JP2003081672A - Inorganic hardened body, and inorganic wall material - Google Patents

Abstract

(57) [Problem] To provide an inorganic hardened material and an inorganic wall material capable of maintaining the antifungal and antialgal performance at a constant level for a long period of time. SOLUTION: In a cured inorganic material 2 obtained by reaction-curing a curable inorganic composition 12 containing an aluminum oxide, a state in which aluminum ions remaining in the reaction and trapped inside after the reaction curing can be gradually released from the surface. And characterized in that the growth of algae can be inhibited.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic cured material and an inorganic wall material.

[0002]

2. Description of the Related Art Various inorganic hardened materials have been known so far. Japanese Examined Patent Publication (Kokoku) No. 4-45471 describes a hydrous molding material mainly composed of an alkali-containing inorganic component for compression molding or casting. Further, JP-A 2000-302523 describes an inorganic curable composition for forming a wall panel. The inorganic curable composition described in the above publication contains a reactive powder containing silicon dioxide and aluminum oxide, an alkali metal silicate and water. In addition, the actual public Sho 59-22817
The publication describes a wall panel made of lightweight aerated concrete (ALC) cured at high temperature and high pressure.

When the above-described inorganic cured body is used as a wall material for a house or the like, a coating film is formed on the surface of the inorganic cured body.
This coating film is composed of an organic compound such as a synthetic polymer. In such an organic coating film, the bonds of polymer chains are broken by the ultraviolet rays contained in the sun rays, so that the coating film gradually deteriorates over time.
This deterioration phenomenon of the coating film not only limits the life of the coating film itself, but also involves the phenomenon that the surface of the coating film loses smoothness and changes into an uneven shape, so that the floating property of green algae, mold, etc. Microorganisms are more likely to land on the coating film, which leads to a weak point that the coating film becomes a place for breeding of these microorganisms. Due to this weak point, the aesthetic appearance of a house or the like is gradually impaired, which causes an adverse effect.

Therefore, recently, building wall materials (outer wall panels, etc.) having antifungal and antialgal properties have been developed and are now on the market. In such building wall materials,
By adding an antifungal agent and an algae preventive agent to the paint used for the surface coating, it is possible to exhibit antifungal and antialgae performance. As a component of the antifungal agent or the antialgal agent, a chlorinated aromatic organic compound having a phenyl group or a pyridine group is generally known, and the antifungal agent or the antialgal agent is contained in the coating film. The effect of inhibiting the growth of molds and algae (mainly green algae) will be maintained for a certain time on the surface of the coating film.

[0005]

[Problems to be Solved by the Invention] However, the above growth inhibitory action (antagonism) against mold and algae
Since it is premised that the surface of the wall material is coated with a paint (antifungal, antialgae paint) to which an antifungal agent or an antialgae agent is added, it is inevitably limited to the surface part. As a result, there is a limit to the amount of the agent or the algae inhibitor added. Therefore, there is a problem that the above growth inhibitory action gradually decreases with the passage of time, and it is extremely difficult to maintain a certain level of antifungal and antialgal properties for a long period of time.

The present invention has been made in view of the above problems in the prior art, and provides an inorganic hardened body and an inorganic wall material capable of maintaining the fungicide-proof and algae-proof performance at a constant level for a long period of time. With the goal.

[0007]

The invention according to claim 1 is
In a cured inorganic material obtained by reaction-curing a curable inorganic composition containing an aluminum oxide, the reaction residual aluminum ions trapped inside after reaction curing are gradually released from the surface, and The feature is that the growth can be inhibited.

In the present invention according to the above-mentioned claim 1, in order to gradually release the reaction residual aluminum ions trapped inside after the reaction curing from the surface, a non-coating specification having no coating film is required. Good to do.

According to a second aspect of the present invention, in the inorganic cured product according to the first aspect, the curable inorganic composition is a reactive powder containing silicon dioxide and aluminum oxide, an alkali metal silicate, and water. It is characterized by including and.

According to a third aspect of the present invention, in the inorganic cured product according to the second aspect, the curable inorganic composition contains an alkali metal silicate in an amount of 0.1 parts by weight per 100 parts by weight of the reactive powder.
Within the range of 2 to 450 parts by weight, 35 parts by weight of water
It is characterized in that it is compounded in the range of 1500 parts by weight.

A fourth aspect of the present invention is an inorganic wall material formed of the inorganic hardened body according to any one of the first to third aspects.

(Function) The inorganic cured product according to claims 1 to 3 is an inorganic cured product obtained by reacting and curing a curable inorganic composition containing an aluminum oxide, and aluminum ions are eluted during the reaction. Cure the inorganic composition. Of the aluminum ions, the part that did not contribute to the curing reaction, that is, the aluminum ions remaining after the reaction, is trapped inside after the reaction curing. This reaction residual aluminum ion is made into a non-coating specification having no coating film so that it can be gradually released from the surface, and the aluminum ion gradually released from the surface is mildew,
It was found to inhibit the growth of algae. The above-mentioned antifungal and antialgal mechanism is a problem in the conventional building materials, that is, the deterioration of antifungal and antialgal performance, that is, various deterioration factors (ultraviolet rays, moisture, heat, oxygen, etc.) in the coating film. Since it is completely unrelated to the phenomenon that the effective concentrations of the antifungal agent and the algae preventive agent are lowered, the antifungal agent and the algae preventive performance can be maintained at a constant level for a long period of time.

In the inorganic hardened bodies according to claims 2 and 3, the curable inorganic composition contains a reactive powder containing silicon dioxide and aluminum oxide, an alkali metal silicate, and water. Therefore, the amount of aluminum ions stored inside the cured body is enormous, and there is no danger of semi-permanent depletion. Therefore, the fungicidal and algae-proofing performance can be maintained at a constant level for a long time.

The inorganic wall material according to claim 4 is characterized by that
Since it is formed of the inorganic cured product according to any one of 3 above, it becomes a wall material that keeps the antifungal and antialgal properties at a constant level for a long period of time.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

1 and 2 show an example of the first embodiment of the present invention. In FIG. 1, reference numeral 1 is a wall panel, and this wall panel 1 is formed from a cured body 2 of an inorganic curable composition described later.

As the inorganic curable composition which is the main component of the cured product (including foamed cured product) used in the present invention, an inorganic curable composition used for general wall panels can be applied. They may be, for example, high temperature and high pressure cured lightweight cellular concrete (ALC) described in Japanese Utility Model Publication No. 59-22817. In addition, special fair 4
It may be a cured product of the water-containing molding material for molding described in Japanese Patent Publication No. 45471.

In the present invention, silicon dioxide and aluminum oxide are used.
SiO containing minium₂-Al ₂O₃System reactive inorganic
Powder (hereinafter abbreviated as reactive powder) and alkali metal silicate
Inorganic curing consisting of water and water, optionally with blowing agent
It may be a cured product formed from the functional composition. Special
Alkali metal silicic acid is added to 100 parts by weight of the reactive powder.
Salt is added in the range of 0.2 to 450 parts by weight, and water is added to 35 parts by weight.
Inorganic curability compounded within the range of 1 to 1500 parts by weight
When forming the panel body from the composition,
To obtain a wall panel that is strong and has excellent fire resistance.
You can

Such a reactive powder contains silicon dioxide in the range of 5% by weight to 85% by weight, aluminum oxide in the range of 90% by weight to 10% by weight, and 5% by weight of other components. % To 10% by weight is preferably used. Examples of such reactive powder include fly ash, metakaolin, kaolin, mullite, corundum, dust when producing an alumina-based abrasive, and pulverized and baked bauxite. However, if the composition is appropriate, it is limited to these. It is not something that will be done.

These reactive powders may be used as they are, but those having a high reaction activity (hereinafter simply referred to as "activity") are classified and used, or a thermal spraying treatment or a pulverization treatment with mechanical energy is carried out. Thus, the one that has been activated is preferably used. These activation means can also be used in combination.

As a method of thermal spraying, a thermal spraying technique applied to ceramic coating is applied. In the thermal spraying technology, the material powder is usually 2000 ° C. to 16000.
Melted at a temperature within the range of 30 ° C., 30 m / sec to 800 m /
Atomized at a rate in the range of seconds. Moreover, the thing activated by the plasma spraying method, the high energy gas spraying method, the arc spraying method, etc. may be used. By such a treatment, the specific surface area of the powder is improved and activated. Suitable specific surface area is 0.1m ² / g~100m ² / g approximately.

As a method of pulverizing and applying mechanical energy, any conventionally known method is adopted. Examples of the crushing means include a jet mill, a roll mill and a ball mill. When using a ball medium mill, medium agitation mill, roll mill, etc., 0.5 kwh / kg to 30 kwh /
When mechanical energy of about kg is applied, activation proceeds properly. If the mechanical energy is low, the powder is hard to be activated, while if the mechanical energy is high, the load on these crushing devices is large. Further, the pulverized powder is classified by the above-mentioned classification means, if necessary. Here, the mechanical energy applied is a numerical value representing the electric power supplied to the ball mill per unit weight of the treated powder.

The fly ash as the raw material powder may be calcined if necessary. When the firing temperature is low, the black color of fly ash remains, making it difficult to color the molded product, and when the firing temperature is high, the reactivity with the alkali metal silicate is low, so the temperature is in the range of 400 ° C to 1000 ° C. It is preferable.

The alkali metal silicate used in the present invention has the general formula M ₂ O.nSiO ₂ (where M is K, Na,
One or more metals selected from Li, n
Indicates a positive number. ) Is a salt. If the value of n is small, a dense foam cannot be obtained, and if it is large, the viscosity of the aqueous solution increases and mixing becomes difficult. Therefore, n is preferably in the range of 0.05 to 8, more preferably 0.5 to 8. It is within the range of 2.5.

The alkali metal silicate may be blended as it is, but it is preferably added as an aqueous solution dissolved in water. Here, when the concentration of this aqueous solution becomes thin, the reactivity with the fly ash powder decreases, while when it becomes thick, solid contents are likely to occur, so a range of 10% by weight to 60% by weight is usually used.

Here, as a method for obtaining an aqueous solution of an alkali metal silicate, a usual method is adopted as it is. For example,
The alkali metal silicate may be directly dissolved in water under pressure and heating. Alternatively, an aqueous alkali metal hydroxide solution may be separately prepared, and SiO2 components such as silica sand and silica stone powder may be dissolved in the aqueous solution under pressure and heating so that n becomes a predetermined value.

Such alkali metal silicates are usually
0.2 to 450 parts by weight per 100 parts by weight of reactive powder
It is compounded within the range of parts by weight. If the content of the alkali metal silicate is small, curing will not proceed sufficiently, while if the content of the alkali metal silicate is large, the water resistance of the resulting foam will be reduced.
The preferable blending amount is 1 with respect to 100 parts by weight of the reactive powder.
Within the range of 0 to 350 parts by weight, more preferably 2
It is in the range of 0 to 250 parts by weight.

Water is added to this inorganic curable composition as an essential component. The blending amount of water is not particularly limited,
Usually, 35 parts by weight to 100 parts by weight of the reactive powder
It is in the range of 1500 parts by weight. If the amount of water to be blended is small, not only curing will not proceed sufficiently, but also mixing will be difficult. On the other hand, if the amount of water added is unnecessarily large, the strength of the cured product tends to decrease. The preferred amount of water is
45 to 1000 parts by weight with respect to 100 parts by weight of reactive powder
Within a range of 50 parts by weight, more preferably 50 parts by weight to 500 parts by weight.
Within the range of parts by weight. This water may be added in the form of the above-mentioned alkali metal silicate aqueous solution, or may be added independently.

In the present invention, the cured product may be a foamed cured product formed by containing a foaming agent. Such a foamed and hardened material has a wall panel having a heat insulating property and the like, and has a high added value. For this reason, a foaming agent is added to the above-mentioned inorganic curable composition together with a foaming aid, if necessary.

As the foaming agent, peroxides such as hydrogen peroxide, sodium peroxide, potassium peroxide and sodium perborate, and Mg,
Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, A
Examples of the metal powder include l, Ga, Sn, Si, and ferrosilicon. These foaming agents may be used alone or in combination of two or more. 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, it is preferable to use a fine powder having a particle diameter of 200 μm or less in order to obtain stable foaming.

In order to obtain a sufficient foamed cured product, it is preferable to use the foaming agent within the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the reactive powder. If the blending amount of the foaming agent is too small, the expansion ratio is too low to obtain a sufficient foamed cured product, while if the blending amount of the foaming agent is too large, the foaming gas becomes excessive and the foaming often occurs. .

A foaming aid is preferably added to the composition used in the present invention, if necessary, in order to uniformly generate foaming. Examples of such foaming aids include fatty acid metal salts such as zinc stearate, calcium stearate and zinc palmitate, silica gel, zeolite, activated carbon, and porous powder such as alumina powder. This foaming aid may be used alone or 2
You may use together more than one kind.

When the amount of the foaming aid is large, the viscosity of the inorganic curable composition may be increased and the foaming may be easily generated. Usually, this foaming aid is 10 parts by weight or less with respect to 100 parts by weight of the reactive powder.

In the present invention, an inorganic filler may be added if necessary. Inorganic filler does not dissolve in water,
There is no particular limitation as long as it does not inhibit the curing reaction of the inorganic curable composition and does not react with the alkali metal silicate. For example, silica sand, river sand, zircon sand, crystalline alumina,
Rock powder, volcanic ash, silica flower, silica fume,
Mixing material for mixed cement such as bentonite and blast furnace slag,
Natural minerals such as sepiolite, wollastonite, mica,
Examples include calcium carbonate and diatomaceous earth. These may be added alone or in combination of two or more.

When a foamed cured product is obtained, the size (average diameter) of the inorganic filler is preferably in the range of 0.01 μm to 1000 μm. When the average diameter is small, the viscosity of the inorganic curable composition increases, and it becomes difficult to obtain a high-magnification foam.
On the other hand, when the average diameter becomes large, foaming may become unstable. In addition, since the strength of the foam obtained is decreased when the amount of the inorganic filler is increased, the compounding amount of the inorganic filler is preferably 700 parts by weight or less relative to 100 parts by weight of the reactive powder. .

For the purpose of further reducing the weight of the cured product, silica foam, perlite, fly ash balloon, shirasu balloon, glass balloon, inorganic foam such as foamed clay, foaming of synthetic resin such as phenol resin, urethane resin, polyethylene and the like. Body, vinylidene chloride balloons and the like may be added. These may be added alone or in combination of two or more. Further, if necessary, alumina cement, γ-alumina, sprayed alumina, alkali metal aluminate or aluminum hydroxide may be added.

By mixing the above-mentioned respective components in an appropriate combination so that the whole inorganic curable composition becomes uniform and the reaction becomes uniform, a paste-like inorganic curable composition can be obtained. . The inorganic curable composition thus obtained is cured at room temperature, but the curing reaction is accelerated by heating. For example, 50 ℃ ~ 110 ℃
At a temperature within the range of, it is cured in about 30 minutes to 8 hours,
The mechanical properties such as the compressive strength of the molded product can be improved.

[0038]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples. The parts in the examples relate to weight unless otherwise specified. Example 1 [Activation treatment of reactive powder] 100 parts of metakaolin (SATINTONE SP 33 manufactured by Engelhard Co., average particle size 3.3 μm, specific surface area 13.9 m ² / g) was added with 25 parts by weight of triethanolamine. % And ethanol 75% by weight
0.5 parts of the mixed solution of
-20 (Mitsubishi Heavy Industries, zirconia ball diameter 10m
25 kwh when used for m, and the ball filling rate is 85% by volume.
Mechanical energy of / kg was applied to obtain ground metakaolin. The mechanical energy applied was represented by the electric power supplied to the ball mill per unit weight of the treated powder.

[Preparation of Inorganic Curable Composition] 100 parts of the obtained ground metakaolin, aqueous potassium silicate solution as alkali metal silicate (molar ratio 1.4, concentration 50% by weight)
165 parts, 1 of wollastonite as an inorganic filler
00 parts, 100 parts of silica sand, vinylon fiber (Kuraray Co.,
Trade name: RM182 × 3) 3 parts, 0.1 part of metallic silicon fine powder having a particle diameter of 200 μm or less as a foaming agent,
3 parts of zinc stearate as a foaming aid was mixed and used as a paste-like inorganic curable composition.

[Manufacture of Wall Panel] The method of manufacturing the wall panel of the present invention will be described with reference to FIG. First, the above-mentioned inorganic curable composition 12 was put into a box-shaped lower mold 11 for wall panels on which a rubber decorative mold 13 was laid. Next, after applying vibration to perform leveling and defoaming, the upper mold 14 is set and heated and solidified, and then the upper mold 14 is removed and the solidified inorganic cured body 2 is taken out from the lower mold 11, and the thickness is 15 mm and the width is 15 mm. 88
A wall panel 1 having a foamed inorganic cured body 2 having a length of 8 mm and a length of 2799 mm was obtained. The specific gravity of this wall panel 1 is 1.0, and the weight per unit area is 15 kg / m ^2.
Therefore, it was light in weight and the workability of mounting on the wall was improved.

[Performance Evaluation] The obtained wall panel 1 was attached to a housing unit according to a conventional method, placed in an area where a lot of algae breeding on the exterior material was observed, and an exposure test was conducted for observation of algae breeding progress. It was As a result, elapsed time 3
No algae were found at this point in the year.

[0042]

Comparative Example A wall panel 10 of a comparative example is shown in FIG.
Reference numeral 2 denotes an inorganic cured body, and this inorganic cured body 2 is the same as the inorganic cured body 2 shown in the above (Example 1).
Reference numeral 3 is a coating film, and this coating film 3 is formed of a coating material in which a decorative surface 1b of the inorganic hardened body 2 is added and mixed with an algae-preventing agent described later.

100 parts of ground metakaolin, aqueous potassium silicate solution as alkali metal silicate (molar ratio 1.4,
(Concentration: 50% by weight), 165 parts, 100 parts of wollastonite as an inorganic filler, 100 parts of silica sand, 3 parts of vinylon fiber (Kuraray Co., Ltd., trade name: RM182 × 3), particle size as a foaming agent. Of a finely divided metal silicon powder having a particle size of 200 μm or less and 3 parts of zinc stearate as a foaming aid are mixed to prepare a paste-like inorganic curable composition, and a rubber decorative mold is laid on the wall panel. It was put into a lower mold (1 m × 1 m, thickness 20 mm), and after leveling and defoaming by applying vibration, the upper mold was set and cured at 85 ° C. for 6 hours. After demolding, an inorganic cured body 2 was obtained.

Furthermore, the surface of the inorganic cured body 2 was uniformly coated with a coating material to which an algae control agent prepared by the method described below was added and mixed by an appropriate coating means such as spraying. The coating amount was set so that the thickness of the coating film 3 was 10 to 1000 μm.

Here, the pulverized metakaolin was prepared in the same manner as in the above (Example 1), and thus its details are omitted.

[Preparation of Algal Repellent] On the wall panel 10 described above, the coating film 3 is formed by the paint in which the algal repellent is added and mixed. The main component of this algal repellent is phenyl group or Chlorine-based aromatic organic compounds or nitrile-based chlorine compounds having a pyridine group or a pyrimidine group. Alternatively, an algae control composition containing a triazine compound and a hindered amine light stabilizer may be used as the main component of the algae control agent.

[Performance Evaluation] The obtained wall panel was attached to a housing unit according to a conventional method, placed in an area where a lot of algae breeding on the exterior material was observed, and an exposure test was conducted for observation of algae breeding progress. . As a result, it was clearly recognized that algae were continuously generated after the elapsed time of one year.

The embodiment of the present invention has been described in detail above with reference to the drawings. However, the specific configuration is not limited to this embodiment, and there may be a design change or the like within a range not departing from the gist of the present invention. Included in this invention.

[0049]

EFFECTS OF THE INVENTION The inorganic hardened product according to claims 1 to 3 and the wall material according to claim 4 can stably secure mold resistance and algae protection performance for a long period of time.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a wall panel according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view relating to a method of manufacturing the wall panel shown in FIG.

FIG. 3 is a cross-sectional view of a wall panel of a comparative example.

[Explanation of symbols]

1 wall panel (wall material) 2 Inorganic cured product 12 Inorganic curable composition

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Claims (4)

[Claims] 1. An inorganic cured product obtained by reactively curing a curable inorganic composition containing an aluminum oxide, so that the reaction-residual aluminum ions trapped inside after the reactive curing can be gradually released from the surface. An inorganic hardened body characterized by being able to inhibit the growth of algae. 2. The cured inorganic material according to claim 1, wherein the curable inorganic composition contains a reactive powder containing silicon dioxide and aluminum oxide, an alkali metal silicate, and water. . 3. The curable inorganic composition comprises a reactive powder 10
0 parts by weight of alkali metal silicate in the range of 0.2 parts by weight to 450 parts by weight and 35 parts by weight of water to 1500 parts by weight.
The inorganic cured product according to claim 2, which is compounded within a range of parts by weight. 4. An inorganic wall material formed of the inorganic cured body according to any one of claims 1 to 3.