JP2686792B2 - 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.

[Prior Art] Conventionally, as a typical example of an inorganic composition that is cured by the addition of water, there is a calcareous raw material alone or a calcareous raw material and a silicic acid raw material as main raw materials. Examples of hard materials include mortar, various concretes, especially lightweight cellular concrete (ALC), glass fiber reinforced concrete (GRC), calcium silicate board, gypsum / slag ore plate, etc. It is manufactured by steam curing, wet curing, air dry curing, etc., and has been widely used as a material for on-site construction in civil engineering and construction work, a block for civil engineering, a panel for construction, roof tiles, tiles, a heat insulating material or a heat insulating material.

However, the above cured products, especially ALC, calcium silicate plate, GRC panel, etc., have a large water supply property, so that they absorb water to lower the heat insulation properties and heat retention properties, cracks due to water intrusion, surface disintegration, and Building panels have the disadvantage of poor dimensional stability, which is why the surface is coated with a water repellent, impregnated with a water repellent, or internally added to prevent water from entering. There was a need.

There is the following invention in which silicone is internally added as a water repellent. For example, in JP-A-58-2252, dimethyl polysiloxane, and in JP-A-57-123851, dimethyl polysiloxane, methylphenyl polysiloxane, methyl hydrogen polysiloxane or methyl carboxyl-modified polysiloxane is used as anionic yarn surface active agent. Emulsified with an agent, in JP-A-55-42272, dimethylpolysiloxane, amino group-containing polysiloxane, olefin-containing polysiloxane, fluorine-containing polysiloxane and alcohol-modified polysiloxane, JP-A-55-8545
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.

4 [Problems to be Solved by the Invention] The present invention aims to eliminate the above-mentioned drawbacks, and a hydraulic inorganic composition capable of producing a cured product having extremely excellent water repellency even if it does not require heating. To supply.

[Means for Solving the Problem and Its Action] The above-mentioned objects are (A) 100 parts by weight of a hydraulic inorganic raw material (B) an alkoxy group or a hydroxyl group bonded to a silicon atom in one molecule. (In the formula, R ¹ is a divalent hydrocarbon group, R ² and R ³ are groups selected from hydrogen atoms and monovalent hydrocarbon groups, and a is a number of 0 to 10.) It is achieved by a hydraulic inorganic composition, characterized in that it comprises from 0.01 to 20 parts by weight of an organopolysiloxane each having one.

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, calcined lime, slaked lime, gypsum, calcium silicate, calcium carbonate and other calcareous raw materials, silica, sand, gravel, silica, clay, perlite, diatomite, rock powder (eg long Examples thereof include siliceous raw materials such as stone powder, quartz powder) and glass powder. 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 an alkoxy group or a hydroxyl group bonded to the silicon atom of its main chain. At least one each of the groups represented by is bonded in one molecule, and these essential groups may be present at any position in the molecular structure. The organopolysiloxane constituting the main chain is preferably linear, but may be partially branched, cyclic, or network. Also, a homopolymer,
It may be 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.

In the formula, R is a group selected from an alkoxy group, a hydroxyl group and a monovalent hydrocarbon group, and as the monovalent hydrocarbon group, a methyl group, an ethyl group, a propyl group, an octyl group, a nonyl group,
Alkyl group such as tridel group and tetradecyl group, 2-
Aralkyl groups such as phenylethyl group and 2-phenylpropyl group, halogen atom-substituted alkyl groups such as 3,3,3-trifluoropropyl group, cycloalkyl groups such as cyclohexyl group, phenyl group, naphthyl group and tolyl group. An aryl group such as a group is exemplified. Preferred monovalent hydrocarbon groups are a methyl group or a combination of a methyl group and an alkyl group having 4 or more carbon atoms. At least one of all Rs must be an alkoxy group or a hydroxyl group, including the case where this R and A described later are R. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an ethoxymethoxy group, and the like, and a methoxy group and an ethoxy group are preferable.
Rather, an alkoxy group is preferable to a hydroxyl group from the viewpoint of water repellency. R ¹ is a divalent hydrocarbon group, which includes alkylene groups such as ethylene group, n-propylene group, isopropylene group and isobutylene group, arylene groups such as phenylene group, alkylenearylene groups such as ethylenephenylene group. Examples of the group include alkylene groups, of which ethylene groups and propylene groups are preferable.

R ² and R ³ are groups selected from a hydrogen atom and a monovalent hydrocarbon group, and the monovalent hydrocarbon group is the same as the examples of the monovalent hydrocarbon group described above. a is 0-10
However, it is preferably 0 to 3. m is 0 to 1000, n
Is 0 to 100, but m + n is 0 to 1000. m + n is 10
If it exceeds 00, the dispersibility becomes poor when it is blended as it is, so that it is preferably in the range of 2 to 1000. A is R
Or Is a group represented by, and either one or both of A In the case of the group represented by, n may be 0. However, in order to make the cured product excellent in water repellency, at least one At least one alkoxy group or hydroxyl group must be present in the group represented by.

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 the form of being previously supported on an emulsion, a solution, or an inorganic or organic powder. There is no particular limitation on the type, method, conditions, etc. of the materials used for this preparation.

As an example of the method for producing the organopolysiloxane as the component (B), a methoxy group and CH _{2 3} NHCH ₂ CH ₂ NH are provided at both ends of the molecular chain.
The production method of the organopolysiloxane having ₂ includes:
By reacting (CH ₃ ) O ₂ (CH ₃ ) SiCH _{2 3} NHCH ₂ CH ₂ NH ₂ with an organopolysiloxane having hydroxyl groups at both ends of the molecular chain, the hydroxyl group and the methoxy group undergo a condensation reaction, resulting in At the end It is possible to easily produce an organopolysiloxane in which is bonded. In addition, when dimethylpolysiloxane is produced by equilibrating octamethyltetracyclosiloxane in the presence of a sodium hydroxide catalyst, the above (CH ₃ O) ₂
By the presence of (CH ₃ ) SiCH _{2 3} NHCH ₂ CH ₂ NH ₂ , dimethylpolysiloxane having a — (CH _{2 3} NHCH ₂ CH ₂ NH ₂ group in the side chain and a hydroxyl group at both ends of the molecular chain is obtained. The organopolysiloxane as the component (B) may be produced by any method and is not limited in any way.

The hydraulic inorganic composition of the present invention comprises the component (A) and the component (B).
It is composed of components, and by adding water thereto, a cured product having excellent water repellency can be obtained. In some cases, crushed ice can be used instead of water. The amount of water added is usually 10 parts by weight per 100 parts by weight of component (A).
˜300 parts by weight is added, but depending on the conditions (for example, a paper-making method such as calcium silicate plate), it may exceed 1000 parts by weight, so it may be added appropriately.

In addition to the water described above, other components can be added to the composition, if necessary. 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.

Example 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 slumped but did not reach absorption, and the water repellency was 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 way, three sheets of each of the organopolysiloxanes were prepared, and one of them was heated without heating with a hot air dryer at 50 ° C. 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, 6 parts of the organopolysiloxane shown in Table 1 used in Example 1 was added and kneaded for 3 minutes, and the mixture was punched and formed into a 100 × 100 × 16 mm 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 70 parts of silica powder and 500 parts of water were added to 30 parts of quicklime and heat-treated in an autoclave at 180 ° C. for 6 hours. Next, 100 parts of asbestos fibers crushed in the cooled slurry, 100 parts of Portland cement and 8 parts each of organopolysiloxane Nos. 3, 4, 5 and 10 (comparative example) used in Example 1 were added. After that (including a non-added one as a comparative example), dehydration molding was performed using felt cloth, and heat treatment was performed again 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 4, all of the molded cured articles according to the present invention exhibited good water repellency.

Example 4 1500 parts of Portland cement, 670 parts of 100-mesh pass silica sand and 3830 parts of sand were placed in a 5 volume Hobart mixer container and kneaded for 2 minutes, then 780 parts of water was added and kneaded for 3 minutes. Next, 18 parts of the organopolysiloxane Nos. 3 and 6 (comparative example) and 8 (comparative example) used in Example 1 were added and mixed 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 5.

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 5 80 parts of Hemihydrate Kou and 20 parts of the organopolysiloxane No. 3 used in Example 1 were premixed uniformly.

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 6.

Example 6 Portland cement 270 parts, perlite 44 parts, asbestos 8
After mixing 6 parts and 250 parts of water with a kneading machine, the mixture
Then, 4 parts of the organopolysiloxane No. 4 used in Step 1 was added and further stirred. Next, the four sides of the filter cloth were stopped, a 100 × 100 × 16 mm formwork was placed on the filter cloth, and the above-mentioned kneaded material was poured flat into the formwork, dewatered, and left as it was for 24 hours. . Then, it was removed from the mold and dried in a hot-air dryer at 105 ° C. for 15 hours to obtain a molded cured product. Water droplets were dropped on the surface to check the state of water repellency.

As a comparative example, the same procedure was performed for organopolysiloxane No. 8 and those without addition. The results are shown in Table 7.

Those to which the organopolysiloxane of the present invention was added exhibited very good water repellency.

[Effects of the Invention] The hydraulic inorganic composition of the present invention comprises an alkoxy group or a hydroxyl group bonded to a silicon atom and a compound of the formula Since an organopolysiloxane having at least one group represented by the formula (1) in each molecule is blended, when cured by addition of water, a cured product having extremely excellent water repellency as compared with a conventional product is obtained. 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 (4)

(57) [Claims] 1. (A) 100 parts by weight of hydraulic inorganic raw material (B) In one molecule, an alkoxy group or a hydroxyl group bonded to a silicon atom. (In the formula, R ¹ is a divalent hydrocarbon group, R ² and R ³ are groups selected from hydrogen atoms and monovalent hydrocarbon groups, and a is a number of 0 to 10.) A hydraulic inorganic composition characterized by comprising 0.01 to 20 parts by weight of an organopolysiloxane each having one. 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 group selected from an alkoxy group, a hydroxyl group and a monovalent hydrocarbon group, A is R or Where R is at least one is an alkoxy group or a hydroxyl group. R ¹ is a divalent hydrocarbon group,
R ² and R ³ are groups selected from hydrogen atoms and monovalent hydrocarbon groups, a is a number from 0 to 10, m is 0 to 1000, and n is 0 to 10.
0, where m + n is 0 to 1000. The hydraulic inorganic composition according to claim 1, which is an organopolysiloxane represented by the following formula: