JPH06248258A - Silicone-based waterproofing treatment agent and method for waterproofing tretment with the same - Google Patents

Abstract

PURPOSE:To obtain a silicone-based waterproofing treatment agent, excellent in preventing properties for water absorption and preservation stability and useful as masonry building materials, etc., by emulsifying a mixture of a specific alkoxytrialkoxysilane, etc., a nonionic emulsifying agent, etc., and water in a specific proportion. CONSTITUTION:The treating agent is obtained by emulsifying (A) 1-70wt.% mixture prepared by mixing (i) an alkyltrialkoxysilane of the formula R<1>SiR<2>3 (R<1> is 4-20C monovalent alkyl; R<2> is 1-6C alkoxy) such as butyltriethoxysilane with (ii) a cyclic dimethylpolysiloxane of the formula n is 3-7 such as octamethylcyclotetrasiloxane at (5/95) to (95/5) weight ratio of the components (i)/(ii) with (B) 1-50wt.% one or two or more mixtures selected from nonionic and ionic emulsifying agents and (C) the remainder of water. Furthermore, this treating agent is preferably used to carry out treatment for preventing the surface of an inorganic porous substrate from absorbing water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silicone-based waterproofing agent, and particularly to a penetrating silicone-based waterproofing agent for masonry materials, etc., which can be stored for a long time because of its excellent storage stability. The present invention relates to a method for preventing surface water absorption of an inorganic porous substrate used.

[0002]

2. Description of the Related Art It is widely known that silanes, especially alkoxysilanes, are useful as water repellents and waterproofing agents for treating stone materials, masonry, etc. Are known to be dissolved in alcohol (see US Pat. No. 3,772,065) and hydrocarbons (see US Pat. No. 4,525,213). There's a problem.

Further, a method of using a hydrolyzed silane aqueous solution as the stonework treating agent (US Pat. No. 4,517,37)
5), a method using an aqueous silane compound (see US Pat. Nos. 4,433,013 and 4,648,904), a method using an aqueous dispersion of an organic polysiloxane (see US Pat. No. 4,476,282). , A method using an aqueous dispersion of a silicon resin (see US Pat. No. 4,529,758) has been proposed, and a method using an aqueous emulsion of a long-chain alkylalkoxysilane (JP-A-62-197369). (See the official gazette)
The use of such a silane emulsion has problems with its storage stability and polymerization due to hydrolysis of silane.

[0004]

Therefore, for the emulsion of the hydrolyzable silane, a method of controlling the pH change by adding an organic acid salt or an inorganic acid as a buffer to the emulsion (Japanese Patent Laid-Open No. 1-292089). Japanese Patent Laid-Open No. 3-188086), and a method of stabilizing an emulsion by blending a hydrolyzable silane with an aqueous thickener such as polyacrylic acid ester and a buffer is also proposed (Japanese Patent Laid-Open No. 3-08863). -8887
(See No. 9), and an emulsion composition obtained by emulsifying with an alkylalkoxysilane and a quaternary ammonium salt group-containing organosilicon compound or a condensate thereof in order to prevent deterioration of the waterproof performance of the substrate surface due to a nonionic emulsifier. The method used (see JP-A-3-159975), it is difficult to obtain a stable emulsion composition only with a nonionic emulsifier, and therefore a method using an anionic emulsifier together (JP-A-3-23)
No. 2527) are also proposed, but all of them have a problem that they are still insufficient for improving the stability of the obtained silane emulsion composition.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a silicone waterproofing agent and a waterproofing method using the same, which solves the above problems and disadvantages. 1) an alkyltrialkoxysilane represented by R ¹ SiR ² ₃ (wherein R ¹ is a monovalent alkyl group having 4 to 20 carbon atoms, R ² is an alkoxy group having 1 to 6 carbon atoms), and 2) general formula

[Chemical 2] (Wherein n is an integer of 3 to 7) and a cyclic dimethylpolysiloxane represented by the following formula: first component / second component (weight ratio) = 5/95
˜95 / 5 of a mixture of 1 to 70% by weight, 3) a nonionic emulsifier and / or an ionic emulsifier of 1 to 50% by weight, and 4) emulsified with water. The waterproof treatment method according to this is characterized in that the surface of the inorganic porous substrate is treated with the silicone waterproof treatment agent.

That is, the present inventors have conducted various studies to develop a penetrating type silicone waterproofing agent for masonry construction materials, which has excellent storage stability, and as a result, has been hitherto known as alkyltrialkoxy. By adding cyclic dimethyl polysiloxane to silane and emulsifying and dispersing it in water using a nonionic emulsifier and / or an ionic emulsifier, a silicone-based waterproofing agent with excellent stability and qualification for treating stone building materials can be obtained. Based on these findings, the present invention has been completed by conducting research on the blending ratios, types of surfactants, and the like. This will be described in more detail below.

[0007]

The present invention relates to a silicone-based waterproofing agent, which is an alkyltrialkoxysilane to which cyclic dimethylpolysiloxane is added and which is emulsified with a surfactant. This is an inorganic porous substrate. , Especially when applied to the surface of stone building materials, it penetrates well into the interior, giving it surface water absorption prevention and water repellency, does not thicken or gels even after long-term storage, and this water absorption inhibitor Since it does not deteriorate in performance, it has an advantage of extremely excellent storage stability.

[0008] alkyltrialkoxysilane as a first component constituting the silicone waterproofing agent of the present invention is represented by the general formula R ¹ SiR ² _3, the R ¹ is a monovalent alkyl group having 4 to 20 carbon atoms , R ² is an alkoxy group having 1 to 6 carbon atoms. The alkyl group as R ¹ has a carbon number of 4 to 20, but when the carbon number is less than 4, the hydrolyzability and volatility are very high, and a part of the alkyl group immediately after coating is used. It reacts with the surface of the base material to delay further penetration, during which unreacted silane components evaporate, resulting in water repellency only on the base material surface, and when the carbon number is 20 or more, the molecular weight is increased. Since it becomes difficult to permeate into the inside of the base material, it is preferable that the carbon number is 4 to 20, more preferably 6 to 20.

Examples of the alkoxy group as R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentanoxy group, and a hexanoxy group, which are particularly preferably a methoxy group or an ethoxy group. Is preferred.

Therefore, as the alkyltrialkoxysilane, the following are exemplified as preferable ones. Butyltriethoxysilane, Pentyltriethoxysilane, Hexyltriethoxysilane, Heptyltriethoxysilane, Octyltriethoxysilane, Nonyltriethoxysilane, Decyltriethoxysilane, Undecyltriethoxysilane, Dodecyltriethoxysilane, Tridecyltriethoxysilane Ethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, eicosyltriethoxysilane, butyltrimethoxysilane,
Pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane Methoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane,
Heptadecyltrimethoxysilane, octadecyltrimethoxysilane, eicosyltrimethoxysilane.

The cyclic dimethylpolysiloxane as the second component which constitutes the silicone waterproofing agent of the present invention is represented by the above-mentioned general formula (2), which is the emulsion composition of the above-mentioned first component. It is added in order to improve the stability, but when the amount of the first component is less than 5%, the composition has a small effect of imparting the water absorption preventive property to the surface of the porous substrate. If it exceeds 95%, the stability of this emulsified composition decreases, so that it is necessary that the compounding ratio (weight ratio) of the first component and the second component be in the range of 5/95 to 95/5. However, the preferred range is
The range is 20/80 to 80/20.

Since the cyclic dimethylpolysiloxane as the second component is gradually volatilized and does not remain on the surface of the base material when the emulsified composition emulsified in the emulsification step described later is applied to the base material, Although it does not adversely affect the water absorption prevention property and the water repellency imparted by the one component, the content of the composition comprising the first component and the second component in the total emulsified composition is less than 1% by weight. It was not possible to give sufficient permeation and water absorption prevention performance to the porous material by applying it twice.
If it is more than 10% by weight, the viscosity becomes high and it becomes difficult to apply, so from the viewpoint of ease of application and economical efficiency, it should be in the range of 1 to 70% by weight, preferably 10 to 50% by weight. Is good.

Next, the emulsifier as the third component constituting the silicone waterproofing agent of the present invention is one or a mixture of two or more selected from nonionic emulsifiers and ionic emulsifiers. Examples of the nonionic emulsifier include polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, sorbitan monoalkylate, sorbitanial chelate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitanial chelate, polyoxyethylene sorbitan tetrachelate. Examples thereof include alkylate and glycerol monoalkylate, which can be used alone or in combination of two or more kinds. In addition to these general nonionic emulsifiers, fluorine-based emulsifiers and silicone-based emulsifiers can be used. Although a nonionic emulsifier can be used, it is preferable that the nonionic emulsifier has an HLB in the range of 1.5 to 20, preferably 7.0 to 19.0.

The ionic emulsifiers include anionic, cationic and zwitterionic ones, and the anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate and dialkylsulfosuccinate. Sodium acid, potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc., as the cationic emulsifier, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride , Lauryl trimethyl ammonium chloride, stearyl amine hydrochloride, coconut amine hydrochloride, cocona DOO amine acetate, stearylamine acetate, etc. alkylbenzene dimethyl ammonium chloride are exemplified.

As the zwitterionic emulsifier, N-
Examples include acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N'-dimethyl-N'-β-hydroxypropylammoniobetaines, and the like. If the amount of the emulsifier used here is less than 0.1% by weight based on the amount of the composition comprising the first component and the second component described above, a stable emulsified composition cannot be obtained, and the amount is more than 50% by weight. If so, sufficient waterproof performance cannot be obtained. Therefore, it is necessary to set this to 1 to 50% by weight, and this preferable range is 5 to 20% by weight.

The silicone waterproofing agent of the present invention comprises 1 to 70% by weight of a predetermined amount of a mixture of the above-mentioned alkyltrialkoxysilane as the first component and cyclic dimethylpolysiloxane as the second component. It can be obtained by dropping water little by little in the presence of the above-mentioned emulsifier in a mixer such as a homomixer while stirring at high speed. The silicone-based waterproofing agent of the present invention thus produced has a porous inorganic substrate, particularly a building component such as brick, drain tile, concrete block, cement, mortar, calcined gypsum product, stone, tile, When it is applied to artificial stone, it penetrates inside,
By binding, an excellent water-absorption-preventing layer is formed after drying, so that deterioration of the base material can be prevented and long-term durability can be imparted, and this product also thickens even after long-term storage. In addition, it has an advantage that it does not gel, and further does not deteriorate its performance as an anti-absorption agent, and has extremely excellent storage stability.

[0017]

EXAMPLES Examples and comparative examples of the present invention will be given below.
The storage stability, water absorption and permeability in the examples show the test results by the following methods.

(Storage stability) 30 g of the emulsified composition was placed in a 50 ml glass bottle and allowed to stand in a thermostatic chamber at room temperature and 50 ° C. to observe the number of days for starting separation. (Water absorption) 5 cm x 5 cm x 2.5 cm mortar test piece (JI
S mortar) with 300 kg / cm ² of the emulsified composition,
Create a test piece by curing for 7 days under the condition of 50% RH,
This was entirely immersed in tap water, and the absorption rate after 1 week was measured. Water absorption = [water absorption (g) / weight of test piece before immersion (g)] x 10
0 (Permeability) The test piece obtained above was divided in half, water was applied to the cross section, and the depth of the water repellent portion was measured.

Example 1 Hexyltriethoxysilane (30.0 g) and octamethylcyclotetrasiloxane (20.0 g) were mixed, and polyoxyethylene tridecyl ether [EO addition mol = 5 mol (HLB10.5): 1.6 g, EO addition] was added. Mol = 50 mol (HLB
18.3): 3.4g] is added to 5.0g, and 1 of 44.0g of water is added to this.
0.0 g was gradually added while stirring at a low speed, and when phase inversion and viscosity increase, the stirring speed was increased to 2,000 rpm or more and the mixture was stirred for several minutes.

Then, the remaining water is added to dilute it,
Add 1.0 g of 30% sodium polyoxyethylene tridecyl ether sulfate (EO addition mol = 5 mol) aqueous solution, mix and stir, then add this with a high pressure homogenizer.
After passing twice under a pressure of 300 kg / cm ² , a white emulsion composition was obtained. The storage stability, water absorption rate and permeation depth of the white emulsion composition were measured. The results are shown in Table 1 below. The following results were obtained.

Example 2 Polyoxyethylene tridecyl ether as an emulsifier in Example 1 was changed to polyoxyethylene sorbitan monooleate (EO addition mol = 6 mol, HLB 10.0), and sodium polyoxyethylene decyl ether sulfate was used. A white emulsifier composition was prepared by treating in the same manner as in Example 1 except that sodium lauryl sulfate was used, and the physical properties of this composition were examined. The results shown in Table 1 below were obtained.

Example 3 The hexyltriethoxysilane used in Example 1 was 30 g of decyltrimethoxysilane, and the octamethyltetracyclosiloxane was hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexahexane. Mixture of siloxane and tetradecamethylcycloheptasiloxane
A white emulsion composition was prepared in the same manner as in Example 1 except that the amount was changed to 20 g, and the physical properties of this composition were examined. The results shown in Table 1 below were obtained.

Example 4 The same procedure as in Example 1 was repeated except that the amounts of hexyltriethoxysilane and octamethylcyclotetrasiloxane in Example 1 were changed to 10 g of hexyltriethoxysilane and 40 g of octamethylcyclotetrasiloxane. After making a white emulsion composition and examining the physical properties of this,
The results shown in Table 1 below were obtained.

Example 5 20.0 g of hexyltriethoxysilane and 8.0 g of decamethylcyclopentasiloxane were mixed, and 10.0 g of a 30% cetyltrimethylammonium clotide aqueous solution was added thereto and mixed, and then 88.0 g of water was added to the mixture. Gradually add 3.0 g while stirring at low speed, and after phase inversion and thickening, stir at a speed of 2,000 rpm or higher for several minutes using a homomixer, add the remaining water to dilute, then stir at low speed for several minutes. Then, using a high-pressure homogenizer, the mixture was passed twice under a pressure of 300 kg / cm ² to prepare a white emulsion composition, and its physical properties were examined. As a result, the results shown in Table 1 below were obtained.

Example 6 The same treatment as in Example 1 except that the amounts of hexyltriethoxysilane and octamethylcyclotetrasiloxane in Example 1 were changed to 40.0 g of hexyltriethoxysilane and 10.0 g of octamethylcyclotetrasiloxane. Then, a white emulsion composition was prepared and its physical properties were investigated. As a result, the results shown in Table 1 below were obtained.

Comparative Example 1 5.0 g of hexyltriethoxysilane, 5.0 g of polyoxyethylene tridecyl ether, the emulsifier used in Example 1
And 1.0 g of 30% sodium polyoxyethylene tridecyl sulfate aqueous solution were treated in the same manner as in Example 1 to prepare a white emulsion composition, and the physical properties of this composition were investigated. As shown in Table 1 below. The result was obtained.

Comparative Example 2 A white emulsion composition was prepared in the same manner as in Comparative Example 1 except that 50.0 g of hexyltriethoxysilane in Comparative Example 1 was changed to 50.0 g of decyltrimethoxysilane, and the physical properties of this composition were examined. However, the results shown in Table 1 described later were obtained.

Comparative Example 3 10.0 g of hexyltriethoxysilane was used as an emulsifier
% Cetyl trimethyl ammonium chloride aqueous solution 2.0 g
Was treated in the same manner as in Example 5 to prepare a white emulsion composition, and the physical properties of this composition were examined. The results shown in Table 1 below were obtained.

Comparative Example 4 Octamethylcyclotetrasiloxane 50.0 g and polyoxyethylene tridecyl ether {EO addition mole 5 mol (HLB10.5) 1.6 g, EO addition mole 50 mol (HLB18.
3) 3.4 g} and 30% sodium polyoxyethylene tridecyl ether sulfate (EO addition mol 5 mol) aqueous solution 1.
Emulsification was performed using 0 g in the same manner as in Example 1 to prepare a white emulsion composition, and the physical properties of this composition were examined. The results shown in Table 1 below were obtained.

[0030]

[Table 1]

[0031]

The present invention relates to a silicone-based waterproofing agent and a waterproofing method using the same. As described above, the silicone-based waterproofing agent comprises 1) an alkyltrialkoxylane and 2) a cyclic dimethylpolysiloxane.
The mixture of 5/95 to 95/5 parts is emulsified with 3) a nonionic surfactant and / or an ionic emulsifier and 4) water. It is characterized by treating the surface of an inorganic porous substrate, which is applied to an inorganic porous substrate, especially a building component, which permeates and binds to the inside, so after drying, It can be made to have excellent water absorption resistance, it does not thicken even after long-term storage, does not gel, and its water absorption prevention property does not decrease, so it has excellent storage stability. It has the advantage that

Claims (2)

[Claims] 1. An alkyltrialkoxy represented by the general formula R ¹ SiR ² ₃ (wherein R ¹ is a monovalent alkyl group having 4 to 20 carbon atoms, and R ² is an alkoxy group having 1 to 6 carbon atoms). Silane, and 2) the general formula: (Wherein n is an integer of 3 to 7) and a cyclic dimethylpolysiloxane represented by the following formula: first component / second component (weight ratio) = 5/95
1 to 70% by weight of a mixture obtained by mixing at 95 to 95/5, 3) one or more mixtures selected from nonionic emulsifiers and ionic emulsifiers
1 to 50% by weight, 4) A silicone waterproofing agent characterized by being emulsified with the balance water. 2. A method for preventing water absorption on a surface of an inorganic porous substrate, which comprises treating the surface of the inorganic porous substrate with the silicone waterproofing agent according to claim 1.