JP2807610B2 - Silicone waterproofing agent and waterproofing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-based waterproofing agent, in particular, a silicone-based waterproofing agent for making an inorganic porous substrate such as concrete waterproof, water-repellent, and soil-resistant. It relates to a processing method.

[0002]

2. Description of the Related Art It is widely known that silanes, especially alkoxysilanes, are useful as a water repellent and a waterproofing agent for treating stones, masonry, and the like. Known are those dissolved in alcohol (see U.S. Pat. No. 3,772,065) and those dissolved in hydrocarbons (see U.S. Pat. No. 4,525,213), which have problems with the toxicity and flammability of the solvent. There is.

A method using a hydrolyzed silane aqueous solution as the masonry treating agent (US Pat. No. 4,517,37)
5, US Pat. No. 4,433,013 and US Pat. No. 4,648,904), and 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 U.S. Pat. No. 4,529,758) and the like, and a method using an aqueous emulsion of a long-chain alkylalkoxysilane (JP-A-62-197369) have also been proposed. Reference) is also proposed,
The use of such a silane emulsion has problems of storage stability and polymerization by hydrolysis of the silane.

[0004]

Therefore, a method of controlling the pH change by adding an organic acid salt or an inorganic acid as a buffer to the emulsion of the hydrolyzable silane (Japanese Patent Laid-Open No. 1-292089). JP-A-3-88086), and a method of stabilizing an emulsion by blending an aqueous thickener such as a polyacrylate and a buffer with a hydrolyzable silane (JP-A-3-88086). No. 88879), and an emulsion composition emulsified with an alkylsiloxysilane and a quaternary ammonium base-containing organosilicon compound or a condensate thereof to prevent the non-ionic emulsifier from deteriorating the waterproof performance of the substrate surface. The method used (see JP-A-3-159975), since it is difficult to obtain a stable emulsified composition only with a nonionic emulsifier, an anionic emulsifier is used in combination. That method (JP-A-3-232527
Japanese Patent Application Laid-Open No. 3-115485), and a method of using a silicone-based or fluorine-based emulsifier in order to minimize the decrease in waterproof performance due to the emulsifier has been proposed. All of them have a problem that they are still insufficient in imparting effects such as water repellency, oil repellency, and antifouling properties to the substrate surface.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a silicone-based waterproofing agent which solves such disadvantages and problems, and a waterproofing method using the same.
An alkyl trialkoxysilane represented by the general formula R ¹ Si (R ² ) ₃ (where 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), and 2) General formula [R ³ (C
_{^{H 2) n] R 4 a}} Si (R 2) 3-a ( here R ² are as defined above, R ³ is a perfluoroalkyl group having 4 to 14 carbon atoms, R ⁴ is 1 to hydrogen or carbon atoms 6 is a monovalent hydrocarbon group, a is 0 or 1)
And a perfluoroalkyl group-containing alkoxysilane represented by the formula: wherein the total amount of the first component and the second component is 1
About 70% by weight, wherein the second component is 0.1 to 30% by weight of the total amount of the first and second components, and 3) 1 to 50% based on the total amount of the first and second components. HLB 1.5% by weight
A silicone-based waterproofing treatment characterized by being dispersed and emulsified in water in the presence of one or more emulsifiers selected from 20 nonionic emulsifiers, anionic, cationic or amphoteric ionic emulsifiers. The present invention provides a waterproofing method comprising treating the surface of an inorganic porous substrate with an agent and a silicone-based waterproofing agent.

That is, the present inventors have conducted various studies to develop a silicone-based waterproofing agent for imparting waterproofness, surface water repellency, and antifouling properties to masonry building materials such as concrete, and as a result, have been known in the art. If a perfluoroalkyl group-containing alkoxysilane is added to the alkyltrialkoxysilane that has been emulsified and dispersed in water using a surfactant, this will efficiently penetrate into the inorganic porous substrate. In order to form a water-repellent layer, it has been found that long-term waterproofness is imparted thereto, and excellent water-repellent, oil-repellent and antifouling properties are imparted to the substrate surface. The present invention was completed by conducting research on the mixing ratio and the like. This will be described in more detail below.

[0007]

The present invention relates to a silicone-based waterproofing agent and a waterproofing method using the same, wherein the silicone-based waterproofing agent is prepared by mixing a perfluoroalkyl group-containing alkoxysilane with an alkyltrialkoxysilane in a weight ratio of 0.1.
-30% by weight, and emulsified and dispersed in water using a surfactant. The method of waterproofing is to treat the surface of an inorganic porous substrate with this silicone-based waterproofing agent. According to this, since the silicone-based waterproofing agent efficiently penetrates into the inside of the inorganic porous substrate to form a water-repellent layer there, it has long-term waterproofness, water-repellency, and oil-repellency. This provides the advantage that antifouling properties are imparted.

As described above, the silicone waterproofing agent of the present invention is obtained by adding a perfluoroalkyl group-containing alkoxysilane as a second component to an alkyltrialkoxysilane as a first component, and using this as an emulsifier as a third component. And emulsified and dispersed in water. The alkyl trialkoxysilane as the first component constituting the silicone waterproofing agent of the present invention is represented by the general formula 1 as R ¹ Si (R ² ) ₃ . (1) 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.

The alkyl group as R ¹ has 4 to 20 carbon atoms. When the alkyl group has less than 4 carbon atoms, the alkyl group has very high hydrolyzability and volatility. The part reacts with the substrate surface to delay further penetration, during which the unreacted silane component evaporates, resulting in water repellency only on the substrate surface, and the carbon number is 20 or more Sometimes, the molecular weight is so large that it is difficult to penetrate into the inside of the base material. Therefore, it is preferable that the carbon number is 4 to 20, 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, and a methoxy group and an ethoxy group are particularly preferable.

Accordingly, the alkyl trialkoxysilanes include butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octeltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane. Ethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, pentadecyltriethoxysilane, octadecyltriethoxysilane, eicosyltriethoxysilane, butyl Trimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysila , Nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxy Preferred are silane, octadecyltrimethoxysilane, eicosyltrimethoxysilane and the like.

The perfluoroalkyl group-containing alkoxysilane as the second component constituting the silicone-based waterproofing agent of the present invention is represented by the following general formula ( ₂ ): [R ³ (CH ₂ ) _n ] R ⁴ _a Si (R ² ) _3-a ... (2) wherein R ² is the same alkoxy group as described above, preferably a methoxy group or an ethoxy group, and R ³ is a C 4-14 carbon atom. Although it is a fluoroalkyl group, the effect of imparting water repellency and oil repellency is not sufficient when the number of carbon atoms is 4 or less, and when the number of carbon atoms is 14 or more, the permeability to the base material is reduced and the cost is high. Therefore, this is preferably one having 4 to 14 carbon atoms, including -C ₄ F ₉ , -C ₆ F ₁₃ , -C ₈ F ₁₇ ,
Examples include -C ₁₀ F ₂₁ , -C ₁₂ F ₂₅ , -C ₁₄ F ₂₉ , and among them, -C ₄ F ₉ and -C ₈ F ₁₇ are particularly preferable.

Further, R ⁴ is a hydrogen atom or a group having 1 to 1 carbon atoms.
The monovalent hydrocarbon group of 6 includes, as the hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and preferably a methyl group, This a is 0 or 1.

The perfluoroalkyl group-containing alkoxysilanes include nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heneicosafluorododecyltrimethoxysilane, and pentacosa. Fluorotetradecyltrimethoxysilane, nonacosafluorohexadecyltrimethoxysilane, nonafluorohexyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, heneicosafluorododecyltriethoxysilane, pentacosa Fluorotetradecyltriethoxysilane, nonacosafluorohexadecyltriethoxysilane, nonafluorohexylmethyldimethoxysilane, Li tridecafluorooctyl methyldimethoxysilane, hepta decal heptadecafluorodecyl methyldimethoxysilane, Heng eicosapentaenoic heptadecafluorodecyl methyldimethoxysilane, penta Cosa fluoro tetradecyl methyl dimethoxy silane, such nona Cosa fluoro hexadecyltrimethylammonium methyldimethoxysilane run is illustrated.

The perfluoroalkyl group-containing alkoxysilane as the second component is added to assist and improve the waterproofness and water repellency of the alkyltrialkoxysilane as the first component. Is the first
If the amount is less than 0.1% by weight of the total amount of the component and the second component, sufficient characteristics cannot be exhibited. If the amount is more than 30% by weight, emulsification becomes difficult, and this becomes expensive.
It is required to be in the range of .about.30% by weight, but the preferred range is 0.5-10% by weight.

The perfluoroalkyl group-containing alkoxysilane as the second component is oriented near the surface of the substrate to give excellent water repellency and oil repellency. Alkyl trialkoxysilane as one component has good permeability to the base material and forms a water-repellent layer even at a deep portion, so that long-term waterproofness can be ensured according to this. When 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 is possible to impart sufficient permeation and water absorption preventing performance to the porous material by one application. If the content is more than 70% by weight, the viscosity increases and the coating becomes difficult.
The range is 70% by weight, preferably 10 to 50% by weight.

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, sorbitan trialkylate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitan trialkylate, and polyoxyethylene sorbitan tetraalkylate. Examples thereof include alkylates, glycerol monoalkylates, and the like. These can be used alone or in combination of two or more. These include, in addition to these general nonionic emulsifiers, a fluorine-based emulsifier and a silicone-based emulsifier. A nonionic emulsifier can also be used, but 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 emulsifier includes anionic, cationic and amphoteric emulsifiers. Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, dialkyl sulfo succinate. Sodium acid, potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc., and cationic emulsifiers such as cetyltrimethylammonium chloride and stearyltrimethylammonium chloride , Lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl tri Examples include tillammonium chloride, stearylamine hydrochloride, coconutamine hydrochloride, coconutamine acetate, stearylamine acetate, and alkylbenzenedimethylammonium chloride. Examples of the zwitterionic emulsifier include N-acylamidopropyl-N, N- Examples thereof include dimethylammoniobetaines, N-acylamidopropyl-N, and N′-dimethyl-N′-β-hydroxypropylammoniobetaines.

The amount of the emulsifier used here is based on the amount of the composition comprising the first and second components.
If the amount is less than 0.1% by weight, a stable emulsified composition cannot be obtained. If the amount is more than 50% by weight, sufficient waterproof performance cannot be obtained. Therefore, it is necessary that the amount be in the range of 1 to 50% by weight. However, the preferred range is 5 to 30% by weight.

The silicone-based waterproofing agent of the present invention is prepared by mixing a mixture of the above-mentioned alkyltrialkoxysilane as the first component and the perfluoroalkyl group-containing alkoxysilane as the second component in the presence of an emulsifier as a third component. It can be obtained by emulsifying and dispersing in water, and is obtained by mixing 1 to 70% by weight of a mixture of the first component and the second component.
Can be obtained by dropping water little by little in a mixer such as a homomixer at a high speed in the presence of 1 to 50% by weight of an emulsifier.

The silicone-based waterproofing agent of the present invention thus prepared can be used for inorganic porous substrates, especially for building components such as bricks, drain tiles, concrete blocks, cement, mortar, calcined gypsum products and stones. , Tiles, artificial stones, etc., this penetrates into the interior,
By bonding, an excellent water absorption preventing layer is formed after drying, so that deterioration of the base material can be prevented, durability can be imparted over a long period of time, and a perfluoroalkyl group-containing alkoxysilane compounded therein can be added. Is oriented near the surface of the substrate, thereby giving the substrate surface excellent water repellency, oil repellency, and antifouling properties.

[0021]

EXAMPLES Examples of the present invention and comparative examples will now be described. In the examples, the physical properties of the objects to be treated are the results of measurements by the following methods. (Water absorption) 5cm x 5cm x 2.5cm mortar test piece (JI
S mortar), apply 300 kg / cm ² of the emulsified composition,
After curing for 7 days under the condition of 50% RH, a test piece was prepared.
The whole was immersed in tap water, and the absorption after one week was measured. Water absorption = [Water absorption (g) / Weight of test specimen 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. (Water repellency) 6 μl of pure water was dropped on the surface of the test piece obtained above, and the contact angle was measured.

Example 1 45.0 g of hexyltriethoxysilane and 5.0 g of heptadecafluorodecyltrimethoxysilane were mixed, and polyoxyethylene tridecyl ether [EO added mole =
1.6 g of 5 mol (HLB10.5), mol of EO added = 50 mol (H
LB 18.3) 3.4 g] and 5.0 g of water, 10.0 g of 44.0 g of water
Was gradually added while stirring at a low speed, and when the phase was inverted and the viscosity was increased, 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 the mixture to dilute it,
1.0 g of an aqueous solution of 30% sodium polyoxyethylene tridecyl ether sulfate (mol of added EO = 5 mol) was added, mixed and stirred, and then further mixed with a high-pressure homogenizer.
After passing twice under a pressure of 300 kg / cm ² , a white emulsion composition was obtained. The water repellency and water absorption of the white emulsion composition were measured. The results were as shown in Table 1 below. Was done.

Example 2 The polyoxyethylene tridecyl ether as an emulsifier in Example 1 was polyoxyethylene sorbitan monooleate (mol of EO added: 6 mol, HLB 10.0), and sodium polyoxyethylene decyl ether sulfate was used. A white emulsion composition was prepared in the same manner as in Example 1 except that sodium lauryl sulfate was used, and the physical properties of the white emulsion composition were examined. The results were as shown in Table 1 below.

Example 3 The amount of hexyltriethoxysilane in Example 1 was changed to 4
A white emulsion composition was prepared in the same manner as in Example 1 except that the amount of heptadecaflororolodecyltrimethoxysilane was changed to 2.5 g, and the physical properties of this composition were examined. The results as shown in Table 1 were obtained.

Example 4 A white emulsion composition was prepared in the same manner as in Example 1 except that hexyltriethoxysilane in Example 1 was changed to decyltrimethoxysilane, and the physical properties of the composition were examined. The results as shown in Table 1 were obtained.

Example 5 A white emulsion composition was prepared in the same manner as in Example 1 except that heptadecafluorodecyltrimethoxysilane in Example 1 was changed to nonafluorohexyltrimethoxysilane, and the physical properties of this composition were examined. As a result, the results as shown in Table 1 below were obtained.

Example 6 19.0 g of hexyltriethoxysilane and 1.0 g of heptadecafluorodecyltrimethoxysilane were mixed, and polyoxyethylene tridecyl ether [EO added mole =
6.0 g of 5 mol (HLB10.5) 4.07 g and EO addition mol = 50 mol (HLB18.3) 1.93 g] were blended, and a white emulsion composition was prepared in the same manner as in Example 1 using 74.0 g of water. Upon examining the physical properties of this product, the results shown in Table 1 below were obtained.

Example 7 The amount of hexyltriethoxysilane according to Example 6 was reduced to 19.
9 g, 0.1 g of heptadecafluorodecyltrimethoxysilane, 0.1 g of polyoxyethylene tridecyl ether
1.0 g [EO addition mol = 5 mol (HLB10.5) 0.68 g, E
O addition mole = 50 mole (HLB18.3) 0.32 g], except that the white emulsion composition was prepared in the same manner as in Example 6.
Upon examining the physical properties of this product, the results shown in Table 1 below were obtained.

Comparative Example 1 A white emulsion composition was prepared in the same manner as in Example 1 except that no perfluoroalkyl group-containing alkoxysilane was added to 50.0 g of hexyltriethoxysilane and the emulsifier used in Example 1 was used. Was prepared, and the physical properties of the product were examined. As a result, the results shown in Table 1 below were 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 was replaced with 50.0 g of decyltrimethoxysilane, and the physical properties of this composition were examined. However, the results as shown in Table 1 below were obtained.

Comparative Example 3 The amount of hexyltriethoxysilane in Comparative Example 1 was 30
g, and emulsification was carried out in the same manner as in Example 1 except that the amount of heptadecafluorodecyltrimethoxysilane was changed to 20 g. In this case, however, emulsification was difficult and a white emulsion composition was obtained. could not.

Comparative Example 4 The amount of the emulsifier in Example 6 was changed to 12 g [mol added EO = 5]
Mol (HLB10.5) 8.2 g, mol of EO added = 50 mol (HL
B18.3) was treated in the same manner as in Example 6 except that the composition was changed to 3.8 g]. A white emulsion composition was prepared, and the physical properties of the composition were examined. The results were as shown in Table 1 below. .

[0034]

[Table 1]

[0035]

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 includes 1) an alkyl trialkoxysilane represented by the general formula 1; 1 to 70% by weight of a mixture of 0.1 to 30% by weight of a perfluoroalkyl group-containing alkoxysilane represented by the general formula 2
And 3) emulsifying and dispersing in water using 1 to 50% by weight of an emulsifier selected from a nonionic emulsifier and an ionic emulsifier. This waterproofing method treats the surface of an inorganic porous substrate with this silicone. It is characterized by being treated with a system waterproofing agent.

When the surface of an inorganic porous substrate such as concrete is treated with this silicone-based waterproofing agent, it efficiently penetrates into the inside of the substrate to form a water-repellent layer. The material can be provided with long-term waterproofness, and since the perfluoroalkyl group-containing alkoxysilane is oriented near the surface of the base material, excellent water repellency, oil repellency, and stain resistance are provided on the base material surface. The advantage is given.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 3/18 B01F 17/54 C09K 3/00 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. An alkyl represented by the general formula: R ¹ Si (R ² ) ₃ (where 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) Trialkoxysilane and 2) a general formula [R ³ (CH ₂ ) _n ] R ⁴ _a Si (R ² ) _3-a (where R ² is an alkoxy group having 1 to 6 carbon atoms, and R ³ is 4 carbon atoms) A perfluoroalkyl group of from 1 to 14, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is a perfluoroalkyl group-containing alkoxysilane represented by 0 or 1). The total amount of the second component is 1 to 70% by weight of the whole, and the second component is 0.1 to 30% of the total amount of the first component and the second component.
3) 1 to 50% by weight based on the total amount of the first and second components
A nonionic emulsifier having an HLB of 1.5 to 20, anionic,
A silicone waterproofing agent characterized by being emulsified and dispersed in water in the presence of one or more emulsifiers selected from cationic or amphoteric ionic emulsifiers. 2. A waterproofing method comprising treating the surface of an inorganic porous substrate with the silicone waterproofing agent according to claim 1.