JPH09124357A - Hardening inorganic-based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hardening inorganic-based composition capable of providing an inorganic-based hardened material excellent in waterproof and weather resistant properties. SOLUTION: This hardening inorganic-based composition consists of 100 pts.wt. SiO2 -Al2 O3 -based reactive powdery material, 0.2-450 pts.wt. alkali metal silicate, 10-1500 pts.wt. water, 0.01-75 pts.wt. alkylalkoxysilane expressed by formula I, R<1> n Si(OR<2> )4-n [R<1> is a 1-18C alkyl; R<2> is a 1-5C alkyl; (n) is a natural number of 1-3] and 0.01-30 pts.wt. alcohol expressed by formula II, R<3> OH (R<3> is a 1-5C alkyl).

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a curable inorganic composition.

[0002]

A curable inorganic composition which is cured by heat in the presence of an alkali is useful because it can form an inorganic cured product suitable for applications such as building materials. As such a curable inorganic composition, for example, JP-A-4-5 can be used.
In 9648, an inorganic solid component such as ash and fly ash of a dust collector generated during the production of metakaolin, corundum, and mullite is mixed with an alkali metal silicate aqueous solution, and a filler and an organic bentonite are added. Compositions for molded bodies are disclosed. In addition, Japanese Patent Laid-Open No. 4-613
Japanese Patent Publication No. 8 discloses a composition comprising an alkali metal silicate aqueous solution, the above-mentioned inorganic solid component and a filler.

However, among the above-mentioned inorganic solid components used in such a curable inorganic composition, fly ash and the like, which are industrial wastes and are required to be effectively utilized, have reactivity with alkali. Since it is low, the obtained inorganic cured product is inferior in water resistance and weather resistance, and it is difficult to obtain an inorganic cured product having a quality suitable for building materials and the like.

[0004]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a curable inorganic composition capable of obtaining an inorganic cured product having excellent water resistance and weather resistance.

[0005]

The gist of the present invention is to provide a curable inorganic composition comprising 100 parts by weight of SiO ₂ -Al ₂ O ₃ -based reactive powder (1), alkali metal silicate (2) 0. Two
˜450 parts by weight, water (3) 10 to 1500 parts by weight, general formula (I) R ¹ _n Si (OR ² ) _4-n (I) (In the formula, R ¹ is an alkyl group having 1 to 18 carbon atoms. Represents
R ² represents an alkyl group having 1 to 5 carbon atoms. n is 1 to
0.01 to 75 parts by weight of an alkylalkoxysilane (4) represented by a natural number of 3) and a general formula (II) R ³ OH (II) (wherein R ³ is a carbon number of 1 to 5). Of the alcohol (5) represented by the formula (1) represents 0.01 to 30 parts by weight.

As the above-mentioned SiO ₂ -Al ₂ O ₃ -based reactive powder (1), 10 to 90% by weight of SiO ₂ and Al ₂ O are used.
₃ 90 to 10 and a weight percent of the composition is preferred. Examples of such a material include (a) fly ash containing 80% by weight or more of powder having a particle size of 20 μm or less, (b)
Fly ash that is fired at 400 to 1000 ° C. and contains 80% by weight or more of powder having a particle size of 20 μm or less, (c)
Inorganic powder obtained by melting fly ash or clay and spraying it in gas, (d) 0.1 to 3 in clay
Inorganic powder obtained by applying mechanical energy of 0 kWh / kg, (e) Inorganic powder obtained by heating the inorganic powder at (d) at 100 to 750 ° C., (f) Metakaolin, etc. However, the present invention is not limited to these as long as the composition and particle size are appropriate. These can be used in combination of two or more.

The alkali metal silicate (2) is represented by the general formula M ₂ O.nSiO ₂ (wherein M represents at least one selected from the group consisting of Li, K and Na, n is a positive value). Represents the rational number of)
It is represented by In the present invention, among these, those having n of 0.05 to 8 are preferable. When n is less than 0.05, the reactivity with the raw material powder is low and the strength of the compact is low, and when n is more than 8, the aqueous alkali metal silicate solution is apt to gel and the viscosity rapidly increases. So the above S
Mixing with the iO ₂ -Al ₂ O ₃ -based reactive powder (1) becomes difficult. It is more preferably 0.1 to 3, and even more preferably 0.5 to 2.5.

The alkali metal silicate (2) is preferably added as an aqueous solution. The concentration of the aqueous solution is not particularly limited, but 1 to 70% is preferable. 1%
If it is less than the above value, the reactivity with the above-mentioned SiO ₂ —Al ₂ O ₃ based reactive powder (1) is lowered, and if it exceeds 70%, a solid content tends to be generated. In order to obtain an aqueous solution of the above alkali metal silicate (2), the above alkali metal silicate (2) may be dissolved in water as it is. Alternatively, an aqueous solution of the alkali metal hydroxide may be added to SiO ₂ such as silica sand or silica stone powder. The components may be dissolved so that n has a value within a predetermined range.

The amount of the alkali metal silicate (2) added is such that the SiO ₂ --Al ₂ O ₃ system reactive powder (1) 10
It is 0.2 to 450 parts by weight with respect to 0 parts by weight. 0.2
If it is less than parts by weight, the amount of alkali necessary for the reaction is too small to cause curing failure, and if it exceeds 450 parts by weight, a large amount of the curing agent causes a problem in the water resistance of the resulting inorganic cured product. Therefore, it is limited to the above range. It is preferably 10 to 350 parts by weight, more preferably 2
0 to 250 parts by weight.

The amount of water (3) added is such that the SiO _2-
1 to 100 parts by weight of Al ₂ O ₃ based reactive powder (1)
0 to 1500 parts by weight. If it is less than 10 parts by weight,
It becomes difficult to mix with the above-mentioned SiO ₂ —Al ₂ O ₃ -based reactive powder (1), and when it exceeds 1500 parts by weight, the mechanical strength of the obtained inorganic cured product decreases, so the content is limited to the above range. It The amount is preferably 10 to 1000 parts by weight, more preferably 10 to 500 parts by weight.

The above alkylalkoxysilane (4) is
It is represented by the general formula (I) R ¹ _n Si (OR ² ) _4-n (I). In the general formula (I), R ¹ has 1 to 1 carbon atoms.
18 represents an alkyl group. R ² represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 3. When the carbon number of R ¹ exceeds 18, it is not a liquid and does not become a product, and when the carbon number of R ² exceeds 5, it is not a liquid and does not become a product. Therefore, each is limited to the above range. It If the carbon number of R ¹ is less than 6, the water-absorption preventing property of the obtained inorganic cured body becomes small, so that R ¹
It is preferable that the carbon number of is 6-18.

The amount of the alkylalkoxysilane (4) added is such that the SiO ₂ -Al ₂ O ₃ -based reactive powder (1) is added.
It is 0.01 to 75 parts by weight with respect to 100 parts by weight.
If the amount is less than 0.01 parts by weight, the water resistance of the resulting inorganic cured product is insufficient, and if it exceeds 75 parts by weight, curing inhibition occurs and the strength of the resulting inorganic cured product is reduced. Limited to Preferably 0.01-5
It is 0 part by weight, more preferably 0.01 to 30 parts by weight.

The alkylalkoxysilane (4) is not particularly limited, and examples of the general formula (I) in which n is 1 include, for example, n-decyltrimethoxysilane, methyltrimethoxysilane and n-propyl. Trimethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, i
so-butyltrimethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-s
ec-butoxysilane, methyltri-t-butoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methacryoxypropyltrimethoxysilane,
And mercaptopropyltrimethoxysilane.

Examples of the above general formula (I) in which n is 2 include, for example, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldi-n-propoxysilane,
Dimethyl-iso-propoxysilane, dimethyldi-n
-Butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-t-butoxysilane, diethyldiethoxysilane, ethylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane and the like can be mentioned.

Examples of the above general formula (I) in which n is 3 include, for example, trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane,
Trimethyl-iso-propoxysilane, trimethyl-
n-butoxysilane, trimethyl-sec-butoxysilane, trimethyl-t-butoxysilane, triethylethoxysilane, diethylphenylethoxysilane, γ-
Examples thereof include glycidoxypropylethylmethylethoxysilane.

The alcohol (5) is represented by the general formula (II) R ³ OH (II). In the present invention, the above alcohol (5)
Can improve the dispersibility of the alkylalkoxysilane (4). In the above general formula (II), R
³ represents an alkyl group having 1 to 5 carbon atoms. When the carbon number of R ³ is more than 5, the dispersibility of the alkylalkoxysilane (4) cannot be improved, so the range is limited to the above range.

The amount of the alcohol (5) added is S
It is 0.01 to 30 parts by weight with respect to 100 parts by weight of the iO ₂ -Al ₂ O ₃ based reactive powder (1). If it is less than 0.01 parts by weight, sufficient dispersibility cannot be exhibited, and if it exceeds 30 parts by weight, curing inhibition occurs and the strength of the resulting inorganic cured product decreases, so the content is limited to the above range. It is preferably 0.01 to 20 parts by weight.

The alcohol (5) is not particularly limited, and examples thereof include methyl alcohol, ethyl alcohol,
Examples include propyl alcohol, butyl alcohol, amyl alcohol and the like.

In the present invention, as a method of adding the alkylalkoxysilane (4) and the alcohol (5), the alkylalkoxysilane (4) is diluted with the alcohol (5) in advance and then added. It is preferable.

In the present invention, if necessary, further,
A foaming agent, an inorganic filler, a reinforcing fiber, a foaming aid, an organic foam, an inorganic foam and the like may be added. The foaming agent is not particularly limited, and examples thereof include peroxides such as hydrogen peroxide, sodium peroxide, potassium peroxide, and sodium perborate; Mg, Ca, Cr, Mn, Fe, Co, Ni,
Examples thereof include metal powders such as Cu, Zn, Al, Ga, Sn, Si and ferrosilicon. Of these, the cost,
Hydrogen peroxide and aluminum powder are preferable from the viewpoint of safety, availability, mixing, and the like.

The amount of the foaming agent added is such that the SiO ₂ -A
l ₂ O ₃ -based reactive powder (1) with respect to 100 parts by weight.
01 to 10 parts by weight is preferable. If it is less than 0.01 part by weight, the expansion ratio is too small and the effect of the addition of the foaming agent is not obtained.
If it exceeds 0 parts by weight, the foaming gas becomes excessive and the bubbles are broken.

When hydrogen peroxide is used as the foaming agent, it is preferably used as an aqueous solution. In this case, the concentration of the aqueous solution is preferably 0.5 to 35%.
If it is less than 0.5%, the amount of water will be too much relative to the amount of hydrogen peroxide, the viscosity will decrease and the foaming will not be stable.
If it exceeds%, it is dangerous because the foaming is too fast and the foaming cannot be performed stably. It is more preferably 1 to 25%, further preferably 5 to 15%. When a metal powder is used as the foaming agent, the average particle size is preferably 1 to 200 μm. If it is less than 1 μm, the dispersibility is lowered, the reactivity is increased, and the foaming is too fast.
If it exceeds m, the reactivity decreases.

The above-mentioned inorganic filling material reduces shrinkage upon curing,
It is possible to improve the fluidity of the slurry, densify the cells, stabilize the bubbles, and the like. The inorganic filler is not particularly limited, for example, silica sand, silica stone powder, fly ash, slag, silica fume, mica, talc, wollastonite, calcium carbonate, aerosil, silica gel, zeolite, activated carbon, porous alumina gel and the like. Quality powder and the like. The inorganic filler has an average particle diameter of 0.01 μm
It is preferably 1 mm. If less than 0.01 μm,
When the amount of adsorbed water increases, the viscosity increases and the workability decreases, and when it exceeds 1 mm, foaming becomes unstable. The addition amount of the inorganic filler is preferably 700 parts by weight or less with respect to 100 parts by weight of the SiO ₂ —Al ₂ O ₃ based reactive powder (1). If it exceeds 700 parts by weight, the strength of the obtained inorganic cured product is reduced. More preferably, 10 to 50
0 parts by weight.

The reinforcing fiber can improve strength, prevent cracks and the like. The reinforcing fiber is not particularly limited, and examples thereof include organic fibers such as vinylon, polypropylene, aramid, acrylic, and rayon; inorganic fibers such as carbon, glass, potassium titanate, alumina, steel, and slag wool. The fiber length of the reinforcing fiber is
1 to 15 mm is preferable, and the fiber diameter is preferably 1 to 500 μm. When the fiber length exceeds 15 mm, the dispersibility decreases, and when the fiber diameter is less than 1 μm, the particles are re-aggregated during mixing and the strength of the inorganic cured product obtained by forming a fiber ball is not improved. If the length is less than 1 mm or the fiber diameter exceeds 500 μm, the reinforcing effect is small. The amount of the reinforcing fiber added is the same as that of the SiO ₂ —Al ₂ O.
_It is preferably 10 parts by weight or less with respect to 100 parts by weight of the ₃ type reactive powder (1). If it exceeds 10 parts by weight, the dispersibility of the fiber will be reduced.

With the organic foam and the inorganic foam, the weight of the resulting inorganic cured product can be reduced.
The organic foam is not particularly limited, for example, vinyl chloride, phenol, urea, styrene, urethane,
Examples thereof include granular foams of synthetic resin such as ethylene. These can be used alone or in combination of two or more. The inorganic foam is not particularly limited, and examples thereof include a glass balloon, a shirasu balloon, a fly ash balloon, a silica balloon, a pearlite, a hillstone, and a granular foamed silica. These can be used alone or in combination of two or more. Further, the organic foam and the inorganic foam may be mixed and used.

The above organic foam and the above inorganic foam
Preferably has a specific gravity of 0.01 to 1. Less than 0.01
It is possible to reduce the mechanical strength of the resulting cured inorganic material.
Inviting, if it exceeds 1, it will reduce the weight of the obtained inorganic cured product.
No effect. More preferably 0.03 to 0.7
Things. Of the organic foam and the inorganic foam
The addition amount is the above-mentioned SiO_Two-Al_TwoO _ThreeSystem reactive powder
(1) 10 to 100 parts by weight is preferable to 100 parts by weight
New When the amount is less than 10 parts by weight, the resulting inorganic cured product is obtained.
If the effect of weight reduction is not obtained and exceeds 100 parts by weight,
The mechanical strength of the obtained inorganic cured product decreases. Better
It is preferably 30 to 80 parts by weight.

In order to obtain an inorganic cured product from the curable inorganic composition of the present invention, for example, the alkali metal silicate (2) is dissolved in the water (3) under heating and pressure, and further,
The SiO ₂ —Al ₂ O ₃ -based reactive powder (1), the alkylalkoxysilane (4) diluted with the alcohol (5), and if necessary, a filler, a reinforcing fiber and the like are mixed, A method of shaping the obtained mixture into a desired shape by a known method such as casting or pressing and then curing the mixture can be employed. In this case, the curing temperature may be room temperature, but may be 50 to 200 ° C. because it can accelerate the curing reaction and improve the mechanical properties of the resulting inorganic cured product.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 2, 4 and 6 SiO ₂ --Al ₂ O ₃ type reactive powder A (SiO ₂ 52.
9% by weight, Al ₂ O ₃ 45.5% by weight, Fe ₂ O ₃ 0.
3% by weight, TiO ₂ 0.6% by weight, other 0.7% by weight, average particle size 3.3 μm, and metakaolin (SA
TINTONESP 33, manufactured by Engelhard)
SiO ₂ -Al ₂ O ₃ based reactive powder B (SiO ₂ 52.
3% by weight, Al ₂ O ₃ 45.0% by weight, Fe ₂ O ₃ 0.
5 wt%, TiO ₂ 1.5% by weight, other 0.7% by weight, an average particle diameter of 2.9 .mu.m), the SiO ₂ -Al
Ultrafine mill AT-20 (using zirconia balls 10 mmφ, ball filling rate 85%, Mitsubishi, together with 10 g of a mixture of triethanolamine 25% / ethanol 75% which is a grinding aid, ₂ O ₃ reactive powder A 1.7 kg. Supplied to Heavy Industries, Ltd., 9.9 kWh / kg (3 hours x
The powder obtained by applying mechanical energy of 3.3 kW / kg was used as SiO ₂ -Al ₂ O ₃ -based reactive powder C (Si
O ₂ 58.7% by weight, Al ₂ O ₃ 24.2% by weight, Fe
₂ O ₃ 6.9% by weight, TiO ₂ 1.1% by weight, other 9.1% by weight, average particle size 5 μm), fly ash (average particle size 20 μm, JIS A 6201 compliant, manufactured by Kandenko Co., Ltd.) The fly ash was classified by a classifier (TC-15, manufactured by Nisshin Engineering Co., Ltd.) and used as fly ash containing 100% by weight of powder having a particle size of 10 μm or less.

SiO ₂ -A with the compounding ratios shown in Tables 1 and ₂
l ₂ O ₃ -based reactive powder A, SiO ₂ -Al ₂ O ₃ -based reactive powder B, SiO ₂ -Al ₂ O ₃ -based reactive powder C, No. 8 silica sand (manufactured by Sekimoto Kenzai Co., Ltd.), silica stone Powder (fine silica, Blaine value 10,000 cm ² / g, manufactured by Sumitomo Cement Co., Ltd.), potassium silicate aqueous solution (SiO ₂ : K ₂ O molar ratio = 1.4: 1,
42% aqueous solution, manufactured by Nippon Kagaku Kogyo Co., Ltd., and the alkylalkoxysilanes shown in Tables 1 and 2 diluted with the alcohols shown in Tables 1 and 2 were respectively supplied to an omni mixer to obtain 5
After mixing for 150 minutes, the resulting mixture is 150 x 50 x 10
It was poured into a mold having a size of mm and heated with a mold in a hot-air dryer at 85 ° C. for 10 hours, to thereby form Examples 1 to 8 and Comparative Examples 2 and 4,
6 inorganic cured products were obtained. Each of the obtained inorganic cured products was demolded and dried at 50 ° C. for 10 hours, and then the physical properties of the following items were examined by the following evaluation methods. The results are shown in Tables 1 and 2.

Evaluation method 1. Contact Angle of Water The contact angle of water with the inorganic cured body surface when water having a diameter of 2 mm was dropped onto the surface of the obtained inorganic cured body was measured by CONTA.
It was measured by CT-ANGLEMETER (manufactured by Kyowa Interface Science Co., Ltd.). 2. The water absorption was determined by the following formula, where a is the weight of the inorganic cured product kept in a hot air dryer at 105 ° C. for 24 hours, and b is the weight of the inorganic cured product immersed in 20 ° C. water for 24 hours. (B−a) / a × 100 (wt%) 3. Hot water test The obtained inorganic cured product was dipped in hot water of 98 ° C for 2 hours and then dried for 24 hours, and the appearance was visually observed. Those doing are marked as x. 4. Accelerated weathering resistance test: The obtained inorganic cured product was subjected to an accelerated weathering resistance test according to JIS K 5400 for 500 hours, and then visually observed for appearance. Those that occurred are marked with x.

Comparative Examples 1, 3, 5 An inorganic cured product was obtained and evaluated in the same manner as in Examples 1 to 8 except that the alkylalkoxysilane and the alcohol were not added. The results are shown in Table 2.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

EFFECTS OF THE INVENTION The curable inorganic composition of the present invention, having the above-mentioned constitution, can provide an inorganic cured product having excellent water absorption prevention properties, water resistance, and weather resistance, and is suitable for applications such as building materials. Can be used.

Claims (1)

[Claims] 1. A SiO ₂ —Al ₂ O ₃ -based reactive powder (1) 100 parts by weight, an alkali metal silicate (2) 0.2.
˜450 parts by weight, water (3) 10 to 1500 parts by weight, general formula (I) R ¹ _n Si (OR ² ) _4-n (I) (In the formula, R ¹ is an alkyl group having 1 to 18 carbon atoms. Represents
R ² represents an alkyl group having 1 to 5 carbon atoms. n is 1 to
0.01 to 75 parts by weight of an alkylalkoxysilane (4) represented by a natural number of 3) and a general formula (II) R ³ OH (II) (wherein R ³ is a carbon number of 1 to 5). Of the alcohol (5) represented by the formula (1) is included in an amount of 0.01 to 30 parts by weight.