent, (C) fly ash or blast furnace slag and (D) water. An inorganic composition having foamability as an active ingredient is described.

However, since the foam obtained using the above composition has a slow curing rate, it is easily broken and lacks uniformity of cells, is poor in water resistance, and has low strength and low expansion ratio. However, there was a problem that a white foam could not be obtained due to the carbon contained in the fly ash, in addition to causing heat shrinkage and cracking during drying.

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a foam which is excellent in cell uniformity, water resistance, high strength, low specific gravity and a small heat shrinkage. The purpose of the present invention is to provide a porous inorganic composition.

[0004]

[Means for Solving the Problems]

The fly ash used in the present invention means fine ash particles collected by a dust collector from a pulverized coal combustion boiler, which is defined in JIS A 6201, and has a silica content of 45% or more and a moisture content of 1% or less. , Ignition loss 5% or less, specific gravity 1.95 or more, specific surface area 2,700 cm ² / g or more,
75% or more passes through a 44 μm standard sieve.

Of the component (A) used in the present invention, fly ash having a particle size of 10 μm or less and reactive inorganic powder containing 80% by weight or more is used as the above-mentioned fly ash. It can be obtained by separating and removing particles larger than 10 μm by using wind force, static electricity or the like. In the above processing, the methods of crushing, classifying and separating may be used together.

When the amount of the reactive inorganic powder having a particle size of 10 μm or less decreases, the reactivity with the alkali metal silicate decreases, and the foam obtained by foaming the expandable inorganic composition is a foam-breaking material during the foaming process. The lack of uniformity of bubbles,
Only those with a low expansion ratio can be obtained. Further, due to the decrease in reactivity, the curing of the above composition also becomes poor, and the strength of the resulting foam becomes weak, so that the particle size is 10 μm.
The amount of reactive inorganic powder of m or less is limited to 80% by weight or more.

Among the components (A) used in the present invention, fly ash fired at 400 to 1,000 ° C. is used. Fly ash is generally black, so if you use it in applications that require coloring,
Although calcination is performed at a temperature of 0 ° C. or higher for decolorization, baking at a temperature of more than 1,000 ° C. lowers the reactivity with the alkali metal silicate, so calcination at a temperature in the above range is preferable.

Of the component (A) used in the present invention, in and in, fly ash and clay are melted and sprayed in a gas to obtain a reactive inorganic powder, which is sprayed in a gas. As a method, thermal spraying techniques applied to ceramic coatings are applied. This spraying technique is preferably carried out by melting the fly ash and clay at a temperature of 2,000 to 16,000 ° C.
It is sprayed at a speed of 800 m / sec, and specifically, a plasma spraying method, a high energy gas spraying method, an arc spraying method or the like is adopted.

The reactive inorganic powder obtained by the above thermal spraying technique generally has a specific surface area of 0.1 to 100 m ² /
g, preferably 0.1 to 60 m ² / g.

Among the components (A) used in the present invention, the clay is composed of SiO ₂ 5 to 5 as a chemical composition.
It is preferable to contain 85% by weight and 90 to 10% by weight of Al ₂ O ₃ . Examples of such clays include kaolin minerals (kaolinite, dickanite, nacrite, halloysite, etc.), mica clay minerals (muscovite, illite, fengite, glauconite, celadonite, paragonite, blancmalite, etc.), smectite. Examples include minerals (montmorillonite, baidate, nontrolite, savonite, sauconite, etc.), chlorite, pyrophyllite, talc, vermiculite, wax rock, shale, etc. It is not limited to these.

Among the components (A) used in the present invention, mechanical energy of 0.1 to 30 kwh / kg is applied to fly ash, clay and kaolin mineral to obtain a reactive inorganic powder. However, in the present invention, the mechanical energy refers to a compressive force, a shearing force, an impact force and the like, and these may be acted alone or in combination of two or more kinds. Examples of equipment that causes these to work concretely include a ball mill, a vibration mill, a planetary mill, a medium stirring type mill, a roller mill, a mortar, and a jet pulverizer.

The particle diameters of the above clay and metakaolin are not particularly limited, but the average particle diameter is preferably 0.01 to 500 μm, more preferably 0.1 to 100 μm in order to effectively apply mechanical energy. .

The mechanical energy acting on the fly ash and clay of the above, and, is 0.1 kwh /
If it is less than kg, the reactivity with the alkali metal silicate decreases, and if it exceeds 30 kwh / kg, the load on the crushing device and the like increases, the wear and damage of the device increases, and the impurities in the clay are increased. Since problems such as the mixture of
Limited to ~ 30 kwh / kg, preferably 1.0-2
Act at 6 kwh / kg.

The reason why the mechanical energy acting on the kaolin mineral is limited to 0.1 to 30 kwh / kg is the same as in the case of the fly ash and clay described above.

When mechanical energy is applied in the present invention, a grinding aid may be added if necessary. The grinding aid is a material that prevents adhesion of the powder of clay or metakaolin to the inside of the apparatus or significant aggregation when mechanical energy is applied, such as methyl alcohol,
Examples thereof include alcohols such as ethyl alcohol, alcohol amines such as triethanolamine, metal soaps such as sodium stearate and calcium stearate, and acetone vapor. These may be used alone or in combination of two or more.

In addition, among the component (A) used in the present invention, the reactive inorganic powder of and, after the mechanical energy is applied to the clay, 100 to 750 is further added.
It is obtained by heating to ℃, but if the heating temperature is less than 100 ℃, the mechanical strength of the molded product after foaming and hardening of the foamable inorganic composition is lowered, and if it exceeds 750 ℃, the above reactive inorganic powder. Since the crystallization of the body is promoted and the solubility in the alkali metal silicate aqueous solution is lowered, the heating temperature is 100
It is limited to 750 degreeC, Preferably it is 200-600 degreeC. Further, when the heating time is shortened, the mechanical strength of the obtained molded article is lowered, and when the heating time is prolonged, the energy cost is increased, so 1 minute to 5 hours is preferable.

The alkali metal silicate (B) used in the present invention is a silicate represented by M ₂ O.nSiO ₂ (M = one or more kinds of metals selected from K, Na and Li). , N does not allow a dense foam to be obtained, while a larger value increases the viscosity of the aqueous solution and makes mixing difficult, so that it is preferably 0.05 to 8, and more preferably 0.5 to 2.
It is 5.

The alkali metal silicate (B) is preferably added in an aqueous solution, and the concentration of the aqueous solution is not particularly limited, but when it becomes thin, the reactivity with the reactive inorganic powder of the component (A) decreases, and the concentration becomes high. If so, solid content is likely to occur, so 10 to 60% by weight is preferable.

The alkali metal silicate aqueous solution may be prepared by dissolving the alkali metal silicate in water as it is under pressure and heating. However, the alkali metal hydroxide aqueous solution may contain SiO ₂ components such as silica sand and silica stone powder as n. You may melt | dissolve under pressure and heating so that it may become a predetermined amount. The amount of alkali metal silicate is
If the amount is too small, the curing will not be sufficient, and if the amount is too large, the water resistance of the resulting foam will decrease. Therefore, the amount is limited to 0.2 to 450 parts by weight with respect to 100 parts by weight of the reactive inorganic powder of the component (A), It is preferably 10 to 350 parts by weight.

Peroxide (C) used in the present invention
Is a generic term for oxides having a negative divalent O ₂ group, and is not particularly limited as long as it decomposes with an alkali metal silicate aqueous solution or heat to release oxygen gas as described above. Examples thereof include inorganic peroxides such as potassium oxide, sodium peroxide, calcium peroxide, and boric acid, organic peroxides such as dialkyl peroxide, acyl peroxide, and the like, which react with an alkali metal silicate aqueous solution even at room temperature. Inorganic peroxides that decompose by the above are preferable.

The above-mentioned peroxide (C) may be used alone or in combination of two or more kinds. If necessary, it may be added as an aqueous solution. When the amount of the peroxide (C) is small, a foam having a low density cannot be obtained, and when the amount is large, the foam is easily broken.
0.01 to 100 parts by weight of reactive inorganic powder
Limited to 10 parts by weight. When hydrogen peroxide is used as the peroxide (C), it is preferably added as an aqueous solution, and the concentration of the aqueous solution is preferably 0.1 to 35% by weight.

The water (D) used in the present invention may be added independently, but as described above, it is preferably added as the above-mentioned aqueous solution of alkali metal hydroxide. Also, water (D)
The amount of addition of 100 is the reactive inorganic powder 100 of the component (A).
If the amount is less than 35 parts by weight, the expandable inorganic composition will not be sufficiently cured and foam breakage will easily occur. If the amount is more than 1,500 parts by weight, the strength of the resulting foam will be increased. Is easily reduced, the amount is limited to 35 to 1500 parts by weight, preferably 45 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, relative to 100 parts by weight of the reactive inorganic powder of the component (A). Is.

In the present invention, a foaming aid may be added if necessary. The foaming aid is not particularly limited as long as it uniformly causes foaming, and examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate, zinc palmitate, silica gel, zeolite, activated carbon, and porous powder such as alumina powder. can give. These may be used alone or in combination of two or more.

When the amount of the foaming aid is large, the viscosity of the foamable inorganic composition becomes large, and the foaming tends to occur during foaming, and a stable foam cannot be obtained. It is preferably 10 parts by weight or less with respect to 100 parts by weight of the hydrophilic inorganic powder.

In the present invention, a filler may be added if necessary. Filler is not soluble in water, preferably does not inhibit the curing reaction of the curable inorganic composition of the present invention, does not significantly inhibit the action of all the components used in the above composition of the present invention, For example, aggregate for cement mortar such as silica sand and river sand, mixture material for mixed cement such as silica flower, silica fume, bentonite, blast furnace slag, sepiolite, wollastonite, zircon sand, silica stone powder, diatomaceous earth, mica, talc Examples thereof include, but are not limited to, rock powder, natural minerals such as volcanic ash (shirasu, anti-firestone, etc.), calcium carbonate, crystalline alumina, and the like.

The filler is required to have low activity especially to the alkali metal silicate aqueous solution, but when the activity is high, gelation of the alkali aqueous solution and the alkali metal silicate aqueous solution progresses rapidly, resulting in foamability. This is because the work of mixing and molding the inorganic composition becomes difficult.

Among the fillers used in the present invention,
The granular particles are easily dissolved in the alkali metal silicate when the average particle size is small, and the thermal contraction cannot be suppressed when the average particle size is large, and therefore the particles are preferably in the range of 0.01 to 30 μm. Further, in the case of having a needle shape, a square shape, or a columnar shape, if the length in the major axis direction becomes shorter, it becomes difficult to prevent heat shrinkage, and if the length becomes longer, kneading becomes difficult, so that it is 1 to 250 μm. It is preferable.

The ratio of the major axis diameter (a) to the minor axis diameter (b) (a /
When the ratio b) is more than 50/1, the molding becomes difficult, the bubbles are not stable, and the mechanical strength of the molded product after foaming and hardening is reduced due to nonuniformity or breakage, and If it is less than 5/1, the resulting molded article has large dry shrinkage and heat shrinkage,
Since the molded body may be distorted or cracked, the ratio (a / b) of the major axis diameter (a) to the minor axis diameter (b) is 50/1 to
Those in the range of 1.5 / 1, preferably 30/1 to 2/1, and more preferably 20/1 to 3/1 are selected.

When the content of the above-mentioned filler is less than 20 parts by weight based on 100 parts by weight of the reactive inorganic powder of the component (A), dry shrinkage of the molded body of the expandable inorganic composition after foam curing, If the heat shrinkage is large and exceeds 800 parts by weight, the mechanical strength of the above-mentioned molded product is lowered, so that it is 20 to 800.
Parts by weight, preferably 30 to 600 parts by weight, more preferably 40 to 400 parts by weight are added.

The above-mentioned fillers may be used alone or as a mixture of two or more kinds for each group as described above, or may be used in combination. When these two groups are used in combination, new effects such as improvement in mechanical strength of the molded product after foaming and hardening are exhibited as compared with the case where only one of the groups is used. The amount of the filler to be added is 20 to 800 parts by weight, preferably 30 to 600 parts by weight, and more preferably 4 parts by weight, based on 100 parts by weight of the reactive inorganic powder of the component (A).
0 to 400 parts by weight.

When both groups of the above-mentioned fillers are used in combination, the blending ratio of 60% by weight or less of the total amount of the inorganic fillers leads to improvement of heat shrinkage,
It is necessary to exert the above new effects.

In the present invention, reinforcing fibers may further be added if necessary. Reinforcement fiber, any one can be used depending on the performance desired to impart to the molded body, for example, vinylon fiber, cellulose fiber, polyamide fiber, polyester fiber, polypropylene fiber, carbon fiber, aramid fiber, glass fiber, potassium titanate fiber, Steel fibers can be used. The fiber diameter of the reinforcing fiber is reaggregated during mixing when it becomes thin, fiber balls are easily formed by entanglement, the strength of the finally obtained foam is not further improved, and when it becomes thicker or shorter, the tensile strength increases. Since the reinforcing effect such as improvement is small and the dispersibility and the orientation of the fiber are reduced when it is long, the fiber diameter is preferably 1 to 500 μm and the fiber length is 1 to 15 mm. Since the dispersibility of the fibers decreases as the amount of the reinforcing fibers added increases, it is preferably 10 parts by weight or less with respect to 100 parts by weight of the reactive inorganic powder of the component (A).

The expandable inorganic composition of the present invention comprises an inorganic foam such as silica balloons, perlite, fly ash balloons, shirasu balloons, glass balloons and foamed clay, a phenolic resin, for the purpose of further reducing the weight of the foam.
Urethane resins, organic foams such as polyethylene and polystyrene, vinylidene chloride balloons and the like may be added. These may be added alone or in combination of two or more.

In order to obtain a foamed product from the composition of the present invention, first, the above alkali metal silicate (B) is dissolved in water (D) under pressure and heating to prepare the reactive inorganic powder (A) and necessary components. The foaming aid, the filler, and the reinforcing fiber are mixed according to the above, and after the peroxide (C) is added, it is foamed into a desired shape by a conventionally known method such as casting, press molding, extrusion molding, and shaping. Then, a method such as curing can be used.

The above curing temperature may be room temperature, but it is 50 to 1
By curing at 10 ° C. for 30 minutes to 8 hours, the curing reaction can be promoted and the mechanical properties can be improved.

[0037]

EXAMPLES The present invention will be described in more detail by way of examples.

Preparation of Reactive Inorganic Powders 1 and 2 Fly ash (manufactured by KANDENKA CORPORATION, average particle size 20 μm; J
A reactive inorganic powder 1 (10% by weight) containing 100% by weight of a powder having a particle size of 10 μm or less is obtained by classifying an IS A 6201) by a classifier (manufactured by Nisshin Engineering Co., Ltd., model: TC-15). ) And 100% by weight of powder having a particle size of more than 10 μm.
% By weight).

Preparation of Reactive Inorganic Powders 1 to 9 The reactive inorganic powders 1 and 2 were mixed in the mixing ratio shown in Table 1, and the mixture was heated in the firing furnace at a temperature rising rate of 200 ° C./hr. 1 to 9 of the reactive inorganic powder 3 is fired at the temperature shown for 2 hours.
Got

[0040]

[Table 1]

Preparation of Reactive Inorganic Powder 4 Fly ash (manufactured by KANDENKA CORPORATION, average particle size 20 μm; J
(According to IS A 6201) is melted at 3,000 ° C. and sprayed into the atmosphere at a speed of 80 m / sec to give an average particle size of 5 μm.
m was obtained, and a reactive inorganic powder 4 having a specific surface area of 9.5 m ² / g was obtained.

Preparation of Reactive Inorganic Powder 5 Kaolin (composition: SiO ₂ 45.7%, Al ₂ O ₃ 3
8.3%, average particle size: 8 μm, BET specific surface area: 5.8
m ² / g) with a combustion temperature of 2,500 ° C. and an injection particle velocity of 50
Sprayed at m / sec, composition: SiO ₂ 49.7%, Al ₂ O
₃ 47.0%, average particle size: 14.8μm, BET specific surface area: to obtain a reactive inorganic powder 5 of 1.96m ² / g.

Preparation of Reactive Inorganic Powder 6 Fly ash (manufactured by KANDENKA CORPORATION, average particle size 20 μm; J
0.5 parts by weight of a mixed solution of 25% by weight of triethanolamine and 75% by weight of ethanol was added to 100 parts by weight of Ultra Fine Mill AT-.
20 (using Mitsubishi Heavy Industries' 10 mm zirconia balls, ball filling rate 85% by volume), 25 kwh /
Mechanical energy of kg was applied to obtain a reactive inorganic powder 6. The mechanical energy applied was expressed by dividing the electric power supplied to the ultrafine mill by the unit weight of the treated powder.

Preparation of Reactive Inorganic Powders 1 to 6 Kaolin (composition: SiO ₂ 45.7%, Al ₂ O ₃ 3
8.3%, average particle size: 5 μm, BET specific surface area: 5.8
m ² / g) or pyrophyllite and quartz (manufactured by Sumitomo Cement Co., Ltd., trade name: soft silica) in a ratio shown in Table 2 of 100 parts by weight of triethanolamine 25% by weight and ethanol 75% by weight Mixed solution 0.
5 parts by weight was supplied to an Ultra Fine Mill AT-20 (manufactured by Mitsubishi Heavy Industries, using zirconia balls 10 mm, ball filling rate 85% by volume), and mechanical energy of the amount shown in the same table was applied to the reactive inorganic powder. Got 1-6 of Body 7.
The mechanical energy applied was expressed by dividing the electric power supplied to the ultrafine mill by the unit weight of the treated powder.

[0045]

[Table 2]

Preparation of Reactive Inorganic Powder 8 Reactive inorganic powders 1 to 6 were heated at 300 ° C. for 3 hours to obtain reactive inorganic powders 1 to 6.

Reactive Inorganic Powder 9 Metakaolin (manufactured by Engelhard, trade name: SATI)
NTONE SP 33, average particle size 3.3μm, BET
Specific surface area: 13.9 m ² / g)

Preparation of Reactive Inorganic Powder 10 Metakaolin (manufactured by Engelhard Co., trade name: SATI)
NTONE SP 33, average particle size 3.3μm, BET
100 parts by weight of specific surface area: 13.9 m ² / g) and 0.5 parts by weight of a mixed solution of 25% by weight of triethanolamine and 75% by weight of ethanol were added to Ultra Fine Mill AT-2.
0 (manufactured by Mitsubishi Heavy Industries, using 10 mm of zirconia balls, ball filling rate 85% by volume), and mechanical energy of 10 kwh / kg was applied to obtain a reactive inorganic powder 10. The mechanical energy applied was expressed by dividing the electric power supplied to the ultrafine mill by the unit weight of the treated powder.

Reactive inorganic powder 11 Fly ash (manufactured by KANDENKA CORPORATION, average particle size 20 μm, specific surface area 1.8 m ² / g, JIS A 6201 equivalent)

Reactive inorganic powder 12 Kaolin (composition: SiO ₂ 45.7%, Al ₂ O ₂ 3
8.3%, average particle size: 8 μm, BET specific surface area 5.8 m
² / g,)

Examples 1 to 7, Comparative Examples 1 to 9 For Examples 1 to 7 and Comparative Examples 1 to 9, a predetermined amount of the reactive inorganic powders 1 and ₂ shown in Tables 3 and 4 and SiO ₂ / K. ₂
Alkali metal silicate aqueous solution having a molar ratio of O of 1.5, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm), mica (manufactured by Suzolite Mica Co., product number: 3)
25S, average particle diameter 40 μm), polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d × 6 mm) and zinc stearate were supplied to a hand mixer and mixed for 5 minutes.
Hydrogen peroxide water or aluminum powder was added to the obtained mixture, stirred for 10 seconds, poured into a mold and foamed for 3 minutes, and then the mold was heated in an oven at 85 ° C. for 20 hours to foam. Got the body The cured state and bubble state at the time of heating for 5 hours were visually observed. The obtained foam was demolded and dried at 50 ° C. for 20 hours.

[0052]

[Table 3]

[0053]

[Table 4]

The obtained foam was evaluated under the following conditions, and the results are shown in Tables 5 and 6.

Foam Evaluation

Cured state: The cured state at the time of heating for 5 hours and the cured state of the foam obtained by heating for 20 hours were visually observed, and those that were sufficiently cured were evaluated as ◯, and those that were insufficiently cured were evaluated as ◯. Δ: A mark was given to a product that was damaged during demolding due to poor curing.

Cellular state The cellular state at the time of heating for 5 hours and the cellular state of the foam obtained by heating for 20 hours were visually observed. A mark is given to those that are marked, and a mark is given to those that have poor foaming.

Density The foam obtained by heating for 20 hours is 50 × 50 × 50 m.
It was cut into m, weighed and divided by the volume.

Compressive strength The foam obtained by heating for 20 hours is 50 × 50 × 50 m.
Cut to m and according to JIS A1108, 23 ℃, 50
Compressive strength was measured in% RH.

Water resistance test The foam obtained by heating for 20 hours was 50 × 50 × 50 m.
After being cut into m and immersed in water at 80 ° C. for 6 hours, the compressive strength was measured in the same manner as above to obtain the strength retention rate.

[0061]

[Table 5]

[0062]

[Table 6]

Examples 8 to 12 and Comparative Examples 10 to 14 Tables 7 and 8 show the results of Examples 8 to 12 and Comparative Examples 10 to 14.
8 the predetermined amount of the reactive inorganic powder 3-1 to 3-9,
Alkali metal silicate aqueous solution having a SiO ₂ / K ₂ O molar ratio of 1.5, talc (manufactured by Sanyo Clay Industry Co., Ltd., product name: talc 83, average particle size 5 μm), mica (manufactured by Kuraray Co., Ltd., product name: Kuraray). Light mica, average particle size 30μm, polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d × 6m)
m) and zinc stearate were supplied to a hand mixer at the concentrations and molar ratios shown in Tables 7 and 8 and were mixed for 5 minutes. A predetermined amount of hydrogen peroxide solution or aluminum powder shown in Tables 7 and 8 was added to the obtained mixture, and the mixture was further stirred for 10 seconds. The obtained mixture was poured into a paper container, foamed at room temperature, sealed, and cured in an oven at 50 ° C. for 10 hours to obtain a foam.
The foam obtained is demolded and dried at 50 ° C. for 20 hours,
The pieces were cut into a size of 00 × 100 × 100 mm and subjected to the following tests.

[0064]

[Table 7]

[0065]

[Table 8]

The obtained foam was evaluated under the following conditions, and the results are shown in Table 9.

Evaluation of foam

Cured state: The foam obtained by curing for 10 hours was visually observed, and ○ was sufficiently cured, Δ was insufficiently cured, and ΔC was poorly cured and destroyed during demolding. The mark x is given.

Cellular state Visual observation of the foam obtained by curing for 10 hours revealed that the cells in which the cells were well dispersed were ◯, those in which the cells were broken were Δ, and those in which the foaming was poor. Marked x.

Density The foam obtained by curing for 10 hours was treated with 50 × 50 × 50.
It was cut into mm, weighed and divided by volume.

Compressive Strength A foam obtained by curing for 10 hours is 50 × 50 × 50.
Cut into mm and according to JISA 1108, 23 ℃, 5
The compressive strength was measured at 0% RH.

Water resistance test The foam obtained by curing for 10 hours was 50 × 50 × 50.
After being cut into mm and immersed in water at 80 ° C. for 6 hours, the compressive strength was measured in the same manner as above to obtain the strength retention rate.

Color of Molded Product A test piece obtained by curing for 10 hours was measured according to JIS Z 87.
L according to method 29 ^*Was measured.

[0074]

[Table 9]

Examples 13 to 19 and Comparative Examples 15 to 21 Tables 1 and 2 show the results of Examples 13 to 19 and Comparative Examples 15 to 21.
Reactive inorganic powders 1, 2, S shown in 0 and 11
Alkali metal silicate aqueous solution having a molar ratio of iO ₂ / K ₂ O of 1.5, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm), mica (manufactured by Szolite Mica Co., product number: 325S, average particle size 40 μm), polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d × 6 mm)
And zinc stearate were fed into the hand mixer and mixed for 5 minutes. A predetermined amount of hydrogen peroxide solution or aluminum powder (manufactured by Toyo Aluminum Co., Ltd., average particle size: 40 μm or less) shown in Tables 7 and 8 was added to the obtained mixture, stirred for 10 seconds, and poured into a mold. After foaming for 3 minutes, the mold was heated in an oven at 85 ° C. for 20 hours to obtain a foam. The cured state and bubble state at the time of heating for 5 hours were visually observed. The obtained foam was demolded and dried at 50 ° C. for 20 hours.

[0076]

[Table 10]

[0077]

[Table 11]

The foams obtained were evaluated under the following conditions, and the results are shown in Tables 12 and 13.

Evaluation of Foams-The same items as in Examples 1 to 7 were carried out.

[0080]

[Table 12]

[0081]

[Table 13]

Examples 20 to 26, Comparative Examples 22 to 27 Tables 1 and 2 show Examples 1 to 20 and Comparative Examples 22 to 27.
A predetermined amount of the reactive inorganic powder 4, 11,
An aqueous solution of an alkali metal silicate having a SiO ₂ / Na ₂ O molar ratio of 0.5, 1.0 or 1.5, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm),
Mica (manufactured by Suzolite Mica, product number: 325S, average particle size 40 μm), polypropylene fiber (manufactured by Daiwa Spinning Co., Ltd.,
(Product number: PZL 2d × 6 mm) and zinc stearate were supplied to a hand mixer and mixed for 5 minutes. The obtained mixture was mixed with a predetermined amount of hydrogen peroxide solution or aluminum powder shown in Tables 14 and 15 (manufactured by Toyo Aluminum Co., Ltd., average particle size: 4).
(0 μm or less), and the mixture was stirred for 10 seconds, poured into a mold and foamed for 3 minutes, and then the mold was heated in an oven at 85 ° C. for 20 hours to obtain a foam. The cured state and bubble state at the time of heating for 5 hours were visually observed. The obtained foam was demolded and dried at 50 ° C. for 20 hours.

[0083]

[Table 14]

[0084]

[Table 15]

The obtained foam was evaluated under the following conditions, and the results are shown in Tables 16 and 17.

Evaluation of Foams-The same items as in Examples 1 to 7 were carried out.

[0087]

[Table 16]

[0088]

[Table 17]

Examples 27 to 33 and Comparative Examples 28 to 33 Tables 1 and 2 show the results of Examples 27 to 33 and Comparative Examples 28 to 33.
8 and 19, the predetermined amount of the reactive inorganic powder 5, 12,
An alkali metal silicate aqueous solution having a SiO ₂ / Na ₂ O molar ratio of 0.5, 1.0 or 1.4, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm),
Mica (manufactured by Suzolite Mica, product number: 325S, average particle size 40 μm), polypropylene fiber (manufactured by Daiwa Spinning Co., Ltd.,
(Product number: PZL 2d × 6 mm) and zinc stearate were supplied to a hand mixer and mixed for 5 minutes. The resulting mixture was mixed with a predetermined amount of hydrogen peroxide solution or aluminum powder shown in Tables 18 and 19 (manufactured by Toyo Aluminum Co., Ltd., average particle size: 4).
(0 μm or less) was added, the mixture was stirred for 10 seconds, poured into a mold and foamed for 3 minutes, and then the mold was heated in an oven at 85 ° C. for 3 hours and 6 hours to obtain a foam. The foam obtained was demolded and dried in a phosphorus pentoxide desiccator.

[0090]

[Table 18]

[0091]

[Table 19]

The foams obtained were evaluated under the following conditions, and the results are shown in Tables 20 and 21.

Evaluation of foam

Cured state The cured state after heating for 3 hours and the cured state of the foam obtained by heating for 6 hours were visually observed. Δ: A mark was given to a product that was damaged during demolding due to poor curing.

Bubble State The bubble state at the time of heating for 3 hours and the bubble state of the foam obtained by heating for 6 hours were visually observed, and ○ was broken when the bubbles were well dispersed. △,
Those with poor foaming were marked with x.

Density The foam obtained after heating for 3 hours and for 6 hours was cut into 50 × 50 × 50 mm, weighed and divided by the volume.

Compressive Strength A foam obtained by heating for 3 hours and after heating for 6 hours was cut into 50 × 50 × 50 mm and JIS A 1108 was used.
The compressive strength was measured at 23 ° C. and 50% RH according to the above.

Water resistance test The foam obtained after heating for 3 hours and after heating for 6 hours was cut into 50 × 50 × 50 mm and immersed in water at 80 ° C. for 6 hours, and the compressive strength was measured in the same manner as described above. The retention rate was calculated.

[0099]

[Table 20]

[0100]

[Table 21]

Examples 34 to 40, Comparative Examples 34 to 41 Tables 2 and 3 are shown for Examples 34 to 40 and Comparative Examples 34 to 41.
1 to 2 of the predetermined amount of the reactive inorganic powder 7 shown in FIGS.
6, an alkali metal silicate aqueous solution having a SiO ₂ / Na ₂ O molar ratio of 1.0, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm), mica (manufactured by Szolite Mica Co., Ltd., Part number: 325S, average particle size 40 μm),
Polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d
X 6 mm) and zinc stearate were fed into a hand mixer and mixed for 5 minutes. The obtained mixture is shown in Tables 22 and 23.
After adding a predetermined amount of hydrogen peroxide water or aluminum powder (manufactured by Toyo Aluminum Co., Ltd., average particle size: 40 μm or less) shown in 1 above, stirring for 10 seconds, injecting into the mold and foaming for 3 minutes, then the mold Each was heated in an oven at 85 ° C. for 2 hours and 4 hours to obtain a foam. The foam obtained was demolded and dried in a phosphorus pentoxide desiccator.

[0102]

[Table 22]

[0103]

[Table 23]

The foams obtained were evaluated under the following conditions, and the results are shown in Tables 24 and 25.

Foam Evaluation

Cured state The cured state after heating for 2 hours and the cured state of the foam obtained by heating for 4 hours were visually observed. Δ: A mark was given to a product that was damaged during demolding due to poor curing.

Cellular state Visually observing the cellular state at the time of heating for 2 hours and the cellular state of the foam obtained by heating for 4 hours, ◯ if the cells were well dispersed, the cell was broken. △,
Those with poor foaming were marked with x.

Density The foam obtained after heating for 2 hours and after heating for 4 hours was cut into 50 × 50 × 50 mm, weighed and divided by the volume.

Compressive Strength The foam obtained by heating for 2 hours and after heating for 4 hours was cut into 50 × 50 × 50 mm and JIS A 1108 was used.
The compressive strength was measured at 23 ° C. and 50% RH according to the above.

Water resistance test Foams obtained by heating for 2 hours and after heating for 4 hours were cut into 50 × 50 × 50 mm and immersed in water at 80 ° C. for 6 hours, and the compressive strength was measured in the same manner as described above. The retention rate was calculated.

[0111]

[Table 24]

[0112]

[Table 25]

Examples 41 to 47, Comparative Examples 42 to 49 Tables 2 and 3 are shown for Examples 41 to 47 and Comparative Examples 42 to 49.
1 to 2 of the predetermined amount of the reactive inorganic powder 8 shown in FIGS.
6, an aqueous solution of an alkali metal silicate having a SiO ₂ / Na ₂ O molar ratio of 1.0, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm), mica (manufactured by Szolite Mica, Part number: 325S, average particle size 40 μm),
Polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d
X 6 mm) and zinc stearate were fed into a hand mixer and mixed for 5 minutes. Tables 26 and 27 show the obtained mixture.
A predetermined amount of hydrogen peroxide solution or aluminum powder (manufactured by Toyo Aluminum Co., Ltd., average particle size: 40 μm or less) shown in 1 is added, stirred for 10 seconds, poured into a mold and foamed for 3 minutes, and then the mold. Each was heated in an oven at 85 ° C. for 2 hours and 4 hours to obtain a foam. The foam obtained was demolded and dried in a phosphorus pentoxide desiccator.

[0114]

[Table 26]

[0115]

[Table 27]

The foams obtained were evaluated under the following conditions, and the results are shown in Tables 28 and 29.

Evaluation of Foams-The same items as in Examples 34 to 40 were evaluated.

[0118]

[Table 28]

[0119]

[Table 29]

Examples 48 to 54, Comparative Examples 50 to 54 Tables 3 and 4 show the results of Examples 48 to 54 and Comparative Examples 50 to 54.
0, 31, the predetermined amount of reactive inorganic powder 10, Si
Alkali metal silicate aqueous solution having a molar ratio of O ₂ / Na ₂ O of 1.0, talc (manufactured by Sanyo Clay Industry Co., Ltd., trade name: talc 83, average particle size 5 μm), mica (manufactured by Suzolite Mica Co., product number: 325S, average particle size 40 μm), polypropylene fiber (manufactured by Daiwa Spinning Co., product number: PZL2d × 6 mm)
And zinc stearate were fed into the hand mixer and mixed for 5 minutes. A predetermined amount of hydrogen peroxide water or aluminum powder (manufactured by Toyo Aluminum Co., Ltd., average particle size: 40 μm or less) shown in Tables 30 and 31 was added to the obtained mixture to give 10
The mixture was stirred for 2 seconds, poured into the mold and foamed for 3 minutes, and then heated together with the mold in an oven at 85 ° C. for 2 hours and 4 hours to obtain a foam. The foam obtained was demolded and dried in a phosphorus pentoxide desiccator.

[0121]

[Table 30]

[0122]

[Table 31]

The foams obtained were evaluated under the following conditions, and the results are shown in Tables 32 and 33.

Evaluation of Foams-The same items as in Examples 34 to 40 were evaluated.

[0125]

[Table 32]

[0126]

[Table 33]

[0127]

The composition of the foamable inorganic composition of the present invention is as described above, and it has excellent cell uniformity and water resistance, a small shrinkage factor due to heating, high heat insulation, high strength and low specific gravity. A foam can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shogaku Kamiya 2-2 Kamitobaue Tonkocho, Minami-ku, Kyoto City Sekisui Chemical Co., Ltd. 2-2 Sekisui Kagaku Kogyo Co., Ltd. (72) Inventor Masakatsu Sakamoto 2-2 Kamitobaue Toko, Minami-ku, Kyoto City Sekisui Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. (A) A powder containing 80% by weight or more of fly ash having a particle size of 10 μm or less, and a fly ash fired at 400 to 1,000 ° C. having a particle size of 10 μm or less. Of 80% by weight or more, powder obtained by melting fly ash and spraying in gas, obtained by applying mechanical energy of 0.1 to 30 kwh / kg to fly ash. Powder, fly ash 0.1 to 30
Powder obtained by applying mechanical energy of kwh / kg to powder obtained by further heating at 100 to 750 ° C., clay melted and sprayed in gas Powder and clay obtained by applying mechanical energy of 0.1 to 30 kwh / kg to the clay.
Powder obtained by applying mechanical energy of 1 to 30 kwh / kg, further heated to 100 to 750 ° C., powder obtained by heating kaolin mineral at 500 to 900 ° C. or powder 0.1 to 3 for metakaolin
100 parts by weight of at least one reactive inorganic powder selected from the group consisting of powder obtained by applying mechanical energy of 0 kwh / kg, (B) 0.2 to 450 parts by weight of alkali metal silicate , (C) peroxide 0.01 to
A foamable inorganic composition comprising 10 parts by weight and (D) 35 to 1,500 parts by weight of water.