JPH02145467A - Hydraulic inorganic composition - Google Patents

Abstract

PURPOSE:To give extremely excellent water repellency even to a body cured without heat by using an organopolysiloxane bearing alkoxy or hydroxy groups and a specific group as an organopolysiloxane to be added to the starting materials for hydraulic inorganic substance. CONSTITUTION:The subject hydraulic inorganic composition is composed of 100 pts.wt. of the starting material for hydraulic inorganic substance and 0.01 to 20 pts.wt. of an organopolysiloxane bearing one or more alkoxy or hydroxy groups and groups of the formula binding Si atoms in one molecule, respectively. In the formula, R<1> is a divalent hydrocarbon group, R<2> and R<3> are H and groups selected from monovalent hydrocarbons, a is a number of 0 to 10. The addition of water to the composition gives a cured product of excellent water repellency.

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. As a hardened material, mortar, various types of concrete, especially lightweight cellular concrete)
(ALC), glass fiber reinforced concrete) (GRC)
, calcium silicate plate 9, gypsum/slag ore plate, etc., which are high pressure steam cured and normal pressure steam cured.

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, so the surface is coated with water repellent, impregnated with water repellent, or water repellent is added internally to prevent water ingress. There was a need.

Regarding products in which silicone is internally added as a water repellent, there are the following inventions. 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.

Silicone◆The addition of acrylic modified varnishes and silicone polyester modified varnishes as water repellents is disclosed.

However, although the cured products added with the various organopolysiloxanes cited above exhibit water repellency,
The degree of the effect is not fully satisfactory, and in the case of a cured product that requires steam curing, steam heating, dry heat, etc. when producing a cured product to which the above-mentioned organopolysiloxane is internally added. Although these have relatively effective water repellency effects, they have the disadvantage that they are difficult to heat or have extremely poor water repellency in the case of cured products that do not require heating.

[Problems to be Solved by the Invention] The present invention aims to solve the above-mentioned drawbacks, and provides a hydraulic structural composition capable of producing a cured product having extremely excellent water repellency even when no heating is required. It's about providing things.

[Means for Solving the Problems and Their Effects] The above-mentioned purpose is to (A) 100 parts by weight of hydraulic inorganic raw material (B
) Alkoxy bonded to a silicon atom in one molecule (in the formula,
R1 is a divalent hydrocarbon group, R2 and R3 are groups selected from hydrogen atoms and monovalent hydrocarbon groups, and a is a number of O to 10. ) 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 formulas.

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.

Magnesia cement, fly ash cement.

Calcareous raw materials such as 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) and 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 at least one alkoxy group bonded to the silicon atom in its main chain in each molecule, and these essential groups can be located at any position in the molecular structure. may exist in The organopolysiloxane constituting the main chain is preferably linear, but a portion thereof may be branched, cyclic, or network-like. It can also be a homopolymer, a block copolymer, or a random copolymer. The organopolysiloxane used in the present invention is preferably 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 examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an octyl group, a nonyl group,
Triple group, alkyl group such as tetradecyl group, 2-
Aralkyl groups such as phenylethyl group, 2-phenylpropyl group, 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.

A preferred monovalent hydrocarbon group is 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 R, including this R and the case where A described below is R, must be an alkoxy group or a hydroxyl group. This alkoxy group includes a methoxy group,
It is a group selected from ethoxy group, propoxy group, butoxy group, and ethoxymetho, and the monovalent hydrocarbon group is the same as the monovalent hydrocarbon group mentioned above. a
is a number from 0 to 10, preferably from 0 to 3. ■ is 0-1000. n! , tO~100, where 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(7). A is R or -R1- (NHC is also preferably an alkoxy group. R
1 is a divalent hydrocarbon group, which includes ethylene group, n-
Examples include alkylene groups such as propylene group, isopropylene group, and isobutylene group, arylene groups such as phenylene group, and alkylene arylene groups such as ethylenephenylene group, among which alkylene group is representative.
Preferred are ethylene and propylene groups.

When R2 and R3 are a hydrogen atom or a monovalent hydrocarbon group, n may be 0. However, in order to give the cured product excellent water repellency, at least one -R1NHCH2CH2+r group or hydroxyl group must be present in one molecule.

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 parts by weight, a cured product with sufficient water repellency 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 preferable addition amount is 0.
05 to 10 parts by weight, more preferably 0.05 to 10 parts by weight. 1-5
Parts by weight.

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

(8) As an example of the method for producing the organopolysiloxane component, a methoxy group (CI (2 juice N)
A method for producing organopolysiloxane having 82 H2CH2N groups is as follows: (CHaO)2(CHa)SiC
By reacting H2h-NHCH2CH2Nl2, a hydroxyl group and a methoxy group undergo a condensation reaction, and both molecular chains CI
(a) Ganoborisiloxane can be easily produced.Also, when producing dimethylpolysiloxane by equilibrating octamethyltetracyclosiloxane in the presence of a sodium hydroxide catalyst, the above (CHaO)2(CH3)
Si Minoh C115'r N1 (CH2CHZNHZ)
11! -(Ct42 ThNHC
Dimethylpolysiloxane having H2CH2NN2 groups and hydroxyl groups at both ends of the molecular chain can be obtained. The organopolysiloxane which is component (B) may be produced by any method and is not limited in any way.

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 300,131 parts, but it may exceed 1,000 parts by weight depending on the conditions (for example, the paper manufacturing method for calcium silicate plates), so it may be added as appropriate.

In addition to the above-mentioned water, other components can be added to the present composition as needed. For example, magnesium oxide,
Metal oxides such as alumina and iron oxide, asbestos, synthetic fibers, and glass fibers.

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

Organopolysiloxanes other than component (8), surfactants, foaming agents such as metal powders, hardening accelerators, rust preventive agents, 9 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. In addition, the components (A), (8) and water can be mixed and cured at a 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. When solidifying, a cured product having excellent water repellency can be produced by drying as it is at room temperature to assimilate it, or by heating and drying or steam curing at a relatively low to high temperature as necessary. In addition, even if it is applied with a trowel like mortar on a wall and left to dry naturally at room temperature, a mortar finish with good water repellency can be achieved. Therefore, the curing method is not particularly limited.

The hydraulic inorganic composition of the present invention is a lightweight cellular concrete (
ALC), glass fiber reinforced concrete) (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 boards, decorative asbestos cement boards, asbestos cement siding, calcium silicate insulation materials , useful as perlite heat insulators, etc.

[Example] Next, an example will be given and explained. Parts in Examples and Comparative Examples 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 10100 x 100 x 16, 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 semispherical, but the water repellency is good.

Δ 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 00 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, demold and store at 25℃ and humidity 8.
It was cured for 3 days in a constant temperature machine at 5±5%.

Then, it was naturally dried indoors at 28° C. for 7 days.

In this way, three sheets of each type of organopolysiloxane were made, one of which was heated to 50°C without heating, and one of which was heated to 50°C.
It was heated in a hot air dryer for 3 hours. The remaining one is 100℃
The mixture was heat-treated 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 exhibited excellent water repellency even without heat treatment compared to the comparative example. In addition, between 50℃ and 1
It showed even more stable water repellency when heated at a low temperature of 00°C.

Table 1 Table 2 Example 2 100 parts of Portland cement, 2 parts of river sand produced for Watarase
00 parts, 300 parts of small gravel with a diameter of 3 to 5 mm were added, and the mixture was allowed to dry for 2 minutes, and then 130 parts of water was added and mixed for 3 minutes. Next, 6 parts of the organopolysiloxane shown in Table 1 used in Example 1 was added and mixed for 3 minutes.
It was cast into a 100X100XL6 stainless steel mold.

After 48 hours, the mold was demolded and cured for one week in a thermostatic oven at 25°C and humidity of 85±5%. Then, in a room at 28°C for 14
Air dried for a day. Water droplets were dropped on the surface of the molded and cured product thus prepared, and the water repellency was observed. The results are shown in Table 3.

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

Table 3 Example 3 Add 70 parts of silica powder and 500 parts of water to 30 parts of quicklime and add 1
Heat treatment was performed in an autoclave at 80°C for 6 hours. Then 100 pulverized asbestos fibers were added to the cooled slurry.
After adding 100 parts of Portland cement and 8 parts each of organopolysiloxanes No. 3, 4.5 and 10 (comparative examples) used in Example 1 - (F) ), dehydrated and molded using felt cloth, and heat-treated again in an autoclave at 140°C for 3 hours. Thereafter, it was dried at 120° C. for 10 hours to produce a molded and cured body. 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 4.

After adding 1,500 parts of silica sand (4th grade cement), 670 parts of silica sand of 100 mesh pass, and 3,830 parts of sand and letting it dry for 2 minutes, 780 parts of water was added and mixed for 3 minutes. Next, 18 parts of organopolysiloxane No. 3.6 (comparative example) and 8 (comparative example) used in Example 1 were added and mixed for 3 minutes.

Thereafter, the additive-free mold (comparative example) and the organopolysiloxane-added mold were cast into stainless steel molds measuring 100×100×16 mm. 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%. Next, it was heat-treated in an oven at 80°C for 1 hour, and then immersed in distilled water at 20°C for 24 hours, and then the weight W1 was measured. Furthermore, the temperature is 105℃
After drying in a constant temperature bath for 25 days, the weight W2 was measured.

From this measured value, the water absorption percentage was determined using the following formula. The results are shown in Table 5.

Example 4 It was confirmed that water penetration was small even when the container of a Hobart mixer with a capacity of 5 mm was immersed in Poldora water.

Table 5 Water droplets were dropped on the surface to examine the water repellency.

Organopolysiloxane No. as a comparative example.

The same procedure was carried out for No. 6 and no additives.

The results are shown in Table 6.

Table 6 Example 5 80 parts of hemihydrate wax and 20 parts of organopolysiloxane No. 3 used in Example 1 were uniformly mixed in advance.

8 parts of hemihydrate wax treated with the above organopolysiloxane were added to 100 parts of hemihydrate wax, and further 100 parts of water were added and kneaded. This is 100X 100X 16m
The molded product was placed in a stainless steel mold of size 1, left at room temperature for 5 hours, and then dried at 60° C. for 20 hours to obtain a molded hardened stone wax body.

Example 6 After stirring 270 parts of Voltland cement, 44 parts of perlite, 86 parts of asbestos, and 250 parts of water using a mixer, 4 parts of organopolysiloxane No. 4 used in Example 1 was added thereto and further stirred. Ta. Next, fix the four sides of the filter cloth and spread it flat on the cloth at 100X 100X 16m.
A mold of size m was placed on the mold, and the above-mentioned kneaded material was poured into the mold evenly, dehydrated, and left as it was for 24 hours. Thereafter, the mold was demolded 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 examine the water repellency.

Organopolysiloxane No. as a comparative example.

The same procedure was carried out for No. 8 and no additives.

The results are shown in Table 7.

The material to which the organopolysiloxane of the present invention was added showed good non-electrolytic water repellency.

Since the organopolysiloxane having at least one organopolysiloxane in each of Table 7 is blended, when cured by adding water, the cured product has extremely superior [a aqueous properties] compared to conventional products.

Therefore, it is extremely useful especially as interior materials, exterior materials, heat insulating materials, heat retaining materials, etc. for buildings.

Patent applicant Thoth Silicone Co., Ltd.

Claims (1)

[Claims] 1. (A) Hydraulic inorganic raw material 100 parts by weight (B) One molecule contains an alkoxy group or hydroxyl group bonded to a silicon atom and a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Formula In the middle, R^1 is a divalent hydrocarbon group, R^2 and R^3
is a group selected from a hydrogen atom and a monovalent hydrocarbon group, a
is a number from 0 to 10. ) A hydraulic inorganic composition comprising 0.01 to 20 parts by weight of an organopolysiloxane having at least one group represented by the following formulas. 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) has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is a group selected from an alkoxy group, a hydroxyl group, and a monovalent hydrocarbon group, A is R or ▲ Numerical formula, chemical formula,
There are tables, etc. Groups shown with ▼, provided that at least one of R is an alkoxy group or a hydroxyl group. R^1 is a divalent hydrocarbon group, R^2 and R^3
is a group selected from a hydrogen atom and a monovalent hydrocarbon group, a
is a number from 0 to 10, m is 0 to 1000, n is 0 to 100,
However, m+n is 0 to 1000. ] The hydraulic inorganic composition according to claim 1, which is an organopolysiloxane represented by the following.