JPS6251310B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a water absorption prevention material that has excellent water absorption prevention properties, permeability, and adhesive properties, and is made of a specific hydrolyzable silane compound such as organoalkoxysilane, organohalogensilane, and organosilicon isocyanate, and a chlorinated polyolefin resin. The present invention relates to a composition. In general, buildings made of materials with high porosity, such as concrete, mortar, brick, slate, calcium silicate board, and ALC (autoclave-cured lightweight concrete), are susceptible to the effects of wind and rain and deteriorate rapidly. In order to prevent this, various treatment agents have been studied to protect especially the outer walls of buildings, and so-called architectural water repellents have been commercially available. This architectural water repellent agent is mainly composed of metal soap or silicone resin, and silicone compounds such as methylpolysiloxane and methylsiliconate are particularly known to have a large water-repellent effect. However, since methylpolysiloxane is a polymer with a large molecular weight, it has poor permeability to the coating precursor, and since it does not chemically bond to the precursor, migration occurs within the precursor and the water absorption prevention effect does not last. Furthermore, methyl siliconate has poor durability and many problems because the polymer once formed reacts with the alkali precursor and decomposes, causing the polymer to be washed away by rainwater. Recently, specific hydrolyzable silane compounds such as organoalkoxysilane, organohalogensilane, and organosilicon isocyanate have been developed and commercially available as water absorption prevention materials. Since these specific silane compounds have a low molecular weight, they penetrate deeply into the precursor through the capillaries of the applied precursor structure, react with moisture contained in the precursor, and bind and condense themselves. At the same time, the free hydroxyl groups (Si-OH) of the precursor structure are bonded to form a network structure, and as a result of being chemically bonded and fixed to the precursor, a deep water absorption prevention layer with excellent retention and durability is formed. Conceivable. However, if the building material has a porous surface and a high porosity, using these specific silane compounds alone will result in poor water repellency on the surface, and sometimes the water absorption prevention effect will be small and the effect may be uneven. Furthermore, when the building material is a cement product, the hydrolysis products of the cement become embedded in the capillaries of the applied surface, eliminating the water repellent effect. Furthermore, there are also disadvantages in that it is difficult to identify the area to be applied during application, and problems such as unpainted areas are likely to occur. Furthermore, a decorative material is sprayed onto the surface of the precursor treated with these specific silane compounds.
When applying paint, etc., the adhesion to the paint is poor and the paint may peel off after application. As a result of intensive research to improve these drawbacks, the present inventors found that a composition containing a chlorinated polyolefin resin mixed with a specific hydrolyzable silane compound showed excellent water absorption prevention properties, and was found to be suitable for spray makeup. The present inventors have discovered that it has good adhesion to materials, paints, etc., and is advantageous in terms of construction without any difficulties, leading to the completion of the present invention. That is, the present invention provides a hydrolyzable compound selected from (A) organoalkoxysilane, organoacetoxysilane, organohalogensilane, organodisilane, organosilane carboxylic acid, organosilantiol, organosilicon isocyanate, and organosilicon isothiocyanate. At least one silane compound to be obtained and (B) a chlorinated polyolefin resin, and the blending ratio A/B is 1/0.1.
10 (parts by weight). When the above-mentioned specific hydrolyzable silane compound contained in the composition of the present invention is applied to concrete, mortar, brick, slate, calcium silicate board, etc., it easily penetrates into the precursor. At the same time, it reacts with water and condenses, and also bonds with free hydroxyl groups of the precursor structure, resulting in a thick water absorption prevention layer (hereinafter referred to as a permeation layer) with a thickness of several mm to several centimeters. Furthermore, due to the presence of the chlorinated polyolefin resin, which is one of the components of the composition of the present invention, it forms a resin film on the surface or surface layer of the building material, or by clogging the porous parts, it significantly prevents water absorption. , water repellency can be improved. In addition, the density of the silane compound on the applied surface may be reduced, and the adhesion to adsorption decorative materials, paints, etc. is dramatically improved. In general, hydrolyzable silane compounds have low molecular weight, low viscosity, and high permeability, forming a deep permeation layer, whereas chlorinated polyolefin resins are polymers, so they have high viscosity and low permeability, forming a shallow permeation layer. Form. As mentioned above, just as a specific silane compound alone does not provide a good water absorption prevention material, applying only a chlorinated polyolefin resin does not show good water absorption prevention properties because the permeation layer is shallow. Only after the water absorption preventive material composition of the present invention comprising a hydrolyzable silane compound and a chlorinated polyolefin resin is applied to a building material is a silane compound layer that can be hydrolyzed in the lower layer, as in chromatography, and an upper layer thereof. When developed with a chlorinated polyolefin resin layer, a synergistic effect appears in order to fully exhibit the functions of each component, and exhibits an excellent water absorption prevention effect that cannot be observed with each component alone. Furthermore, the presence of chlorinated polyolefin resin on the coating surface has the effect of increasing the strength of the surface and improving the adhesion with spray decorative materials and paints. This is an effect not seen with preventive materials. Next, organoalkoxysilanes, organoacetoxysilanes, organohalogensilanes, organodisilanes, organosilane carboxylic acids, organosilantiols, organosilicon isocyanates, and organosilicon isothiocyanates used in the present invention will be described. Organoalkoxysilanes have the general formula R ² Si(OR ¹ ) _4-o . (In the formula, n=0 to 3, R ¹ is an alkyl group, and R ² is an alkyl group, an alkylene group, an aryl group, or a cycloalkyl group.) Specific examples of such organoalkoxysilane include, for example, methoxytrimethylsilane, Dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, methoxytriethylsilane, dimethoxydiethylsilane, trimethoxyethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, Methoxytrinormalpropylsilane, dimethoxydinormalpropylsilane, trimethoxynormalpropylsilane, trimethoxyisopropylsilane, trimethoxynormalbutylsilane, trimethoxyisobutylsilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiphenylsilane, triethoxyf Examples include enylsilane, dimethoxydivinylsilane, triethoxyvinylsilane, dimethoxydiphenylsilane, dimethoxydicyclopentylsilane, and dimethoxydicyclohexylsilane. In terms of storage stability, permeability, and rate of formation of a permeable layer, the best alkoxy group is methoxy group, followed by ethoxy group, and examples of compounds include trimethoxymethylsilane, trimethoxyethylsilane, trimethoxyn-propylsilane, and trimethoxy group. Normal butylsilane, trimethoxyisobutylsilane and the like are preferred. Organoacetoxysilane is a compound represented by the general formula RnSi(OCO CH ₃ ) _4-o . (In the formula, n is 1 to 3, R is an alkyl group,
They are an alkylene group, an aryl group, and a cycloalkyl group. ) Specific examples of such organoacetoxysilane include acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, triacetoxyethylsilane, triacetoxyn-propylsilane, triacetoxyn-butylsilane, triacetoxyisobutylsilane, triacetoxy Examples include vinylsilane, triacetoxycyclohexylsilane, triacetoxyphenylsilane, and diacetoxydiphenylsilane. Organohalogensilane is a compound represented by the general formula RnSiX _4-o .
(In the formula, n is 1 to 3, R is an alkyl group, alkylene group, aryl group, or cycloalkyl group, and X is F, Cl, or Br.) Specific examples of such organohalogensilanes include trichloromethyl, Silane, dichlorodimethylsilane, chlortrimethylsilane, trichloroethylsilane, trichloron-propylsilane, trichloron-butylsilane, trichloroisobutylsilane, trichlorovinylsilane, trichlorophenylsilane, trichlorocyclohexylsilane, dichloromethylphenylsilane, dichlor Ethyl phenylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorosilane, difluorodimethylsilane, trifluoromethylsilane, trifluorophenylsilane, dibromdimethylsilane , tribromomethylsilane, tribromophenylsilane, etc. Organodisilane is a compound represented by the general formula _R3 -Si-Si- _R3 . (In the formula, R is an alkyl group, an aryl group, or a cycloalkyl group.) Specific examples of such organodisilane include hexamethyldisilane, hexaethyldisilane, hexanormalpropyldisilane, hexaphenyldisilane, hexacyclohexyldisilane, etc. There is. Organosilane carboxylic acid is a compound represented by the general formula R ₃ Si COOH. (In the formula, R is an alkyl group, an aryl group, or a cycloalkyl group.) Specific examples of such organosilane carboxylic acids include triphenylsilylcarboxylic acid, trimethylsilylcarboxylic acid, triethylsilylcarboxylic acid, and tri-n-propylsilylcarboxylic acid. acids, such as tricyclohexylsilylcarboxylic acid. Organosilantiol is a compound represented by the general formula R ₃ SiSH. (In the formula, R is an alkyl group, an aryl group, or a cycloalkyl group.) Specific examples of such organosilantiol include trimethylsilanethiol, tripropylsilanethiol, triphenylsilanethiol, and the like. Organosilicon isocyanate is a compound with the general formula RnSi(NCO) _4-o . (In the formula, n is 1 to 3, and R is an alkyl group, an aryl group, or a cycloalkyl group.) Specific examples of such organosilicon isocyanates include trimethyl silicon isocyanate, dimethyl silicon diisocyanate, methyl Silicon triisocyanate, ethyl silicon triisocyanate, normal propyl silicon triisocyanate, normal butyl silicon triisocyanate, isobutyl silicon triisocyanate, phenyl silicon triisocyanate, cyclohexyl silicon triisocyanate, diphenyl silicon diisocyanate ,and so on. Organosilicon isothiocyanate is a compound represented by the general formula RnSi(NCS) _4-o . (In the formula, n is 1 to 3, R is an alkyl group,
They are an aryl group and a cycloalkyl group. ) Specific examples of such organosilicon isothiocyanates include trimethylsilicon isothiocyanate, dimethylsilicon diisothiocyanate, methylsilicon triisothiocyanate, ethylsilicon triisothiocyanate, normal propylsilicon tolysothiocyanate, normal Butyl silicon triisothiocyanate, isobutyl silicon triisothiocyanate, phenyl silicon triisothiocyanate,
Examples include cyclohexyl silicon triisothiocyanate and diphenyl silicon diisocyanate. Organoalkoxysilanes are generally preferred over other compounds in terms of the balance between permeation layer formation rate and product storage stability, as well as the odor and toxicity of hydrolysis reaction by-products. Among compounds other than organoalkoxysilane, organoacetoxysilane, organodisilane, and organosilicon isocyanate can be preferably used. The chlorinated polyolefin resin used in the present invention is chlorinated polyethylene or chlorinated polypropylene, and a polyolefin resin with a degree of polymerization of 100 or more and a chlorine content of 20% by weight or more can be preferably used for chlorine. If the chlorine content is low, the water absorption prevention property will be low, which is not preferable. Since the film of chlorinated polyolefin resin is generally hard and brittle, it is desirable to use a plasticizer together. Commonly used plasticizers can be used, such as phthalate esters such as dibutyl phthalate and dioctyl phthalate, phosphate esters such as tributyl phosphate and octyl diphenyl phosphate, epoxies, and paraffin chloride. . The water absorption preventing material composition of the present invention is put to practical use as a water absorption preventing material solution dissolved in an organic solvent at an arbitrary concentration, and examples of the organic solvent include the following. Toluene, xylene, benzene, ethyl acetate,
Butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, cellosolve acetate, carbon tetrachloride, trichlorethylene, perchlorethylene, chloroform, tetrahydrofuran, ethyl ether, dimethyl formamide, solvent naphtha, etc. It is of course possible to use these alone or in combination. Furthermore, the water absorption preventing material composition of the present invention can be freely colored, and by coloring, it is also possible to clearly distinguish between the water absorption preventing treated surface and the non-treated surface, which is a preferred method. As the coloring agent, ordinary dyes and pigments are used. The water absorption prevention material composition according to the present invention has a blending ratio of the silane compound and chlorinated polyolefin of 1/1.
It needs to be 0.1 to 10 (parts by weight). If this blending ratio is less than 1/0.1, the packing effect of the chlorinated polyolefin resin on the surface of the building material will be small, resulting in a marked decrease in the water absorption prevention effect and the adhesion of spray-on decorative materials. On the other hand, if it exceeds 1/10, sufficient chromatographic development of the chlorinated polyolefin resin in the surface layer and the silane compound in the lower layer cannot be obtained, resulting in a decrease in the water absorption prevention effect. Further, the amount of the silane compound contained in the water absorption preventing material solution is preferably 3 to 20% by weight. When this content is less than 3%, the water absorption prevention effect is no longer satisfactory, and when it is more than 20%, the effect reaches a saturated state, and it is often impractical due to price considerations. However, in cases where the material has a particularly large porosity with high water absorption, and is intended for additional purposes such as anti-freezing, it may be desirable to increase the content of the silane compound to 50% or more. The anti-water absorption solution according to the invention is applied to the surface of the building material to be prevented from absorbing water by known methods, ie by spraying, coating or dipping. The coating amount is about 0.2 to 1 Kg/m ² when the concentration of the silane compound in the water absorption prevention material solution is 3 to 20% by weight, and can of course be changed arbitrarily depending on the surface condition of the building material. In general, relatively dense materials such as concrete are about 0.2 to 0.4 Kg/ ^m2 ,
For porous materials such as ALC, a coating amount of about 0.4 to 1 kg/m ² is preferable from the viewpoint of workability. Building materials to which the water absorption prevention material composition of the present invention is applied include concrete having voids (water absorption) on the surface, mortar, ALC, cellular concrete, bricks, roof tiles, slate, calcium silicate plates, ceramics,
These include tiles, stones, and other materials containing Si-OH. The surface coated with the water absorption prevention material composition of the present invention has good adhesion and adhesion with the spraying material, so the following materials can be applied directly, and the primer treatment that is often carried out in painting is unnecessary. Necessary and economical. Examples of sprayed decorative boards and paints applied to the above surfaces include decorative cement sprayed materials, synthetic resin emulsion sand wall-like sprayed materials, cement-based multi-layer pattern sprayed materials, synthetic resin emulsion-based multi-layered pattern sprayed materials,
Reaction-curing synthetic resin emulsion-based multilayer pattern spraying material, reaction-curing synthetic resin solution-based multilayer pattern spraying material,
There are sprayed rock wool materials, lightweight aggregate-containing sprayed boards, fibrous topcoats, and on-site mixed mortars. The present invention will be specifically explained below with reference to Examples. All parts and percentages in the examples are by weight.
It is. Moreover, the test method in the examples is as follows. 1 Water Absorption Rate (ALC Precursor) ALC has a large saturated water absorption amount, and since the saturated water absorption amount differs depending on the sampling site, it was tested and measured as follows. Absolutely dry ALC precursor (length 10cm, width 10cm, thickness 5cm) whose saturated water absorption has been measured in advance
After applying the water absorption prevention material solution evenly over the entire surface and drying it indoors at 20℃ for 7 days, immerse it in a water tank to a depth (a) of 3 cm as shown in Figure 1, and measure the weight increase due to water absorption after 24 hours. was measured to determine the water absorption rate. Water absorption rate (%) = Increased weight due to water absorption / Saturated water absorption amount of test specimen × 100 2 Water absorption rate (preservatives other than ALC) A water absorption prevention material solution was evenly applied to the entire surface of the completely dry precursor material, and the water absorption prevention material solution was applied indoors for 20 minutes. After drying at ℃ for 7 days, it was completely immersed in a water tank 2 cm below the water surface, and the amount of water absorbed after 24 hours was measured to determine the water absorption rate. Water absorption rate (%) = Increased weight due to water absorption / Test weight before water absorption x 100 3 Water permeability As shown in Figure 2, apply a water pressure of 200 mm (b) of water head to the coated surface and measure the difference in water level in a measuring pipette after 24 hours. Based on this, water permeability is calculated. The water permeability was expressed in / ^m2 . 4 Adhesion with finishing material The water absorption prevention material was applied uniformly, and after air drying, the finishing material was immediately applied and dried indoors at 20°C for 14 days. Adhesive strength was measured in an air-dried state using a Kenken type tensile tester. The adhesion test after immersion in water was carried out by immersing the precursor in water for 24 hours, then taking it out and immediately examining whether it peeled off by hand. Example 1 Triethoxymethylsilane as shown in Table-1
A water absorption prevention material solution was prepared by mixing and dissolving 10 parts of chlorinated polyethylene as a chlorinated polyolefin resin, and 10 parts of chlorinated paraffin as a plasticizer in 70 parts of toluene. Spray this material onto the ALC board with air spray to give 0.6kg/
The water absorption prevention performance was measured according to the above-mentioned test method, and the results are shown in Table ¹ . It exhibited excellent water absorption prevention performance with low water absorption and water permeability. Examples 2 to 10 Using the hydrolyzable silane compounds shown in Table-1 and the chlorinated polyolefin resins shown in Table-1,
A water absorption prevention material solution was prepared using a solvent. These were sprayed onto various building materials and evaluated according to the test method described above. All showed excellent water absorption prevention performance. Examples 11 to 20 The water absorption prevention material solutions prepared in Examples 1 to 10 were sprayed, and immediately after air drying, various finishing materials were sprayed by air spray. The adhesion to finishing materials and building materials was evaluated using the above test method and is shown in Table 2. When air-dried, the base material of the building material or finishing material was destroyed, and it showed excellent adhesion even after immersion in water. Comparative Examples 1 to 6 As shown in Table 3, the water absorption prevention performance against ALC and mortar was similarly evaluated for uncoated, hydrolyzable silane compound alone, and chlorinated polyolefin resin alone. In all cases, the water absorption prevention performance was significantly inferior to Examples 1 to 10. Comparative Examples 7 to 13 As shown in Table 4, the adhesion to various finishing materials was evaluated for ALC and mortar sprayed with no coating, a hydrolyzable silane compound alone, and a chlorinated polyolefin resin alone. All from Example 11
Although inferior to No. 20, the adhesion was low even when air-dried when the hydrolyzable silane compound was used alone, and after immersion in water when the chlorinated polyolefin resin was used alone.

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Figure 1 is a schematic diagram of the equipment for measuring water absorption.
indicates the test specimen, 2 indicates the water tank, 3 indicates water, and a indicates the immersion depth (3 cm) of the test sample. Figure 2 is a schematic diagram of the equipment for measuring water permeability, 1 is a measuring pipette,
2 is a funnel, 3 is a sealant, 4 is a treated surface, 5
indicates the test specimen, b indicates the water head of 200 mm, and c indicates the diameter of the test surface of the test sample of 75 mmφ. Figure 3 shows the structure of a test specimen for measuring adhesion with finishing materials.
1 is a jig for measuring adhesive strength, 2 is an epoxy adhesive, 3 is a finishing material, 4 is a treated surface, and 5 is a building material.

Claims (1)

[Claims] 1 Consisting of the following A and B, and their blending ratio A/
A water absorption preventing material composition characterized in that B is 1/0.1 to 10 (parts by weight). A At least one hydrolyzable silanide selected from organoalkoxysilane, organoacetoxysilane, organohalogensilane, organodisilane, organosilane carboxylic acid, organosilantiol, organosilicon isocyanate, and organosilicon isothiocyanate. B Chlorinated polyolefin resin.