KR101162347B1 - Curable inorganic composition - Google Patents

Abstract

The curable inorganic composition according to the present invention is made by mixing 25 to 35 parts by weight of a fly ash with a metal oxide in advance with respect to 100 parts by weight of water glass, and as a result, good workability as an adhesive, paint, coating agent or filler having heat resistance and fire resistance. While providing a curable inorganic composition that can be used at low cost.

Description

Curable inorganic composition

FIELD OF THE INVENTION The present invention relates to curable inorganic compositions used as adhesives, paints, coatings, fillers, and the like, and more particularly to those having heat resistance and fire resistance.

Conventionally, the adhesive used for building materials, such as a plywood and a wallpaper, for example, was mostly organic. While this organic adhesive has good workability, such as drying property and applicability | paintability, there existed a fault which is inferior to heat resistance. In recent years, with the rise of awareness of disaster prevention, the Building Standard Act has been amended, and heat resistance and fire resistance have been demanded more than ever before for building materials and structures of buildings. For this reason, although the adhesive used in the construction field is required to be excellent in heat resistance more than conventionally, there is a limit to the improvement of heat resistance as an organic type adhesive agent, and it has not fully satisfied the request.

On the other hand, an inorganic adhesive is known conventionally as an adhesive agent which has the outstanding heat resistance and fire resistance. Generally as this inorganic adhesive agent, water glass and colloidal silica are used as a binder, and what mixed oxides, such as alumina, as a filler is known. Among them, inorganic adhesives using water glass have been used for adhesives such as glass or ceramics, fireproof coatings, etc., because water glass absorbs carbon dioxide gas in the air, precipitates gel silicic acid to form a glass, and exhibits strong adhesive force. In addition, since inorganic adhesives using water glass generally have a low curing rate, proposals for increasing the curing rate by adding antimony pentoxide, as described in Japanese Patent Application Laid-open No. Hei 6-25610 (hereinafter referred to as 'Patent Document 1'), etc. It is.

However, the conventional inorganic adhesive has a problem that it becomes much more expensive than the organic adhesive in that an oxide such as alumina is used. For this reason, it was not possible to use it in the manufacturing field for the construction field which uses a large amount of adhesives, for example, manufacture of plywood, affixing of a wallpaper, etc. In addition, the conventional inorganic adhesives were not able to withstand the use in building sites, which are often exposed to rain because of poor workability due to the low curing rate. Therefore, the conventional inorganic adhesive has rarely used as an adhesive or a coating agent in the construction field while having excellent heat resistance and fire resistance.

In addition, the inorganic adhesive described in Patent Document 1 improves the workability by increasing the curing rate (drying speed), but the manufacturing process is complicated, such as using alcohol as the reaction aid of water glass and antimony pentoxide and controlling temperature during stirring. It became more expensive than before. Therefore, it could not be used in the field of construction used in large quantities.

SUMMARY OF THE INVENTION The present invention has been made in view of these problems, and it is an object of the present invention to provide a curable inorganic composition that can be used at low cost and with good construction properties as an adhesive, paint, coating agent or filler having heat resistance and fire resistance.

The present invention is a curable inorganic composition, characterized in that the fly ash is mixed with 25 to 35 parts by weight and a metal oxide in advance with respect to 100 parts by weight of water glass.

In the curable inorganic composition of the said means, this invention WHEREIN: Zinc oxide is previously mixed with 15-25 weight part with respect to 100 weight part of water glass as said metal oxide, and 5-15 weight part of zircon flowers with respect to 100 weight part of water glass further. Characterized in that the mixture was made in advance.

The present invention also provides a curable inorganic composition of the above means, in which at least the water glass, the fly ash, the zinc oxide and the zircon flower are mixed, 22 to 40 wt% of silicon dioxide and 10 to 15 wt% of zinc oxide. 3 to 15% by weight of sodium oxide, 3 to 10% by weight of aluminum oxide, 2 to 8% by weight of zirconium oxide, and water.

The present invention is also characterized in that in the curable inorganic composition of the above means, the fly ash, the metal oxide and the zircon flower each include particles having a particle diameter of 45 μm or less.

According to the curable inorganic composition which concerns on this invention, it can exhibit the outstanding effect that it can be used at low cost with favorable workability as an adhesive agent, coating material, coating agent, filler etc. which have heat resistance and fire resistance.

1 is a view showing the results of the adhesive strength test.

The water glass used for the curable inorganic composition of this embodiment is a concentrated aqueous solution of sodium silicate, and is obtained by dissolving sodium silicate in water and heating. The composition of the water glass is Na ₂ O? NSiO ₂ , and in the water glass, Na ₂ O (sodium oxide) and SiO ₂ (silicon dioxide, silica) are present. Although commercially available water glass can be used, when the value of the molar ratio (n) is small, the produced composition is hard to be cured. When the value of the molar ratio (n) is large, the stability during storage of the produced composition is deteriorated. do. Therefore, in view of the balance between the curing rate and the stability of the curable inorganic composition, the water glass is, for example, JIS K1408 No. 1 (17 to 19 wt% Na ₂ O, 35 to 38 wt% SiO ₂ ) or No. 2 (Na ₂ O is 14-15 wt%, SiO ₂ is preferably defined as 34-36% by weight), it is also the molar ratio (n) value is more preferable as far as between 2 and 2.3.

Fly ash is coal ash collected by the dust collector from the combustion gas of the pulverized coal combustion boiler of a coal-fired power plant, for example. The ash particles produced when the pulverized coal is combusted in the pulverized coal combustion boiler are suspended in the hot combustion gas in a molten state and then cooled at the boiler outlet to become spherical fine particles. The spherical fine particles are fly ash, and the composition thereof is, for example, 40.1-74.4 wt% of SiO ₂ (silicon dioxide, silica), 15.7-35.2 wt% of Al ₂ O ₃ (aluminum oxide, alumina), and Fe ₂ O ₃ (iron oxide) is 1.4-17.5 weight%, MgO (magnesium oxide) is 0.2-7.4 weight%, and CaO (calcium oxide) is 0.3-10.1 weight%.

Fly ash is a material produced by high-temperature combustion in a boiler or the like, and since the flammable component hardly remains, it can be mixed to improve the heat resistance and fire resistance of the curable inorganic composition. Moreover, since fly ash is spherical microparticles | fine-particles, the fluidity | liquidity of curable inorganic composition can be improved by mixing. Therefore, in the curable inorganic composition of this embodiment, using the fly ash improves the stirring property at the time of manufacture, and improves the coating property and filling property at the time of construction.

In addition, by mixing fly ash with conventional concrete, Ca (OH) ₂ (calcium hydroxide) generated by reacting CaO with water and pozzolanic reaction in which SiO ₂ or Al ₂ O ₃ reacts slowly at room temperature result in long-term strength. It is known. In addition, when the mixing of fly ash in concrete, semi-stable SiO ₂ and the alkali ions in the concrete aggregate? Is known that the alkali silica reaction to hydroxyl ions reaction inhibition.

In the curable inorganic composition of the present embodiment, by utilizing such fly ash characteristics, it is possible to balance the curing rate and the stability at the time of storage and to maintain the stability at the time of storage while increasing the curing rate. Moreover, it is possible to raise the long-term strength and adhesive force of the inorganic composition after hardening.

Fly ash is produced as a by-product of coal-fired power plants and can be purchased at a much lower cost than silica or alumina, and commercially available products are available. In order to sufficiently mix the fly ash in the composition to improve the homogeneity of the curable inorganic composition and to stably exhibit the performance of the curable inorganic composition, the fly ash preferably has a particle diameter of 45 μm or less (for example, 1 to 45 μm), It is more preferable if particle diameter is 30 micrometers or less (for example, 1-30 micrometers).

Fly ash having a particle diameter of 45 µm or less or 30 µm or less can be obtained using, for example, a 45 µm sieve or a 30 µm sieve. In addition, the particle diameter of the fly ash does not necessarily need to be 45 micrometers (30 micrometers) or less, and it goes without saying that 45 micrometers (30 micrometers) or more may be contained partially.

Therefore, in consideration of cost and availability, fly ash is, for example, Class II of JIS A6201 (SiO ₂ ratio is 45% or more, 45μm sieve residue is 40% or less, and the specific surface area by the brain method 2500 cm 2 / g or more) or Class I (the ratio of SiO ₂ is 45% or more, the 45 μm sieve residue is 10% or less, and the specific surface area of the brain method is preferably 5000 cm 2 / g or more).

The metal oxide uses zinc oxide (ZnO) in the curable inorganic composition of this embodiment. This zinc oxide is a fine powder oxide and is generally used as a coating film reinforcing agent for coatings. In this embodiment, by mixing zinc oxide as appropriate, the viscosity of the curable inorganic composition is adjusted to improve the coating property and adhesiveness at the time of construction. Although zinc oxide can use a commercially available thing, in order to fully mix and disperse | distribute homogeneously in a composition, it is preferable that particle diameter is 45 micrometers or less (for example, 1-45 micrometers), and particle diameter is 30 micrometers or less (for example, 1-30 micrometers). Is more preferable.

The metal oxide whose particle diameter is 45 micrometers (30 micrometers) or less can be obtained, for example using a sieve, and the thing of 45 micrometers (30 micrometers) or more may be contained similarly to the fly ash mentioned above.

The metal oxide is not limited to the zinc oxide described above, and oxides of other metals such as magnesium, calcium, iron, and boron can be used, for example. In addition, only one type of metal oxide may be used or a plurality of types of metal oxides may be used.

In the curable inorganic composition of this embodiment, the zircon flower is further mixed in addition to the component mentioned above. This zircon flower is powder zircon (zirconium silicate, ZrSiO ₄ ) which mechanically grinds zircon sand. Since zircon flowers have a high melting point and low thermal expansion, they contribute to the improvement of the heat resistance and fire resistance of the curable inorganic composition. Moreover, since a zircon flower is water insoluble, it contributes to the improvement of the water resistance of a curable inorganic composition.

In addition, since the zircon flower has the effect of lowering the glass softening point of the mixed glass, it is possible to increase the flexibility when the curable inorganic composition is heated and vitrified to prevent embrittlement. Thereby, when the curable inorganic composition is used as a fireproof coating, it can improve the holding property of the coating film at the time of heating, for example, and can prevent it from peeling off easily.

Zircon flowers can be purchased relatively cheaper than silica and alumina, and commercially available ones can be used, but in order to be sufficiently mixed and homogeneously dispersed in the composition, particles having a particle diameter of 45 μm or less (for example, 1 to 45 μm) are preferable. Moreover, it is more preferable if particle diameter is 30 micrometers or less (for example, 1-30 micrometers).

A zircon flower having a particle diameter of 45 μm (30 μm) or less can be obtained by, for example, a sieve, and some of 45 μm (30 μm) or more may be included in the same manner as the fly ash and metal oxide described above.

The curable inorganic composition of the present embodiment is prepared by mixing 25 to 35 parts by weight of fly ash, 15 to 25 parts by weight of zinc oxide, and 5 to 15 parts by weight of zircon flower in a container with respect to 100 parts by weight of water glass. Is done.

It is preferable that the ratio of the fly ash with respect to 100 weight part of water glass is 25-35 weight part from the point of balance of the hardening speed and stability of a curable inorganic composition. When the ratio of the fly ash is less than 25 parts by weight, the curing rate is lowered, and when the ratio of the fly ash is greater than 35 parts by weight, the stability at the time of storage deteriorates and long-term storage becomes difficult, which is not preferable.

The ratio of the metal oxide with respect to 100 weight part of water glass is not specifically limited, A ratio can be suitably determined so that it may become a viscosity according to the use of curable inorganic composition. Moreover, a ratio can be determined suitably according to the kind of metal oxide to be used.

Moreover, the ratio at the time of using zinc oxide as a metal oxide is preferable at the point which becomes 15-25 weight part with respect to 100 weight part of water glass, and becomes the suitable viscosity which can acquire favorable workability. However, the ratio of zinc oxide may be changed according to the use of curable inorganic composition. For example, when using a curable inorganic composition as a putty or a filler, you may add zinc oxide 25 weight part or more with respect to 100 weight part of water glass.

Although the ratio of a zircon flower with respect to 100 weight part of water glass is not specifically limited, It is preferable that it is 5-15 weight part from the point which acquires suitable fire resistance and sets an appropriate glass softening point.

Moreover, in order to adjust the viscosity of curable inorganic composition, you may add a small amount of water (for example, about 1 to 15 weight%).

The mixing method can use a well-known method. In addition, mixing can be performed at room temperature. Moreover, after mixing each component sufficiently, it is left to stand in a cool dark place for about 1 day in a closed container, and the property of a composition is stabilized and predetermined viscosity and gloss appear.

The obtained curable inorganic composition contains 22 to 40% by weight of silicon dioxide (SiO ₂ ), 10 to 15% by weight of zinc oxide (ZnO), 3 to 15% by weight of sodium oxide (Na ₂ O), and aluminum oxide (Al ₂ O ₃₎ 3 to 10% by weight, zirconium oxide (ZrO ₂₎ 2 to 8 wt%, and which contains water preferably in view of balance, and the workability of the curing speed and stability, and 25 to 36 of silicon dioxide It is more preferable if it contains weight%, 12-13 weight% of zinc oxide, 6-11 weight% of sodium oxide, 5-6 weight% of aluminum oxide, 4-5 weight% of zirconium oxide, and water.

Example 1

Next, an embodiment of the present invention will be described.

In this example, water glass is a commercial cement fastener, fly ash is JIS standard II type, zinc oxide is JIS standard 1 type, and zircon flower is 98% or more and particle size 45μm or less.

100 g of water glass, 30 g of fly ash, 20 g of zinc oxide, 10 g of zircon flower, and a small amount of water were placed in a container and stirred for about 3 minutes at room temperature using a stirrer. After stirring, the composition was transferred to a closed container and stored in a cold dark for about 1 day to prepare a curable inorganic composition.

The obtained composition was a gray, viscous liquid, which was spread on the surface of various materials with a spatula or a brush, and was found to have good workability. In addition, the obtained composition has a specific gravity of about 1.8, a pH of about 12.2, and a component and content of 25 to 36% by weight of SiO ₂ , 12 to 13% by weight of ZnO, 6 to 11% by weight of Na ₂ O, and Al ₂ O. ₃ and 5 to 6% by weight, ZrO ₂ was a 4-5% by weight.

The adhesive strength at the time of using the obtained composition as an adhesive agent was tested based on JISK6849, K6850, and K6857, and the result was shown in FIG. As shown in FIG. 1, sufficient adhesive strength was obtained after drying for 72 hours at normal temperature, and the adhesive strength did not fall extremely even under high temperature. Moreover, it was confirmed that it has sufficient water resistance by baking for 1 hour.

Moreover, when a vinyl wallpaper was affixed on a wooden plywood as an adhesive with the obtained composition, and the wallpaper was heated for 2 minutes continuously with a gas burner (about 800 degreeC), the heating part of the wallpaper only carbonized and there was no change in the plywood. . In addition, even when heated for three minutes in a gas burner, the heating part of the wallpaper and the plywood only carbonized, and the plywood did not burn. This is because the curable inorganic composition of the present embodiment vitrifies and foams by heating, and prevents combustion of the plywood by forming an insulating non-combustible layer between the wallpaper and the plywood. That is, by using the curable inorganic composition of a present Example as an adhesive agent of a plywood or a wallpaper, it was possible to make these building materials fireproof.

As described above, the curable inorganic composition of the present invention can be produced at a lower cost than conventional inorganic adhesives without deteriorating quality or function by using a fly ash. For this reason, it can be used as an adhesive excellent in heat resistance and fire resistance also in the field where the inorganic adhesive was not used so much in the conventional cost like the construction field.

Moreover, by mixing each component in an appropriate ratio, it is possible to increase the curing rate and to have good workability, so that it can be widely used as a coating agent, paint, filler, etc. in addition to the adhesive. Moreover, since stability at the time of storage can also be provided, long-term storage is attained by storing in a cool dark place.

The curable inorganic composition of the present invention can be further stored for a long time by refrigerated at a temperature of 5 to 10 ° C.

In addition, since the curable inorganic composition of the present invention is vitrified and foamed when heated, and forms an insulating non-combustible layer, by applying it as an adhesive or a coating material to various building materials or structural materials, the fire resistance of these members can be increased to prevent fire in case of fire. have.

Moreover, the fireproof board excellent in fire resistance can be manufactured by using the curable inorganic composition of this invention as a binder of a molding.

In addition, the curable inorganic composition which concerns on this invention is not limited to said embodiment, Of course, various changes can be added within the range which does not deviate from the summary of this invention.

The curable inorganic composition according to the present invention can be used in fields such as adhesives, paints, coating agents or fillers requiring heat resistance and fire resistance in addition to the construction field.

Claims (4)

A curable inorganic composition, comprising 25 to 35 parts by weight of a fly ash and a metal oxide, based on 100 parts by weight of water glass. The method according to claim 1,
15-25 parts by weight of zinc oxide is mixed with 100 parts by weight of water glass as the metal oxide,
Furthermore, the zircon flower was mixed by 5-15 weight part with respect to 100 weight part of water glass, The curable inorganic composition characterized by the above-mentioned. The method according to claim 2,
As a result of mixing at least the water glass, the fly ash, the zinc oxide and the zircon flower,
22 to 40% by weight of silicon dioxide, 10 to 15% by weight of zinc oxide, 3 to 15% by weight of sodium oxide, 3 to 10% by weight of aluminum oxide, and 2 to 8% by weight of zirconium oxide. Curable inorganic composition. The method according to claim 2 or 3,
The fly ash, the metal oxide and the zircon flower are each curable inorganic composition, characterized in that it comprises a particle diameter of 45μm or less.

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