JP2640514B2 - Hydraulic inorganic composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hydraulic inorganic composition which is cured by adding water to form a cured product having extremely excellent water repellency.

[Related Art] Conventionally, as a typical example of an inorganic composition which is hardened by addition of water, there is a calcareous material alone or a material mainly composed of a calcareous material and a siliceous material. Examples of the cured product include mortar, various types of concrete, particularly lightweight cellular concrete (ALC), glass fiber reinforced concrete (GRC), calcium silicate plate, and stone slag / slag ore plate. These are high-pressure steam curing, normal pressure Manufactured by steam curing, warm curing, air drying curing, etc., it has been widely used as a material for on-site construction in civil engineering construction, a block for civil engineering, a panel for construction, a tile, a tile, a heat insulating material or a heat insulating material.

However, the above-mentioned cured product, especially ALC, calcium silicate plate or GRC panel, etc. has a large water absorption, so that heat absorption lowers heat insulation, lowers heat retention, cracks due to water intrusion, surface collapse, and The drawback is that the dimensional stability of the building panels is poor, so that the surface is coated with a water repellent, impregnated with a water repellent, or internally added with a water repellent to prevent water intrusion. Needed.

There is the following invention in which silicone is internally added as a water repellent. For example, JP-A-58-2252 discloses dimethylpolysiloxane, and JP-A-57-123851 discloses dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane or methylcarboxyl-modified polysiloxane as anionic surfactants. JP-A-55-42272 discloses dimethylpolysiloxane, amino-containing polysiloxane, olefin-containing polysiloxane, fluorine-containing polysiloxane and alcohol-modified polysiloxane.
No. 2 discloses methylphenylpolysiloxane and chlorophenylmethylpolysiloxane, and JP-A-55-90460 discloses methylsilicone varnish, phenylmethylsilicone varnish, silicone-epoxy modified varnish, silicone-alkyd-modified varnish, silicone acrylic. It is disclosed that a modified varnish and a silicone / polyester modified varnish are added as a water repellent.

However, although the cured products to which the various organopolysiloxanes cited above are added exhibit water repellency, the degree of the effect is not sufficiently satisfactory, and the above-mentioned organopolysiloxane is added internally. When producing a cured product, if the cured product requires heating by steam curing, steam heating, or dry heat, the effect of water repellency is relatively effective, but heating is difficult or requires heating. However, in the case of a cured body which does not have the above, there is a disadvantage that the water repellency is extremely poor.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks, and to provide a hydraulic inorganic composition capable of producing a cured product having extremely excellent water repellency even without heating. To offer.

[Means for Solving the Problems and Action Thereof] The object described above is as follows: (A) 100 parts by weight of a hydraulic inorganic material (B) Formula -R ¹ -Si (R) _a (X) bonded to a silicon atom
_3-a (wherein R is a monovalent hydrocarbon group, R ¹ is a divalent hydrocarbon group, X is a hydrolyzable group, and a is 0.1, 1 or 2). It is achieved by a hydraulic inorganic composition comprising 0.01 to 20 parts by weight of an organopolysiloxane having at least one organopolysiloxane therein.

Explaining this, the hydraulic inorganic raw material of the component (A) is the main material of the present invention, which includes Portland cement, alumina cement, magnesia cement,
Fly ash cement, blast furnace cement, silica cement, quicklime, slaked lime, calcareous materials such as limestone, calcium silicate, calcium carbonate, silica, sand, gravel, silica stone, clay, perlite, diatomaceous earth, rock powder Silicic raw materials such as stone powder and quartz powder) glass powder are exemplified. Note that the calcareous raw material also includes a composite material of the calcareous raw material and the silica raw material. If it has hydraulic properties by itself, the calcareous raw material and the siliceous raw material may be used independently, or the calcareous raw material and the siliceous raw material may be mixed and used.

The organopolysiloxane (B) used in the present invention is a component that imparts extremely excellent water repellency when a cured product is obtained by adding water to the present composition. This organopolysiloxane has the formula —R ¹ —Si added to a silicon atom in its main chain.
(R) _a (X) _a compound in which at least one group represented by (a) is bound in one molecule, and the position thereof is only at the molecular chain terminal, only at the side chain, or at the position between the molecular chain terminal and the side chain It may be present in both. The organopolysiloxane constituting the main chain is preferably linear, but is partially branched, cyclic,
It may be reticulated. Further, it may be a homopolymer, a block copolymer, or a random copolymer. The organopolysiloxane used in the present invention is preferably a liquid at room temperature, and those represented by the following general formula are preferably used.

Wherein R is the same or different monovalent hydrocarbon groups, including methyl, ethyl, propyl, octyl,
Nonyl group, Tridel group, alkyl group such as tetradecyl group, 2-phenylethyl group, aralkyl group such as 2-phenylpropyl group, 3,3,3, halogen atom-substituted alkyl group such as trifluoropropyl group, Examples thereof include a cycloalkenyl group such as a cyclohexyl group, and an aryl group such as a phenyl group, a tolyl group and a naphthyl group. Preferred is a methyl group or a combination of a methyl group and an alkyl group having 4 or more carbon atoms. In order to further increase the water repellency of the cured product, a combination of a methyl group and an alkyl group having 4 or more carbon atoms is preferable. R ¹ is a divalent hydrocarbon group, and examples thereof include an alkylene group such as an ethylene group, an n-propylene group, an isopropylene group, and an isobutylene group, and an ethylene group is typical.

X is a hydrolyzable group, which includes an alkoxy group, a ketoxime group, an aminooxy group, an alkenyloxy group, an amino group, an amide group, an imide group, a lactam group and the like, among which an alkoxy group, a ketoxime A group selected from a group, an aminooxy group and an alkenyloxy group is preferred, and an alkoxy group is particularly preferred.

a is 0, 1 or 2, but preferably 0 or 1. m is 0 to 1000, n is 0 to 100, but m + n is 0 to 1000
It is. If m + n exceeds 1000, the dispersibility becomes poor when blended as it is, so that the range is preferably from 2 to 1,000. A is R or -R ¹ -Si (R) _a (X)
A group represented by the _3-a, is a group represented by both either or both of ^{A -R 1 -Si (R) a} (X) 3-a may be an n is 0. However, in order to make the cured product excellent in water repellency, at least one -R ¹
—Si (R) _a (X) The group represented by _3-a must be present.

The organopolysiloxane as the component (B) is
(A) It is added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the component. If the amount is less than 0.01 part by weight, a cured body having sufficient water repellency cannot be obtained.If the amount exceeds 20 parts by weight, not only the strength of the cured body is reduced, but also it is not economically preferable. The amount is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

The organopolysiloxane as the component (B) may be added as it is, or may be added in a form previously supported by an emulsion, a solution, or an inorganic or organic powder. There is no particular limitation on the types, methods, conditions, etc. of the materials used for this adjustment.

As an example of the method for producing the organopolysiloxane of the component (B), one end, both ends, side chains or both ends and side chains have Si.
CH ₂ CHCH—Si is added to organopolysiloxane having H group.
(X) It can be easily produced by adding a vinyl group-containing organosilicon compound such as ₃ using an addition reaction catalyst.

Further, after CH ₂ CHCH—SiCl ₃ is added to the SiH group, for example, methyl ethyl ketoxime may be bound by a dehydrochlorination reaction. If there is no problem, 1
Different X groups may be mixed in the organopolysiloxane in the molecule.

If the organopolysiloxane having SiH groups is bonded only to lower alkyl groups such as methyl groups,
During the above reaction, by simultaneously addition reaction of _{CH 2 = CH (CH 2)} 7 high molecular weight α- olefins, such as CH _3, by introducing a higher alkyl group, impart a more excellent water repellency by this can do.

The water-curable inorganic composition of the present invention comprises the component (A) and the component (B), and a water-repellent cured body can be obtained by adding water thereto.
In some cases, crushed ice can be used instead of water. The amount of water to be added is usually 10 to 300 parts by weight per 100 parts by weight of the component (A), but may exceed 1000 parts by weight depending on conditions (for example, a paper making method such as a calcium silicate plate). May be appropriately added.

In addition to the above-mentioned water, other components can be added to the present composition as needed. For example, metal oxides such as magnesium oxide, alumina, iron oxide, asbestos,
Reinforcing agent such as synthetic fiber, glass fiber, synthetic resin powder, etc.
Wood chips, mineral oil, organopolysiloxanes other than the component (B), surfactants, foaming agents such as metal powders, curing accelerators,
Rust inhibitors, coloring agents, and the like.

According to the present invention, the mixture of the components (A) and (B) is transported to a curing work site, where the mixture can be cured by adding water. Further, the three components (A), (B) and water can be mixed and cured at the curing work site. A slurry obtained by adding water may be poured into a mold for molding, or may be applied, sprayed, or impregnated without using a mold. In the case of solidification, a cured product having excellent water repellency can be produced by drying at room temperature as it is and solidifying it, or by heat drying or steam curing at a relatively low or high temperature as required. Moreover, even if it is applied with a trowel like a wall mortar and naturally dried at room temperature as it is, a mortar finish with good water repellency can be obtained.
Therefore, the curing method is not particularly limited.

The hydraulic mineral composition of the present invention includes lightweight cellular concrete (ALC), glass fiber reinforced concrete (GRC), other various concretes, mortar, slate, block,
Cement tile, wool cement board, asbestos cement perlite board, asbestos cement calcium silicate board, stone slag ore board, decorative asbestos cement board, asbestos cement siding,
It is useful as a calcium silicate heat insulator, perlite heat insulator, and the like.

Next, an example will be described. In the examples and comparative examples, “parts” means “parts by weight”, and the viscosity is a value at 25 ° C.

In the water repellency test, approximately 0.03 g of water droplets were dropped on each of three places on the surface of the molded cured product that had been solidified to 100 × 100 × 16 mm, and the water repellency was observed. did.

◎ After 30 minutes, the water droplets are kept spherical, and the water repellency is very good.

○ After 20 minutes, the water droplet becomes hemispherical, but has good water repellency.

△ After 10 minutes, the water droplets are broken but not absorbed, and the water repellency is slightly good.

× After 2 to 3 minutes, water droplets are absorbed and diffused, and the water repellency is poor.

×× Water droplets are immediately absorbed and diffused, and their water repellency is very poor.

Example 1 300 parts of Portland cement, 600 sand from Watarase river
And kneading for 2 minutes, then adding 150 parts of water and adding 3 parts.
The mixture was kneaded for a minute. Next, 9 parts of the organopolysiloxane shown in Table 1 was added and kneaded for 3 minutes.
It was stamped into a 0 × 100 × 16 mm stainless steel mold.
After 48 hours, the mold was removed and cured in a thermo-hygrostat at 25 ° C. and 85 ± 5% humidity for 3 days. Next, it was air-dried in a room at 28 ° C. for 7 days. In this manner, three sheets of each of the organopolysiloxanes were prepared, one of them was heated, and one was heated with a 50 ° C. hot air drier for 3 hours. The remaining one is 10
Heat treatment was performed at 0 ° C for 3 hours. Water droplets were dropped on the surface of each of the thus-prepared cured moldings to check the water repellency, and the results are shown in Table 2.

The molded cured product according to the present invention showed remarkably good water repellency even without heat treatment as compared with the comparative example. In addition, 50 ℃ ~ 10
Even at a low temperature of 0 ° C., more stable water repellency was exhibited.

Example 2 100 parts of Portland cement, 200 river sand from Watarasegawa
Then, 300 parts of small gravel having a diameter of 3 to 5 mm were added and kneaded for 2 minutes, and then 130 parts of water was added and kneaded for 3 minutes. Then, 4.2 parts of the organopolysiloxane shown in Table 1 used in Example 1 was added, and the mixture was kneaded for 3 minutes to obtain 100 × 100 × 16 mm.
Of the stainless steel mold.

After 48 hours, the mold was removed and cured in a thermo-hygrostat at 25 ° C. and a humidity of 85 ± 5% for one week. Next, it was air-dried in a room at 28 ° C. for 14 days. Water droplets were dropped on the surface of the molded cured product thus prepared, and the water-repellent state was observed. The results are shown in Table 3.

The molded cured product according to the present invention exhibited good water repellency without heating.

Example 3 90 parts of Portland cement, 10 parts of silica powder passing through 100 mesh, and 1 part of aluminum fine powder were slowly mixed in a mixing tank having a propeller-type stirrer, and then 15 parts of water and an organo compound shown in Table 1 of Example 1 were mixed. Two parts of each polysiloxane were added and mixed at high speed for 3 minutes. 100 × 100 this slurry
It was poured into a × 16 mm formwork, cured at 25 ° C. in a thermo-hygrostat of 85 ± 5% humidity for 5 days and foam-hardened. Next, after the molded cured product was removed from the mold, it was naturally dried at room temperature for 14 hours, and further heated at 100 ° C. for 3 hours to perform heat treatment. Each of the molded cured products was firm and had a specific gravity of about 0.73 g / cm ³ . Water droplets were dropped on the cured molded body, and the water-repellent state was examined. The results are shown in Table 4. All of the cured moldings according to the present invention exhibited extremely good water repellency when heated at a low temperature.

Example 4 To 30 parts of quick lime, 70 parts of silica stone powder and 1500 parts of water were added, and 180 ° C.
In an autoclave for 6 hours. Next, 100 parts of ground asbestos fiber, 100 parts of Portland cement and 8 parts of each of the organopolysiloxanes of the organopolysiloxanes Nos. 1, 2, 3 and 9 (comparative examples) used in Example 1 were added to the cooled slurry. Thereafter (including those without addition as a comparative example), dehydration molding was performed using a felt cloth, and heat treatment was again performed in an autoclave at 140 ° C. for 3 hours. Thereafter, the molded product was dried at 120 ° C. for 10 hours to produce a molded cured product. A water repellency test was performed on the molded cured product.
As shown in Table 5, all of the molded cured articles according to the present invention exhibited good water repellency.

Example 5 1500 parts of Portland cement, 670 parts of silica sand and 3830 parts of 100 mesh pass sand and 5830 parts of sand were placed in a 5-volume Hobart mixer container, kneaded for 2 minutes, and then 780 parts of water were added and kneaded for 3 minutes. Next, 18 parts of the organopolysiloxane Nos. 1, 6 (Comparative Example) and 8 (Comparative Example) used in Example 1 were added, and kneaded for 3 minutes. Thereafter, a mold made of 100 × 100 × 16 mm made of stainless steel without addition (comparative example) and an organopolysiloxane added were punched and formed. 48
After an hour, the mold was released, and then cured in a thermo-hygrostat at a temperature of 20 ° C. and a humidity of 85% for 15 days. Then in an 80 ° C oven
And time heat treatment was then measured by weight W ₁ after soaking for 24 hours in distilled water at 20 ° C.. In addition, 2
5 days and then dried to measure the weight W ₂ from. From this measured value, the water absorption% was determined by the following equation. The results are shown in Table 6.

The water absorption of the molded cured product according to the present invention was extremely low, and it was confirmed that water penetration was small even when immersed in water.

Example 6 80 parts of hemihydrate stone and 20 parts of the organopolysiloxane No. 1 used in Example 1 were uniformly mixed in advance.

To 100 parts of hemihydrate stone, 8 parts of hemihydrate stone treated with the above organopolysiloxane was added, and 100 parts of water was further added and kneaded. This was put in a 100 × 100 × 16 mm stainless steel mold, left at room temperature for 5 hours, and then dried at 60 ° C. for 20 hours to obtain a molded hardened stone. Water droplets were dropped on the surface to check the state of water repellency.

As a comparative example, an organopolysiloxane No. 6 and an additive-free product were similarly prepared. The results are shown in Table 7.

Example 7 A molded cured product was produced using the organopolysiloxane shown in Table 8 under the same conditions as in Example 1, and its water repellency was examined. The results are shown in Table 9.

As in Example 1, all of the samples to which the organopolysiloxane of the present invention was added exhibited excellent water repellency.

Example 8 Using the organopolysiloxanes shown in Table 8,
As a result of examining the water-repellent state of the molded and cured body of masonry stone manufactured under the same conditions as in Example 6, all showed excellent water-repellency as in Example 6.

[Effect of the Invention] The hydraulic inorganic composition of the present invention has the formula -R ¹ -Si (R)
_a (X) Since an organopolysiloxane having at least one group represented by _3-a in one molecule is compounded,
When cured by the addition of water, the cured product has extremely excellent water repellency as compared with conventional products. Therefore, it is particularly useful as an interior material, an exterior material, a heat insulating material, a heat insulating material and the like for a building.

Claims (5)

(57) [Claims] (A) 100 parts by weight of a hydraulic inorganic raw material (B) a formula -R ¹ -Si (R) _a (X) bonded to a silicon atom
_3-a (wherein R is a monovalent hydrocarbon group, R ¹ is a divalent hydrocarbon group, X is a hydrolyzable group, and a is 0.1, 1 or 2). A hydraulic inorganic composition comprising from 0.01 to 20 parts by weight of an organopolysiloxane having at least one organopolysiloxane therein. 2. The hydraulic inorganic composition according to claim 1, wherein the component (A) is a mixture of a calcareous raw material and a siliceous raw material. 3. The hydraulic mineral composition according to claim 2, wherein the calcareous raw material is cement and the siliceous raw material is sand or silica powder. (4) The component (B) has a general formula [Wherein, R is a monovalent hydrocarbon group, A is R or -R ¹ -Si
(R) _a (X) a group represented by _3-a , R ¹ is a divalent hydrocarbon group, X is a hydrolyzable group, a is 0, 1 or 2, m is 0 to 10
00, n is 0 to 100, where m + n is 0 to 1000. The hydraulic inorganic composition according to claim 1, which is an organopolysiloxane represented by the following formula: 5. The method according to claim 1, wherein the hydrolyzable group of the component (B) is a group selected from an alkoxy group, a ketoxime group, an aminooxy group and an alkenyloxy group. Hydraulic inorganic composition.