JPS6320872B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a permeable waterproofing composition comprising an organoalkoxysilane and a specific acrylic resin. When building materials are exposed to the outside air, they not only lose their weather resistance but also are very likely to be damaged by water. That is, when water from wind and rain enters into building materials, the water expands in volume by as much as 10% due to freezing in winter, damaging the building materials. Furthermore, corrosive substances such as sulfur dioxide gas, nitrogen dioxide, salt, etc. in the air penetrate deeply into the materials and cause severe damage to the building materials. Conventionally, organoalkoxysilane has been used as a water-repellent treatment agent to prevent corrosion of building materials due to water penetration. Building materials treated with such organoalkoxysilane compounds are water repellent to liquid water and permeable to water vapor, so they can be waterproofed without impairing the breathability of the building materials. There are advantages that can be achieved. However, the disadvantages of water repellent treatment agents made of organoalkoxysilane are that the weather resistance is poor and the water repellent effect on the surface disappears in a short period of time, and when the building material has a porous surface, organoalkoxysilane is only used. However, if the building material is a cement product, the hydrolyzed product of the cement will get stuck in the water-repellent capillaries and the water-repellent effect will be lost. It is difficult to identify and tends to cause problems such as unpainted parts. As a result of extensive research in order to improve these drawbacks, the present inventors found that a composition made by adding a specific acrylic resin to organoalkoxysilane showed a remarkable and durable waterproofing effect, and it was found that The inventors have found that the above is also advantageous without any drawbacks, and have completed the present invention. That is, the present invention provides (A) organoalkoxysilane and
(B) Consists of an acrylic resin obtained by polymerizing a monomer mixture containing 10% by weight or more and less than 50% by weight (hereinafter abbreviated as %) of an acrylic acid alkyl ester whose alkyl group has 1 to 10 carbon atoms, This permeable waterproofing composition is characterized in that the blending ratio of the acrylic resin is 0.1 to 10 parts by weight (hereinafter referred to as "parts") per 1 part by weight of the silane compound (A). By using organoalkoxysilane in the present invention, the surface of the building material to be waterproofed is generally covered with an extremely thin layer of water molecules.
The organoalkoxysilane applied on it causes a hydrolysis reaction with the water and becomes water repellent, and when integrated with the material, it exhibits an extremely excellent water repellent effect and is reactive to water, so it can be used in small quantities. It easily penetrates into building materials containing water, resulting in a thick water-repellent permeable layer (hereinafter referred to as the permeable layer) with a thickness of mm to several cm. Furthermore, because it has a low molecular weight, it also has the great feature of excellent permeability. In addition, in the present invention, by using acrylic resin in combination, it is possible to remove microscopically not water-repellent parts of building materials that cannot be made sufficiently water-repellent by organoalkoxysilane alone, especially building materials with porous surfaces. By covering it with a resin film to make it water resistant, and further covering the water-repellent areas with the resin film, it exhibits an extremely durable waterproof effect. In other words, by forming a waterproof permeable layer in the building material using organoalkoxysilane, and further coating the surface with an acrylic resin, the waterproof effect is significantly enhanced. Organoalkoxysilane has a low molecular weight, so it has low viscosity and high permeability, so it forms a deep penetration layer.
Because acrylic resin has a high molecular weight, it has high viscosity and low permeability, forming a thin permeable layer. If only acrylic resin is used as a waterproofing material, it will not have a water-repellent effect and will not be able to perform its function. In the present invention, (A) organoalkoxysilane and
(B) After the waterproof composition mixed with acrylic resin is applied to the surface of the building material, it is chromatographically developed to form an organoalkoxysilane layer in the lower layer and an acrylic resin layer in the upper layer. , which exhibit a remarkable synergistic effect on waterproofing in order to fully exhibit their respective functions. Furthermore, by using an acrylic resin, it is possible to impart excellent weather resistance, and the film can be highly resistant to cracking, yellowing, peeling, etc. In addition, the acrylic resin film has the effect of increasing the strength of the surface of building materials, and this effect is particularly noticeable in building materials with porous surfaces, and even when exposed to the outside air, it is resistant to deterioration due to wind and rain. This is an effect that cannot be obtained by applying a water repellent treatment agent consisting of organoalkoxysilane alone. Next, the organoalkoxysilane used in the present invention will be described. Organoalkoxysilanes have the general formula R ² nSi(OR ¹ ) ₄ - _o . (In the formula, n=0 to 3, R ¹ and R ² are an alkyl group, an aryl group, and a cycloalkyl group.) Specific examples of such organoalkoxysilane include methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethyl Silane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, isobutyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, methoxytriphenylsilane,
Diethoxydiphenylsilane, triethoxyphenylsilane, trimethylphenoxysilane, diethyldiphenoxysilane, n-butyltriphenoxysilane, triphenylphenoxysilane, diphenyldiphenoxysilane, phenyltriphenoxysilane Sisilane, methoxytricyclohexylsilane, diethoxydicyclopentylsilane, trimethoxycyclohexylsilane, ethyltricyclohexyloxysilane, dimethyldicyclopentyloxysilane, tributylcyclohexyloxysilane, tricyclopentylcyclohexyloxysilane, dicyclopropyldicyclopentyloxy Examples include silane, cyclohexyltriphenoxysilane, dicyclopentyldiphenoxysilane, phenyltricyclopentyloxysilane, and triphenylcyclohexyloxysilane. Note that triethoxymethylsilane, isobutyltrimethoxysilane, tetraethoxysilane, and the like are particularly preferred in terms of permeability to building materials and water repellency. The acrylic resin used in the present invention is obtained by polymerizing a monomer mixture containing 10% or more and less than 50% of an acrylic acid alkyl ester in which the alkyl group has 1 to 10 carbon atoms. If the content of acrylic acid alkyl ester in the monomer mixture is less than 10% by weight, problems will occur in weather resistance, and phenomena such as yellowing and decreased water resistance will occur during long-term outdoor exposure, resulting in problems in durability. There is. On the other hand, if the content exceeds 50% by weight, the formed resin film will become soft and stickiness will remain on the film surface.
When exposed outdoors, there are problems such as dirt and the like adhering to it in a short period of time. Further, the amount of acrylic resin added is 0.1 to 10 parts, preferably 0.5 to 3 parts, per 1 part of organoalkoxysilane; if it is less than 0.1 part, the coverage with the acrylic resin will be small and there will be problems in durability. . Ten
If the water exceeds 50%, the coating effect of the acrylic resin is sufficient, but the water-repellent effect of the organoalkoxysilane on the surface of the building material is small, and the surface becomes easily wetted by water, resulting in an increase in water absorption and water permeability, resulting in a decrease in water resistance. become inferior to Used in the present invention. As the acrylic acid alkyl ester, acrylic acid methyl, ethyl, n
-propyl, iso-propyl, n-butyl, iso-
Esters include butyl, sec-butyl, n-amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and the like. Other monomers that can be used in the present invention include monomers that can be copolymerized with the above-mentioned acrylic acid alkyl esters, such as methyl, ethyl, n-propyl, and iso-methacrylate. Propyl, n-butyl, iso-butyl, sec-butyl, n
- Esters such as amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, and ethylene, propylene, butene-1, pentene,
Isobutylene, 1,4-butadiene, dimethylbutadiene, 1,2-butadiene, vinyl methyl ether, vinyl propyl ether, vinyl acetate,
Vinyl chloride, vinylidene chloride, acrylonitrile, styrene, acrylic esters other than those listed above,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. are used. Particularly preferred acrylic resins in the present invention are copolymers of at least two acrylic esters of acrylic acid, such as methyl, ethyl, n-propyl, butyl, and 2-ethylhexyl, or copolymers of these acrylic esters. Ester and methyl methacrylate, styrene, 1,4-butadiene,
It is a copolymer made of a combination with other vinyl monomers selected from vinyl chloride, acrylonitrile, etc. The resin of the present invention can be obtained by polymerization by a commonly known method. It is preferable to use the waterproofing composition of the present invention by dissolving it in an organic solvent or by further diluting it, but if a large amount of organic solvent is used during the production of the acrylic resin, it may be necessary to use it in addition. There isn't. Examples of organic solvents include the following: 60
For example hexane, heptane, octane, nonane, with a boiling point range of ~180°C/760mmHg (absolute pressure)
Paraffinic hydrocarbons such as decane; aromatic hydrocarbons such as toluene, xylene and trimethylbenzene; chlorinated hydrocarbons such as trichlorethylene, perchlorethylene; e.g. ethyl, n-propyl, iso-propyl, n-butyl; ,
Examples include alcohols such as iso-butyl and sec-butyl, alcohols such as diacetone alcohol, ketones such as methyl ethyl ketone, and esters such as ethyl acetate. Of course, they can be used alone or in combination. Furthermore, the waterproof composition of the present invention can be freely colored, and common dyes and pigments can be used as the coloring agent. The waterproofing composition according to the invention is applied in known manner to the surface of the building material to be waterproofed by spraying, painting or dipping. Of course, it is possible to change it arbitrarily depending on the condition of the surface of the building material. Building materials to which the waterproofing composition of the present invention can be applied include concrete, mortar, foamed concrete, glass, ceramics, stone, brick, slate board,
These include silica plates, glass fibers, and other materials with Si—O— bonds. Furthermore, it is of course possible to further construct the following on the building material which has been waterproofed by applying the waterproofing composition of the present invention. Cosmetic cement spray material, synthetic resin emulsion sand wall spray material, cement-based multi-layer pattern spray material, synthetic resin emulsion-based multi-layer pattern spray material, reaction-curing synthetic resin emulsion-based multi-layer pattern spray material, reaction-curing synthetic resin These include solution-based multi-layer pattern spraying materials, rock wool spraying materials, lightweight aggregate-containing spraying materials, fibrous topcoating materials, and on-site mixed mortar. The present invention will be specifically explained below with reference to Examples. All parts and percentages in the examples are by weight. Moreover, the test method in the examples is as follows. 1. Viscosity of waterproofing composition: Measured at a liquid temperature of 20°C using a viscometer (NK-2 type viscometer manufactured by Iwata Painting Co., Ltd.). 2. Water absorption: A completely dry material measuring 15 cm long, 15 cm wide, and 10 cm thick was treated with a waterproofing composition on its entire surface, cured at room temperature for 3 days, and then completely immersed in water for 24 hours. After that, the weight change was measured. The water absorption rate was expressed in volume %. 3. Water permeability: Only one side of an absolutely dry material measuring 10 cm long, 10 cm wide, and 10 cm thick was treated with a waterproofing composition, and after curing at room temperature for 3 days, a transparent pipe with a diameter of 3 cm and a height of 35 cm was treated. Stand it on a surface and seal it with epoxy adhesive. Pour water so that the water head is 30 cm, and measure the water permeability after 24 hours. Water permeability was expressed in l/m ² . 4 Weather resistance: The above treated sample was tested using WE-SUN manufactured by Toyo Rika Co., Ltd.
- At a rate of 6 minutes of water injection per hour using a DC Ducycle Sunshine Weather-Ometer.
After 500 hours of irradiation, water absorption and water permeability were measured as described in 2) and 3), and yellowing of the treated surface was observed. 5 Stickiness of treated surface Test 3) A polyethylene sheet was manually crimped onto the treated surface of the sample prepared based on water permeability, and then peeled off.The stickiness of the waterproof composition treated surface was evaluated based on the resistance at that time. 6. Stain resistance One side of an absolutely dry material measuring 30 cm long, 10 cm wide and 3 cm thick was treated with a waterproofing composition, cured at room temperature for 1 day, and then exposed to the south at an angle of 45°C. After being exposed for several months, the surface was washed with water and visually inspected for dirt (adhesion of dust, etc.) on the treated surface. Example 1 As shown in Table 1, monomers such as 0.5 part of triethoxymethylsilane as organoalkoxysilane, 0.5 part of isobutyltrimethoxysilane, 0.35 part of acrylic acid ethyl ester, 0.3 part of methyl methacrylate, and 0.35 part of styrene as acrylic resin were used. The components were polymerized using a conventional method in 5.0 parts of isopropyl alcohol as a solvent, and the viscosity reached 13.
A second waterproofing composition was prepared. This is Siporex manufactured by Siporex Co., Ltd.
An amount of 0.3 kg/m ² was sprayed onto the ALC board using air spray. The performance of this waterproofing composition was measured according to the above test method, and the results were good as shown in Table 1. Examples 2 to 5 According to the procedure of Example 1, waterproofing compositions were prepared using the organoalkoxysilane compounds shown in Table 1 and acrylic resins made of the monomers shown in Table 1, and the results were similarly tested. are shown in Table 1. Comparative Examples 1 to 5 As shown in Table 2, organoalkoxysilane alone (Comparative Example 1), a large amount of resin (Comparative Example 2), and a small amount (Comparative Example 3) were added to Siporex ALC board as a building material. ), and the content of acrylic acid alkyl ester in the added resin is 10%
(Comparative Example 4), 50% or more (Comparative Example 5), and those using high molecular weight methylpolysiloxane instead of organoalkoxysilane (Comparative Examples 6 to 7). The performance as a waterproofing composition was investigated. As shown in Table 2, the results are unfavorable due to defects in waterproof performance, weather resistance, stickiness of the treated surface, and stain resistance.

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Claims (1)

[Scope of Claims] 1. A monomer mixture containing 10% by weight or more and less than 50% by weight of (A) organoalkoxysilane and (B) acrylic acid alkyl ester whose alkyl group has 1 to 10 carbon atoms is polymerized. A permeable waterproofing composition comprising the obtained acrylic resin and having a blending ratio of 0.1 to 10 parts by weight of (B) acrylic resin to 1 part by weight of (A) organoalkoxysilane. .