JPH02160651A - Hydraulic inorganic composition - Google Patents

Abstract

PURPOSE:To obtain a hydraulic inorganic composition, hardenable by addition of water and providing hardened bodies having excellent water repellency by blending a hydraulic inorganic raw material with a specific organopolysiloxane. CONSTITUTION:A composition consisting of (A) 100 pts.wt. hydraulic inorganic raw material and (B) 0.01-20 pts.wt. organopolysiloxane having at least one group, expressed by the formula (R is monofunctional hydrocarbon group; R<1> is bifunctional hydrocarbon group; X is hydrolyzable group; a is 0, 1 or 2) and linked to Si in one molecule. Lime raw material, such as Portland cement, quick lime, gypsum or calcium carbonate, and siliceous raw material, such as sand, clay, perlite or glass powder, are exemplified as the hydraulic inorganic raw material (A). The organopolysiloxane which is the component (B) is a component capable of imparting excellent water repellency in adding water to the above-mentioned composition and forming hardened bodies.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydraulic inorganic composition that is cured by the addition of water to form a cured product having extremely excellent water repellency.

[Prior Art] Conventionally, as typical examples of inorganic compositions that harden by the addition of water, there are compositions containing only a calcareous raw material or a calcareous raw material and a silicic acid raw material as main raw materials. Its hardened material includes mortar, various types of concrete, especially lightweight aerated concrete (ALC), and glass fiber reinforced concrete (GRC).
, Calcium silicate temporary limestone/slag mineral temporary, etc. These are high pressure steam curing and normal pressure steam curing.

It is manufactured by moist curing, air dry curing, etc., and has been widely used as on-site construction materials in civil engineering construction work, civil engineering blocks, construction panels, roof tiles, tiles, insulation materials, and heat-retaining materials.

However, since the above-mentioned hardened bodies, especially ALC, calcium silicate plates, or GRC panels, have high water absorption, water absorption causes a decrease in heat insulation and heat retention, and cracks occur due to water intrusion.9 Occurrence of surface collapse. Architectural panels have the disadvantage of poor dimensional stability;
It was necessary to apply a water agent, impregnate a water repellent, or add a water repellent internally to prevent water from entering.

Regarding products in which silicone is internally added as a TA solution, there is the following invention. For example, JP-A-58-2252 discloses dimethylpolysiloxane.

JP-A-57-123851 discloses emulsified dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrodienepolysiloxane or methylcarboxyl-modified polysiloxane with an anionic surfactant; JP-A-55-42272 discloses Dimethylpolysiloxane, amino group-containing polysiloxane, olefin-containing polysiloxane, fluorine-containing polysiloxane and alcohol-modified polysiloxane; 55-90460
The publications include methyl silicone varnish, phenyl methyl silicone varnish, silicone/epoxy modified varnish, and silicone/alkyd modified varnish.

It has been disclosed that a silicone-acrylic modified varnish and a silicone-polyester modified varnish are added as an Fa water agent.

However, although the cured products to which the various organopolysiloxanes cited above are added exhibit TA aqueous properties, the degree of the effect is not fully satisfactory;
In addition, when producing a cured product to which the above-mentioned organopolysiloxane is internally added, the effect of I8 aqueous is relatively effective in the case of a cured product that requires steam curing, steam heating, dry heat, etc. However, in the case of a cured product that is difficult to heat or does not require heating, the water repellency is extremely poor.

[Problems to be Solved by the Invention] The present invention aims to solve the above-mentioned drawbacks, and provides a hydraulic inorganic composition that can produce a cured product with extremely excellent water repellency even when no heating is required. It is on offer.

[Means for solving the problem and their effects] The above-mentioned purpose is (A) 100 parts by weight of hydraulic inorganic raw material (B
) The formula bonded to the silicon atom -R'-5+(R)a(X)3-- (wherein, R is 1
R1 is a divalent hydrocarbon group, x is a hydrolyzable group, a is 0. 1 or 2. ) This is achieved by a hydraulic inorganic composition characterized by comprising 0.01 to 20 parts by weight of an organopolysiloxane having at least one group represented by the following in one molecule.

To explain this, component (A), the hydraulic inorganic raw material, is the main material of the present invention, and includes Portland cement and alumina cement.

Calcareous raw materials such as magnesia cement, fly ash cement, blast furnace cement, silica cement, quicklime, slaked lime, calcium silicate, calcium carbonate, silica, sand, gravel, silica stone.

Clay, perlite, diatomaceous earth, rock powder (e.g. feldspar powder 1
Examples include silicic acid raw materials such as quartz powder) glass powder. Note that the calcareous raw material also includes a composite material of a calcareous raw material and a silicic acid raw material.

As long as they themselves have hydraulic properties, the calcareous raw material and the silicic acid raw material may be used independently, or the calcareous raw material and the silicic acid raw material may be used in combination.

The organopolysiloxane (B) component used in the present invention is a component that imparts extremely excellent water repellency when water is added to the present silicate to form a cured product. This organopolysiloxane has one formula -R'-Si in the silicon atom of its main chain.
At least one group represented by (R)s(X)31 is bonded in one molecule, and its position is only at the end of the molecular chain, only on the side chain, or on both the end and side chain of the molecular chain. May exist. The organopolysiloxane constituting the main chain is preferably linear, but a portion thereof may be branched, cyclic, or network-like. It also includes homopolymers, block copolymers, and random copolymers. The organopolysiloxane used in the present invention is preferably liquid at room temperature, and those represented by the following general formula are preferably used.

Si(R)a(X)3-a In the formula, R is the same or different monovalent hydrocarbon group, including methyl group, ethyl group, propyl group, octyl group, nonyl group, triple group, tetradecyl group, Alkyl groups such as 2-phenylethyl, aralkyl groups such as 2-phenylpropyl, 3, 3. 3. Examples include a halogen atom-substituted alkyl group such as a trifluoropropyl group, a cycloalkenyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a naphthyl group, and an alkaryl group such as a tolyl group and a xenyl 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 Fa aqueous property of the cured product, a combination of a methyl group and an alkyl group having 4 or more carbon atoms is preferred. R1 is a divalent hydrocarbon group, exemplified by alkylene groups such as ethylene group, n-propylene group, isopropylene group, and isobutylene group, with ethylene group being representative.

× is a hydrolyzable group, which includes an alkoxy group,
Examples include a ketoxime group, an aminooxy group, an alkenyloxy group, an amino group, an amide group, an imide group, a lactam group, and among these, a group selected from an alkoxy group, a ketoxime group, an aminooxy group and an alkenyloxy group is preferable. , an alkoxy group is particularly preferred.

a is 0, 1 or 2, preferably 0 or 1. ■ is 0-1000. n is 0 to 100°, but m+n
is from 0 to 1000. If m+n exceeds 1000, the dispersibility will be poor when blended as is, so it is preferably in the range of 2 to 1000. A is R or -
It is a group represented by R'-Si(R)a(X)3-1, and either one or both of A's are -R'-Si(R
)a(X) In the case of a group represented by 3-a, n may be 0. However, in order to make the cured product excellent water repellency, at least one -R'-5t(R
)a(X)3-a must be present.

This (B) component organopolysiloxane is (A
) is added in an amount of 0.01 to 20 parts by weight per 100 parts by weight of component. If it is less than 0.01 part by weight, a cured product with sufficient F8 aqueous properties cannot be obtained, and if it exceeds 20 parts by weight, it not only reduces the strength of the cured product but is also economically unfavorable. The preferred amount added is 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight.
It is 5 parts by weight.

The component (B), orcappolysiloxane, may be added as it is, or may be added in advance in the form of being supported on an emulsion 1) solution or an inorganic or organic powder. There are no particular limitations on the types of materials, methods, conditions, etc. used for this adjustment.

One example of the method for producing the organopolysiloxane component (B) is to use Si at one end, both ends, a side chain, or both ends and side chains.
Cfh=C)l in organopolysiloxane having H group
It can be easily produced by adding a vinyl group-containing organosilicon compound such as -Si(X)3 using an addition reaction catalyst.

Alternatively, after an addition reaction of CH2''CI (-SiCh to Si)I group, for example, methyl ethyl ketoxime may be bonded by dehydrochlorination reaction. Different X groups may be mixed in the siloxane.

If the organopolysiloxane having SiH groups has only lower alkyl groups such as methyl groups bonded,
During the above reaction, a higher alkyl group is introduced by simultaneous addition reaction with a high molecular weight α-olefin such as CH2:CH(CH2)-CH3, thereby imparting -N excellent water repellency. Can be done.

The hydraulic inorganic composition of the present invention consists of component (A) and component (B), and by adding water to it, a cured product with excellent water repellency can be obtained. In some cases, crushed ice can be used instead of water. The amount of water added is usually 1 per 100 parts by weight of component (A).
It is added in an amount of 0 to 300 parts by weight, but it may exceed 1000 parts by weight depending on the conditions (for example, the paper manufacturing method for calcium silicate plates), so it is advisable to add it as appropriate.

In addition to the water mentioned above, other components can be added to the zero morning composition as needed. For example, magnesium oxide,
Alumina, metal oxides such as iron oxide, asbestos, synthetic fibers, and glass fibers.

Reinforcing agents such as synthetic resin powder, wood chips, and mineral oil.

Other than component (B), organopolysiloxanes, surfactants, foaming agents such as metal powders, hardening accelerators, rust preventive agents, colorants, etc. can be mentioned.

In the present invention, a mixture of components (A) and (B) can be transported to a curing work site, where water can be added and cured. Furthermore, the components (A), (B) and water can be mixed and cured at the curing work site. It may be formed by adding water to form a slurry and pouring it into a mold, or it may be applied, sprayed, or impregnated without using a mold. In the case of solidification, it is possible to produce a cured product having excellent water repellency by drying it as it is at room temperature to solidify it, or by heat drying or steam curing at a relatively low to high temperature as necessary. Further, even if it is applied with a trowel like mortar on a wall and allowed to dry naturally at room temperature, a mortar finish with good tz water-based properties can be obtained.

'Therefore, the curing method is not particularly limited.

The hydraulic inorganic composition of the present invention is used for lightweight cellular concrete)
(ALC), glass fiber reinforced concrete 1 (GRC),
Other types of concrete, mortar, slate, blocks, cement tiles, wood wool cement boards, asbestos cement perlite boards, asbestos cement calcium silicate boards, gypsum slag plates, decorative asbestos cement [4, asbestos cement siding, calcium silicate insulation] It is useful as a perlite heat insulating material, etc.

Next, an example will be given and explained. In Examples and Comparative Examples, parts mean parts by weight, and the viscosity is the value at 25°C.

In the water repellency test, water droplets of approximately 0.03 grams were dropped at three locations on the surface of a molded cured product solidified to a size of 100 x 100 x 16 non, and the water repellency was observed and evaluated on the following five scales.

◎ Water droplets remain spherical even after 30 minutes, and water repellency is very good.

0 After 20 minutes, the water droplets become hemispherical, but 18 water quality is good.

△ Water droplets break down after 10 minutes, but are not absorbed, and water repellency is somewhat good.

* Water droplets are absorbed and diffused after 2 to 3 minutes, resulting in poor water repellency.

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

Example 1 300 parts of Portland cement, 6 parts of river sand produced for Watarase
After adding 150 parts of water and letting it dry for 2 minutes, 150 parts of water was added and kneaded for 3 minutes. Next, 9 parts of the organopolysiloxane shown in Table 1 were added, mixed for 3 minutes, and the mixture was cast into a 10100 x 100 x 16 stainless steel mold. After 48 hours, it was demolded and cured for 3 days in a thermostatic oven at 25°C and 85±5% humidity. Then,
It was naturally dried indoors at 28°C for 7 days. In this way, three sheets were made for each type of organopolysiloxane, one of which was not heated, and one of which was heated in a hot air dryer at 50° C. for 3 hours. The remaining one was heat treated at 100°C for 3 hours. Water droplets were dropped on the surface of each of the molded and cured bodies prepared in this way to examine the water repellency, and the results are shown in Table 2.

The molded and cured product of the present invention showed excellent F5 aqueous properties even without heat treatment compared to the comparative example. In addition, even more stable water repellency was shown when heated at a low temperature of 50°C to 100°C.

Table 1 Table 2 Example 2 100 parts of Portland cement, 2 parts of river sand produced for Watarase
00 parts, small gravel a with a diameter of 3-5 mm.

After adding 0 parts and letting it dry for 2 minutes, 130 parts of water was added and kneaded for 3 minutes. Next, 4.2 parts of the organopolysiloxane shown in Table 1 used in Example 1 was added and mixed for 3 minutes, and the mixture was cast into a 10100 x 100 x 16 stainless steel mold.

After 48 hours, it was removed from the mold and cured for one week in a thermostatic oven at 25°C and 85±5% humidity. Then, it was naturally dried indoors at 284C for 14 days. Water droplets were dropped on the surface of the molded and cured body prepared in this way, and the water repellency was observed.
The results are shown in Table 3.

The molded and cured product of the present invention showed good water repellency even without heating.

Table 3 Mixed for 3 minutes. This slurry is 10100x100x
The mixture was poured into a No. 16 mold and cured for 5 days in a constant temperature and humidity machine at 25°C and 85±5% humidity to foam and harden. Next, the molded cured product was removed from the mold, air-dried at room temperature for 14 hours, and further heat-treated at 100°C for 3 hours. Both molded and cured products are solid and have a specific gravity of approximately 0.73.
g/cm3. Drop water droplets onto this molded and cured body,
We checked the water repellency. The results are shown in Table 4. All of the molded and cured products of the present invention showed extremely good [a aqueous properties] when heated at low temperatures.

Example 3 90 parts of Portland cement, 10 parts of silica powder that had passed through 100 meshes, and 1 part of fine aluminum powder were slowly mixed in a mixing tank equipped with a propeller type stirrer, and then mixed with 15 parts of water and the organopolymer shown in Table 1 of Example 1. After adding 2 parts each of siloxane and adding 8 parts each of organopolysiloxanes of polysiloxane No. L 2.3 and 9 (comparative examples) in Table 4 at high speed (including those without additives as comparative examples), felt It was dehydrated using a cloth and heat-treated again in an autoclave at 140°C for 3 hours. Then 12o.

C. for 10 hours to produce a molded and cured product. A water repellency test was conducted on this molded and cured body.

All of the molded and cured products of the present invention exhibited good water repellency as shown in Table 5.

Table 5 Example 4 To 30 parts of quicklime, 70 parts of silica powder and 1500 parts of water were added and heat treated in an autoclave at 180"C for 6 hours. Next, ml of crushed asbestos was added to the cooled slurry.
1500 parts of Portland cement, 670 parts of silica sand of 100 mesh bath,
After adding 3,830 parts of sand and letting it dry for 2 minutes, 780 parts of water was added and mixed for 3 minutes.

Next, organopolysiloxane No. used in Example 1
, 1.6 (Comparative Example) and 18 parts of 8 (Comparative Example) were added and mixed for 3 minutes. Then 10100X100X1
A mold without additives (comparative example) and a mold with organopolysiloxane added were cast into the stainless steel molds of No. 6. The mold was removed after 48 hours, and then cured for 15 days in a thermostatic oven at a temperature of 20°C and a humidity of 85%. then 8
Heat treated in an oven at 0°C for 1 hour, then heated at 20°C.
The weight W1 was measured after immersing it in distilled water of C for 24 hours. Furthermore, the weight W2 was measured after drying in a constant temperature bath at a temperature of 105°C for 25 days. From this measured value, the water absorption percentage was determined using the following formula. The results are shown in Table 6.

It was confirmed that the molded and cured product of the present invention had an extremely low water absorption rate, and little water permeated even when immersed in water.

Table 6 Example 6 80 parts of hemihydrate powder and 20 parts of organopolysiloxane No. 1 used in Example 1 were uniformly mixed together in advance.

8 parts of hemihydrate treated with the above organopolysiloxane were added to 100 parts of hemihydrate, and 100 parts of water was added.
PJ was added and kneaded. This is 10100X100X
The mixture was placed in a stainless steel mold (No. 16), left at room temperature for 5 hours, and then dried at 60° C. for 20 hours to obtain a molded and cured plaster body. Water droplets were dropped on the surface to examine the water repellency.

As a comparative example, organopolysiloxane N016 and an additive-free one were also tested in the same manner. The results are shown in Table 7.

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

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

Table 9: The cured product has extremely excellent water repellency. Therefore, it is extremely useful especially as interior materials, exterior materials, heat insulating materials, heat retaining materials, etc. for buildings.

Claims (1)

[Claims] 1. (A) Hydraulic inorganic raw material 100 parts by weight (B) Formula bonded to silicon atom -R^1-Si(R)_a(X)_3_-_a (in the formula,
R is a monovalent hydrocarbon group, R^1 is a divalent hydrocarbon group, X is a hydrolyzable group, and a is 0, 1 or 2. ) A hydraulic inorganic composition characterized by comprising 0.01 to 20 parts by weight of an organopolysiloxane having at least one group represented by formula (1) in one molecule. 2. The hydraulic inorganic composition according to claim 1, wherein component (A) is a mixture of a calcareous raw material and a silicic acid raw material. 3. The hydraulic inorganic composition according to claim 2, wherein the calcareous raw material is cement and the silicic acid raw material is sand or silica powder. 4. Component (B) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a monovalent hydrocarbon group, A is R or -R^1
-Si(R)_a(X)_3_-_a group, R
^1 is a divalent hydrocarbon group, X is a hydrolyzable group, a is 0
, 1 or 2, m is 0-1000, n is 0-100, provided that m+n is 0-1000. ] The hydraulic inorganic composition according to claim 1, which is an organopolysiloxane represented by the following. 5. The hydraulic inorganic material according to claim 1 or 4, wherein the hydrolyzable group of component (B) is a group selected from an alkoxy group, a ketoxime group, an aminooxy group, and an alkenyloxy group. Composition.