JPH115206A - Manufacture of inorganic curable material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily manufacture a product having excellent external appearance with satisfactory mold releasability by casting composition containing SiO2 -Al2 O3 reactive inorganic powder, alkali metal silicate and water in a mold at a specific contact angle, and thermally curing it. SOLUTION: SiO2 -Al2 O3 reactive inorganic powder contains 5 to 85 wt.% of SiO2 , 90 to 10 wt.% of Al2 O3 and alkali metal silicate M2 O-nSiO2 (one or more types of metal selected from M=K, Na and Li). In this case, if a value of the n is small, dense foam cannot be obtained, while if it is large, density of water solution is raised so that mixing becomes difficult, and hence the n is 0.05 to 8 or further preferably 0.5 to 2.5. The water may be added independently as alkali metal silicate water solution. If a contact angle of a foam material 1 is large, small foam is generated, while if it is small, its surface is notched so that its external appearance is deteriorated. The angle is preferably 60 to 165 degrees or further preferably 65 to 150. After foam heating, the external appearance of the inorganic foam 2 after cured and mold released does not appear a fault.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an inorganic cured material used for, for example, building materials.

[0002]

2. Description of the Related Art Japanese Patent Laid-Open No. 6-239655 discloses a method for producing an inorganic cured material used for building materials and the like. In this production method, a cured product is obtained from fly ash, an aqueous solution of an alkali metal silicate, and a filler.

[0003]

However, in order to use the cured inorganic material obtained by using the above composition as an inorganic building material, it is necessary to transfer the cured product to a mold in order to impart design properties. Therefore, depending on the mold material, a large force is required at the time of demolding, so that the surface is likely to be chipped and the appearance may be deteriorated.

The present invention has been made in view of such a problem, and it is an object of the present invention to provide a method for producing an inorganic cured product capable of easily producing a product having excellent appearance by improving the releasability. Aim.

[0005]

Means for Solving the Problems To achieve the above object, the invention of claim 1 provides a composition comprising a SiO ₂ —Al ₂ O ₃ -based reactive inorganic powder, an alkali metal silicate, and water. The object is put into a mold having a contact angle of 55 to 170 degrees and is heated and cured.

[0006] The invention of claim 2 of the present invention is based on claim 1.
The method for producing an inorganic cured product according to the above, is characterized in that after the composition is charged into a mold having a contact angle of 55 to 170 degrees, the charged composition is foamed and then cured by heating.

Further, the invention according to claim 3 of the present invention provides (A) S
100 parts by weight of iO ₂ —Al ₂ O ₃ -based reactive inorganic powder,
(B) 0.2 to 450 parts by weight of an alkali metal silicate, and (C)
A composition consisting of 35 to 1500 parts by weight of water has a contact angle of 55.
It is characterized in that it is put into a mold frame having a temperature of up to 170 degrees and heat-cured.

According to the first and third aspects of the present invention,
100 parts by weight of a SiO ₂ —Al ₂ O ₃ -based reactive inorganic powder, 0.2 to 450 parts by weight of an alkali metal silicate,
The composition is composed of 5 to 1500 parts by weight, and the composition is heated and cured in a mold having a contact angle of 55 to 170 degrees, so that a large force is not required at the time of demolding. For this reason, the surface of the inorganic cured body is not chipped at the time of demolding, and an inorganic cured body having excellent design can be obtained.

According to the second aspect of the present invention, since the composition charged in the mold is foamed, the weight of the inorganic cured product can be reduced.

In the present invention, the contact angle refers to the angle between the solid and the liquid surface at the contact point when the free surface of the liquid contacts the solid.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the method for producing an inorganic cured product according to the present invention will be described below.

In this embodiment, the composition of the inorganic cured product is (A) SiO ₂ —Al ₂ O ₃ -based reactive inorganic powder 100
Parts by weight, (B) 0.2 to 450 parts by weight of an alkali metal silicate, and (C) 35 to 1500 parts by weight of water. This composition is put into a mold having a contact angle of 55 to 170 degrees and cured by heating. This inorganic cured product was prepared by adding the composition to a contact angle of 5
After being placed in a mold at 5 to 170 degrees, the composition is foamed and then cured by heating.

Hereinafter, (A) 100 parts by weight of an SiO ₂ —Al ₂ O ₃ type reactive inorganic powder and (B) an alkali metal silicate 0.1 part by weight.
2 to 450 parts by weight and (C) 35 to 1500 parts by weight of water will be described.

[SiO ₂ —Al ₂ O ₃ -based Reactive Inorganic Powder (A)] As the SiO ₂ -Al ₂ O ₃ -based reactive inorganic powder (A), 5-85% by weight of SiO ₂ and Al ₂ O ₃
Those having 90 to 10% by weight are suitably used. As such powder, fly ash, metakaolin, kaolin, mullite, corundum, dust for producing an alumina-based abrasive, pulverized and fired bauxite, and the like can be used, but are not limited thereto if the composition and particle size are appropriate. Not something. Further, these powders may be used as they are, but in order to activate them, thermal spraying treatment, pulverization classification, and mechanical energy may be applied.

As a method of thermal spraying, a thermal spraying technique applied to ceramic coating is applied. The spraying technique is preferably such that the material powder is 2000-16000.
It is melted at a temperature of ° C. and sprayed at a speed of 30 to 800 m / sec, and a plasma spraying method, a high energy gas spraying method, an arc spraying method and the like are possible. The specific surface area of the obtained powder is preferably from 0.1 to 100 m ² / g.

As a method of classification and pulverization, any conventionally known method is employed, and examples thereof include classification using a sieve, specific gravity, wind power, wet sedimentation, and the like, and pulverization using a jet mill, a roll mill, and a ball mill. These means may be used in combination.

As a method of applying mechanical energy, a ball medium mill, a medium stirring type mill, a roller mill, or the like is used.
kwh / kg to 30 kwh / kg is preferred. If the particle size is small, it is difficult to activate the powder, and if the particle size is large, the load on the device is large.

The fly ash may be fired as required. If the firing temperature is low, the fly ash remains black, and if the firing temperature is high, the reactivity with the alkali metal silicate (B) becomes low.

[Alkali metal silicate (B)] This embodiment
The alkali metal silicate (B) used for_Two O ・
nSiO _Two (At least one selected from M = K, Na, Li)
Wherein the value of n decreases
And dense foam cannot be obtained.
Rises and mixing becomes difficult, so 0.05 to 8 is preferred.
And more preferably 0.5 to 2.5.

The alkali metal silicate (B) is preferably added in the form of an aqueous solution. The concentration of the aqueous solution is not particularly limited, but the reactivity with the reactive inorganic powder (A) decreases as the concentration decreases, and the solidity decreases as the concentration increases. 10 minutes
~ 60% by weight is preferred.

The aqueous alkali metal silicate solution may be prepared by dissolving the alkali metal silicate (B) in water as it is under pressure and heating. However, the aqueous alkali metal hydroxide solution may contain SiO2 components such as silica sand and silica powder. You may melt | dissolve under pressure and heating so that n may become predetermined amount. If the amount of the alkali metal silicate (B) is too small, the curing is not sufficiently performed, and if the amount is too large, the water resistance of the obtained foam is reduced. .2-4
It is limited to 50 parts by weight, preferably 10 to 350 parts by weight, more preferably 20 to 250 parts by weight.

[Water (C)] The water (C) used in the present embodiment may be added as the alkali metal silicate aqueous solution or may be added independently. If the amount of water (C) is too small, it will not be sufficiently cured and mixing will be difficult, and if it is too large, the strength of the cured product will tend to decrease. ~
Limited to 1500 parts by weight, preferably 45 to 1000 parts
Parts by weight, more preferably 50 to 500 parts by weight.

[Blowing agent] In the cured product composition of the present embodiment, a blowing agent may be added as necessary. As foaming agents, peroxides (hydrogen peroxide, sodium peroxide, potassium peroxide, sodium perborate, etc.), metal powders (Mg, C
a, Cr, Mn, Fe, Co, Ni, Cu, Zn, A
l, Ga, Sn, Si, ferrosilicon) and the like are used. If the amount is too large, the foaming gas becomes excessive and the foam breaks.
It is preferably from 0.01 to 10 parts by weight. When hydrogen peroxide is used as a foaming agent, it is preferably used as an aqueous solution in consideration of safety and stable foaming. When using a metal powder, 200 μm
The following is preferred.

[Foaming Aid] In the cured product composition of the present embodiment, a foaming aid may be added as necessary.
The foaming aid is not particularly limited as long as it causes foaming uniformly, and examples thereof include zinc stearate, calcium stearate, fatty acid metal salts such as zinc palmitate, silica gel, zeolite, activated carbon, and porous powders 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 increases, the viscosity of the composition increases and foam breakage easily occurs. Therefore, the amount is preferably 10 parts by weight or less based on 100 parts by weight of the reactive inorganic powder (A).

[Inorganic Filler] In the cured product composition of the present embodiment, an inorganic filler may be added as necessary. The inorganic filler is not particularly limited as long as it does not dissolve in water, does not inhibit the curing reaction of the expandable inorganic composition, and does not react with the alkali metal silicate.
River sand, zircon sand, crystalline alumina, rock powder, volcanic ash, mixed materials for mixed cement such as silica flour, silica fume, bentonite, blast furnace slag, natural minerals such as sepiolite, wollastonite, mica, calcium carbonate, diatomaceous earth, etc. Can be These may be added alone or in combination of two or more.

When the amount of the inorganic filler increases, the strength of the obtained cured product decreases. Therefore, the amount is preferably 700 parts by weight or less based on 100 parts by weight of the reactive inorganic powder (A).

[Reinforcing Fiber] In the cured product composition of the present embodiment, a reinforcing fiber may be added as necessary.
Any reinforcing fiber can be used depending on the performance to be imparted to the molded article, and examples thereof include vinylon fiber, polyamide fiber, polyester fiber, polypropylene fiber, carbon fiber, aramid fiber, glass fiber, potassium titanate fiber, and steel fiber. Can be used.

If the fiber diameter of the reinforcing fiber becomes thinner, it reagglomerates upon mixing, and fiber balls are easily formed by entanglement. The ultimate strength obtained is not further improved. Since the reinforcing effect such as improvement is small, and if the length is long, the dispersibility and orientation of the fiber decrease, the fiber diameter is 1 to 500 μm and the fiber length is 1 to
5 mm is preferred. Since the dispersibility of the fiber decreases as the amount of the reinforcing fiber increases, it is preferably 10 parts by weight or less based on 100 parts by weight of the reactive inorganic powder (A).

[Other Additives] In order to further reduce the weight of the cured product, inorganic natural foams such as silica balloons, perlite, fly ash balloons, shirasu balloons, glass balloons, calcined clay and the like, phenolic resins, urethanes Resins, foams of synthetic resins such as polyethylene, and vinylidene chloride balloons may be added. These may be added alone or in combination of two or more.

In the cured product composition of the present embodiment,
If necessary, alumina cement, γ-alumina, sprayed alumina, alkali metal aluminate and aluminum hydroxide may be added.

[Mold] The mold used in the present embodiment is limited to those having a contact angle of 55 to 170 degrees, preferably 60 to 165 degrees, more preferably 6 to 165 degrees.
5 to 150 degrees. When the contact angle is large, small bubbles are generated to deteriorate the appearance, and when the contact angle is small, the surface is chipped and the appearance is deteriorated.

[Production method of foamed cured product] In order to obtain the cured product of the present invention, first, the above alkali metal silicate (B) is pressurized,
It is dissolved in at least a part of water (C) under heating, and the above-mentioned reactive inorganic powder (A) and, if necessary, the remaining water (C),
After mixing foaming aids, foaming aids, reinforcing fibers, inorganic fillers, and the like to form a paste, the mixture is poured into a mold having a contact angle of 55 to 170 degrees by a conventionally known method such as casting, pressing, or extrusion. And shaping into a desired shape and curing.

The curing temperature may be room temperature, but may be 50 to 110.
By curing at 30 ° C. for 30 minutes to 8 hours, the curing reaction can be accelerated and the mechanical properties can be improved.

[Examples and Comparative Examples] Next, examples and comparative examples of the present invention will be described.

FIG. 1 shows a situation in which a paste of an inorganic powder is injected into the decorative mold 1 used in the embodiment, and after the foaming is heated, the cured inorganic foam 2 is taken out and the tensile force is measured. This is schematically shown. The length of the inorganic foam 2 formed by the mold 1 was 2880 mm, which was substantially the same size and shape as the outer wall panel of the building.

The composition and blending parts by weight of the inorganic foam are as follows: 100 parts by weight of the inorganic powder 1 and 75 parts of an alkali metal silicate.
Parts by weight, 80 parts by weight of water, 80 parts by weight of walathnite, 40 parts by weight of silica powder, 40 parts by weight of No. 8 silica sand, 2 parts by weight of zinc stearate, 2 parts by weight of vinylon fiber, and 0.1 part by weight of a foaming agent did.

As the inorganic powder, metakaolin (SATINTONE SP 33 manufactured by Engelhard Co., average particle size 3.3 μm, specific surface area 13.9 m 2 / g) 100
Parts by weight and 0.5 parts by weight of a mixed solution of 25 parts by weight of triethanolamine and 75 parts by weight of ethanol are mixed with Ultra Fine Mill AT-20 (manufactured by Mitsubishi Heavy Industries, zirconia ball diameter 10 mm, ball filling rate 85 vol%). The inorganic powder 1 was obtained by supplying 25 kwh / Kg of mechanical energy. The applied mechanical energy is represented by the electric power supplied to the ball mill per unit weight of the treated powder.

As a method for preparing the inorganic powder, a predetermined amount of nSiO ₂ / M ₂ O (n = 1.5, M = Na, K; molar ratio: 1: 1) is placed in an autoclave at 130 ° C. and 7 kPa.
g / cm ² , dissolved in a predetermined amount of water, wollastonite, vinylon fiber (trade name: RM182 × 3, manufactured by Kuraray Co., Ltd.),
Silica powder, No. 8 silica sand, SiO ₂ —Al ₂ O ₃ based inorganic powder (A), aluminum hydroxide (particle diameter 100 μm or less),
Zinc stearate was mixed with an omni mixer (manufactured by Chiyoda Giken Co., Ltd.) to obtain a uniform paste. After adding aluminum powder containing 100% by weight of powder having a particle size of 70 μm or less to the paste, stirring the mixture for 40 seconds, injecting into a mold having a decorative mold, and foaming for 3 minutes. Each in an oven at 85 ° C. for 6 hours, (288
(00 × 889 × 30) mm inorganic cured product 2 was obtained.

The contact angle of the mold 1 used in the experiment was as shown in Example 1.
100 degrees in Example 2, 130 degrees in Example 2, 60 degrees in Example 3, 20 degrees in Comparative Example 1, and Comparative Example 2.
Was 175 degrees. The contact angle was measured by dropping water with a dropper on the cavity forming wall surface of the mold 1 and observing it with a microscope.

As a method of measuring the force required to release the inorganic foam 2, the wires 3 are hooked near both ends of the inorganic foam 2 and pulled upward to cure the cured inorganic foam 2.
Of the mold 1 was measured.

FIG. 1 shows the results of Examples 1 to 3 and Comparative Examples 1 and 2. In the mold 1 of the first embodiment, the tensile force (K
gf) was 28 kgf (270 N), and there was no abnormality in the appearance of the inorganic foam 2 after release. Contact angle 1 of Example 2
In the mold 1 of 30 degrees, the force required for release is 24 kgf (2
40N), and there was no abnormality in the appearance after release. The contact angle of the mold 1 of Example 3 was 60 degrees, and the force required for release was 40 kgf (390 N). However, there was no abnormality in the appearance of the inorganic foam 2 after release. The contact angle of the mold 1 of Comparative Example 1 was 20 degrees, and the tensile force required for release was 70K.
gf (690N). The appearance of the inorganic foam 2 of Comparative Example 1 was defective. The contact angle of the mold 1 of Comparative Example 2 was 175 degrees, and the tensile force required for releasing the mold was 28K.
gf (270 N), but air bubbles were generated on the surface of the inorganic foam 2, resulting in poor appearance.

The inorganic cured body 2 is used particularly for panels having high decorativeness, and is suitable for a wall panel for the interior of a building, a wall panel for an exterior, and a panel constituting a building.

[0044]

As described above, according to the first and _third aspects of the present invention, 100 parts by weight of the SiO ₂ —Al ₂ O ₃ -based reactive inorganic powder and 0.2 to 0.2 parts of the alkali metal silicate are used.
Consisting of 450 parts by weight and 35 to 1500 parts by weight of water,
Since this composition is charged into a mold having a contact angle of 55 to 170 degrees and heated and cured, a large force is not required at the time of demolding. For this reason, the surface of the inorganic cured body is not chipped at the time of demolding, and an inorganic cured body having excellent design can be easily obtained.

According to the second aspect of the present invention, since the composition charged in the mold is foamed, the weight of the inorganic cured product can be reduced.

[Brief description of the drawings]

FIG. 1 is a diagram showing the evaluation of the contact angle, the tensile force at the time of releasing, and the appearance of Examples 1-3 of the present invention and Comparative Examples 1 and 2.

FIG. 2 shows an example of the use of an inorganic foam 2 from a mold used in an embodiment of the present invention.
Figure showing the measurement state of the tensile force when releasing the mold

[Explanation of symbols]

 1 type body 2 inorganic foam

Claims (3)

[Claims] 1. A composition comprising a SiO ₂ —Al ₂ O ₃ -based reactive inorganic powder, an alkali metal silicate, and water is charged into a mold having a contact angle of 55 to 170 degrees and heated. A method for producing an inorganic cured product, which comprises curing. 2. The inorganic curing method according to claim 1, wherein said composition is charged into a mold having a contact angle of 55 to 170 degrees, and then said composition is foamed and then cured by heating. How to make the body. 3. A composition comprising 100 parts by weight of an SiO ₂ —Al ₂ O ₃ type reactive inorganic powder, 0.2 to 450 parts by weight of an alkali metal silicate, and 35 to 1500 parts by weight of water, Contact angle 5
A method for producing an inorganic cured product, wherein the inorganic cured product is put into a mold at a temperature of 5 to 170 degrees and cured by heating.