JP2685852B2 - Penetrating waterproofing agent composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention, when applied to a porous inorganic material such as concrete or mortar, exhibits excellent water repellency immediately after application and has a long water repellency. The present invention relates to a permeable waterproofing agent composition that can last for a period of time.

[Technical background of the invention and its problems] In recent years, it has become a serious problem that structures made of porous inorganic materials such as concrete and mortar deteriorate due to salt damage, frost damage, alkali-aggregate reaction, and the like.

Deterioration of these porous inorganic materials is caused by the intrusion of water into the inorganic materials. That is, salt damage is ionic chloride was dissolved in water with water (Cl ^-) were generated by penetration, freezing damage is caused by water that has entered freezes, alkali-aggregate reaction water and aggregate that intrusion It is generated by causing a chemical reaction.

Therefore, in order to solve these problems, it is necessary to prevent moisture from entering the inside of the inorganic material, and some methods based on it are known.

For example, a method of imparting water repellency by applying a resin solution such as an acrylic resin or a silicone resin or a sodium organosiliconate solution to the surface of an inorganic material to impart the water repellency has been performed. However, these methods have a problem that the water-repellent layer formed is thin and the durability is poor.

Recently, RTV silicone rubber has 1 to 4 carbon atoms.
A method has been proposed in which a low-molecular-weight alkylalkoxysilane is mixed and applied to an inorganic material (Japanese Patent Publication No. 63-40232).
Reference). It is considered that this method can form a deep waterproof layer and a film having excellent initial water repellency.

However, although these low molecular weight alkylalkoxysilane compounds form a deep waterproof layer, a sufficient water-repellent effect cannot be obtained due to the low hydrophobicity of the alkyl group. Therefore, the water-repellent effect substantially depends only on the RTV silicone rubber and is no different from the conventional method.

[Object of the Invention] The present invention solves the above-mentioned problems, exhibits water repellency immediately after coating, is deep and has excellent durability (water repellency can be maintained for a long time). An object is to provide a permeable waterproofing agent composition capable of forming a layer.

[Structure of the Invention] As a result of research to achieve the above-mentioned object, the inventors of the present invention have found that the water-repellent performance of the waterproof layer largely depends not only on the penetration depth of the waterproof agent but also on the hydrophobicity of the silane compound itself. I focused on. Then, as a result of further research, it was found that the above object can be achieved by including an organosilane containing an alkyl group having 5 to 18 carbon atoms as a constituent of the waterproofing agent composition, and the present invention has been completed.

The penetrating waterproofing agent composition of the present invention comprises (A) general formula (I): (R ¹ ) aSiX _4- a (wherein, R ¹ represents a monovalent hydrocarbon group having 5 to 18 carbon atoms,
X represents a hydrolyzable group, and a represents 1, 2 or 3) 50 to 100% by weight of an organosilane represented by the formula: and general formula (II): R ² SiX ₃ (wherein R ² is a carbon number) 1 to 4 represents a substituted or unsubstituted monovalent hydrocarbon group, and X represents a hydrolyzable group) 0 to 50% by weight of organosilane, and 100 parts by weight of organosilane, (B) 1 to 100 parts by weight of a linear polyorganosiloxane containing at least two hydroxyl groups bonded to silicon atoms in the molecule and having a viscosity at 25 ° C of 500 to 200,000 cSt, (C) 0.01 to 10 parts by weight of a hydrolysis catalyst And (D) 50 to 2,000 parts by weight of an organic solvent.

The component represented by the general formula (I) among the component (A) used in the present invention is an organosilane or a mixture thereof.

The component represented by the general formula (I) is a main component that has the ability to penetrate into the surface layer of the inorganic material and suppress the intrusion of water and chloride ions coexisting with it.

R ¹ in the general formula (I) is a monovalent hydrocarbon group having 5 to 18 carbon atoms, and if the carbon number is outside this range, a sufficient waterproof layer is not formed and the water repellency effect is reduced. As the monovalent hydrocarbon group having 5 to 18 carbon atoms, a pentyl group, a hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Alkyl groups such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group; β-phenylethyl group, β-phenylpropyl An aralkyl group such as a group can be exemplified. Of these, an alkyl group is preferred for the purpose of imparting excellent water repellency, and the water repellency is particularly excellent, and the alkyl group having 6 to 10 carbon atoms is particularly preferable because it is easy to obtain the raw material and to synthesize and purify it. preferable. When a is 2 or 3 in the general formula, R ¹
May be the same or different.

Examples of the hydrolyzable group represented by X in the general formula (I) include
Examples thereof include an alkoxy group, an acyloxy group, an amino group, an aminoxy group, an oxime group, a ketoxime group, an amide group, an alkenyloxy group and a halogen atom. Among these, an alkoxy group is preferable because it does not damage building materials, has a weak odor generated during the curing reaction, and has good storage stability, and a methoxy group is preferable because it gives an appropriate curing rate. Particularly preferred.

Of the component (A) used in the present invention, the component represented by the general formula (II) is an organosilane or a mixture thereof.

The component represented by the general formula (II) penetrates into the surface layer of the inorganic material together with the compound represented by the general formula (I), and exerts the ability to suppress entry of water and chloride ions coexisting with it. It is an ingredient.

Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms of R ^{2 in} the general formula (II) include a methyl group, an ethyl group,
Alkyl group such as propyl group, butyl group; vinyl group,
Examples thereof include alkenyl groups such as allyl group; and substituted hydrocarbon groups such as γ-aminopropyl group and γ-glycidoxypropyl group.

Examples of the hydrolyzable group X in the general formula (II) are the same as the hydrolyzable group X in the general formula (I).

As for the mixing ratio of the organosilanes represented by the general formulas (I) and (II) constituting the component (A), the proportion of the organosilane represented by the general formula (I) needs to be 50% by weight or more. is there. If this blending ratio is less than 50% by weight, a sufficient water repellent effect cannot be obtained.

The component (B) used in the present invention is a linear polyorganosiloxane having at least two hydroxyl groups bonded to silicon atoms in the molecule.

In this linear polyorganosiloxane, the hydrocarbon group directly bonded to the silicon atom is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group or a hexyl group; a vinyl group or an allyl group. Alkenyl group;
An aryl group such as a phenyl group; a β-phenylethyl group, a 3,3,3-trifluoropropyl group, a chloromethyl group, and a β-cyanoethyl group can be exemplified.

Methyl group, vinyl group or phenyl group is preferred because it is easy to synthesize among these hydrocarbon groups directly bonded to a silicon atom, and more preferably 85% or more of all hydrocarbon groups are methyl groups, Most preferably, substantially all of the hydrocarbon groups are methyl groups. The raw material intermediate is most easily obtained when all of the hydrocarbon groups are methyl groups, and thus the linear polyorganosiloxane of the component (B) has a viscosity of 500 to 200,000 cSt. If the viscosity is less than 500 cSt, the elongation of the rubber-like elastic body after curing is insufficient, and 200,
If it exceeds 000 cSt, a uniform composition cannot be obtained, and the workability of extrusion is deteriorated. The viscosity of component (B) is 3,000 to 15
It is preferably 0,000 cSt.

Further, the component (B) preferably contains a silanol group at the terminal in order to achieve the object of the present invention.

The blending amount of the component (B) is 1 to 100 parts by weight, preferably 5 to 75 parts by weight, relative to 100 parts by weight of the component (A). If the blending amount of the component (B) is less than 1 part by weight, the durability of the waterproof layer may be insufficient, and if it exceeds 100 parts by weight, the compatibility with the component (A) decreases.

The component (C) is a hydrolysis catalyst. The component (C) is the component (A) that has penetrated into the inorganic material, the inner surface of the gap in the inorganic material, the hydroxyl group of the component (B), the hydrolyzable group of the component (A) and the inorganic material or the air. It is a component for promoting a reaction with water and a component for promptly exhibiting water repellency.

As the component (C), dibutyltin dilaurate, dibutyltin diacetate, butyltin tri-2-ethylhexoate, stannous caprylate, tin naphthenate,
Tin oleate, iron-2-ethylhexoate, lead-2
-Ethyl octoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-
Metal salts of organic carboxylic acids such as ethylhexoate, titanium naphthenate, zinc naphthenate, cobalt naphthenate, zinc stearate; tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) ) Organic titanates such as titanates; organotitanium compounds such as organosiloxytitanium and β-carbonyltitanium;
Aminoalkyl group-substituted alkoxysilanes such as γ-aminopropyltriethoxysilane and n- (trimethoxysilylpropyl) ethylenediamine; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof;
Quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, lithium oxalate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; guanidine compounds such as tetramethylguanidine And guanidyl group-containing silane and siloxane compounds.

The blending amount of the component (C) is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component (A). If the blending amount of the component (C) is less than 0.01 parts by weight, the development of water repellency will be delayed, and if it exceeds 10 parts by weight, the inorganic material will have a wet color or will be deposited on the surface to impair the appearance.

The component (D) is an organic solvent. This (D) component is
It is a component for uniformly mixing and dissolving the components (A) and (B), and for facilitating the work of coating and penetrating the composition into the inorganic material.

As the component (D), alcohols such as methanol, ethanol and isopropanol; ether alcohols and ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran and dioxane; acetone, methyl ethyl ketone and diethyl ketone Ketones; Esters such as methyl acetate, ethyl acetate, n-butyl acetate; Aliphatic hydrocarbons such as n-hexane, gasoline, rubber volatile oil, mineral spirits, kerosene; Aroma such as benzene, toluene, xylene Group hydrocarbons can be exemplified.

The compounding amount of the component (D) is 50 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight, based on 100 parts by weight of the component (A). If the blending amount of the component (D) is less than 50 parts by weight, the component (B) tends to precipitate at low temperatures, and if it exceeds 2,000 parts by weight, the concentrations of the components (A) and (B) become too low. The application workability is deteriorated because the coating must be applied again.

Examples of the inorganic material to which the composition of the present invention can be applied include those containing cement, that is, concrete and cement mortar generally used in various fields at present.

As a method of applying the composition of the present invention to an inorganic material,
A usual method such as brush coating, roller coating, or spray coating can be applied.

The composition of the present invention, when applied to the surface of an inorganic material, quickly penetrates into the inorganic material and hardens to form a water-repellent layer. The water-repellent layer prevents the entry of water and chloride ions. However, excellent water repellency can be maintained for a long time.

EFFECTS OF THE INVENTION The composition of the present invention rapidly exhibits water repellency when applied to a porous inorganic material such as concrete and mortar, and the water repellent layer formed is deep and excellent in durability. There is.

Therefore, even if rain is encountered shortly after the coating operation, the water repellency can be sufficiently exerted and the water repellency can be maintained for a long period of time, which is extremely useful in practice.

[Examples of the Invention] The present invention will be described in more detail below with reference to Examples. In addition,
In the following, “part” means “part by weight”.

Reference Example 1 To 100 parts of silanol-terminated polydimethylsiloxane having a viscosity of 12,000 cSt at 25 ° C, 0.2 parts of dibutyltin dilaurate, 8.0 parts of methyltrioxime silane, 2.0 parts of γ-aminopropyltriethoxysilane, and 100 parts of toluene were added to obtain moisture. The mixture was uniformly mixed while being blocked. This is B-1.

Reference Example 2 100 parts of silanol-terminated polyorganosiloxane having a viscosity of 700 cSt at 25 ° C. and 0.2 parts of tetrabutyl titanate
Parts, 8.0 parts of methyltrimethoxysilane, and 2.0 parts of γ-glycidoxypropyltriethoxysilane were added and uniformly mixed in a state of blocking moisture. This is B-2.

Examples 1 to 4 and Comparative Examples 1 to 3 The components shown in Table 1 were mixed to produce compositions of Examples and Comparative Examples consisting of organosilane, room temperature curable silicone rubber, hydrolysis catalyst and organic solvent. did.

Using each of the obtained compositions and two different kinds of inorganic materials, water repellency was evaluated by the following method.

Water repellency confirmation test (1) First, knead concrete with a mixing ratio of ordinary Portland cement: river gravel (surface dry state): river sand (surface dry state): water = 270: 1,111: 653: 175 (weight ratio), Dimension 10 x 10 x
A 10 cm compact was obtained. Next, this molded body is cured according to JCI-SE4 [accelerated strength test method for concrete by hot water method (70 ° C)], and then dried for 7 days (20 ° C, 50-60 ° C).
% RH) and cured to obtain a concrete specimen.

After that, each composition was applied to the surface of the test piece with a brush so that the application amount was 400 g / m ² . After application, 25 ℃, 50%
After drying in an RH atmosphere for 1 hour, the contact angle of water on the coated surface was measured.

In addition, the contact angle of water on the coated surface of the specimen that had been aged for 7 days in the above atmosphere (25 ° C, 50% RH) and then immersed in water at 25 ° C for 28 days or exposed outdoors for 128 days Was measured.

Further, the depth of the water repellent portion (depth of the water repellent layer) when the test piece was divided into two and water was sprayed on the split surface was measured.

 The results are shown in Table 1.

Water repellency confirmation test (2) Ordinary Portland cement: Toyoura standard sand = 1: 3 (weight ratio) The mortar was mixed and the water-cement ratio was adjusted so that the flow value was 170 ± 5. Then, this was kneaded and molded and cured in the same manner as in Examples 1 to 4 to prepare a specimen. Next, Examples 1 to 4 and Comparative Example 1 were applied to this test piece.
Each of the compositions 3 to 3 was applied, and the water repellency was evaluated by the same method as in the test (1). The results are shown in Table 2.

Claims (1)

(57) [Claims] (A) General formula (I): (R ¹ ) aSiX _4- a (wherein R ¹ represents a monovalent hydrocarbon group having 5 to 18 carbon atoms,
X represents a hydrolyzable group, and a represents 1, 2 or 3) 50 to 100% by weight of an organosilane represented by the formula: and general formula (II): R ² SiX ₃ (wherein R ² is a carbon number) 1 to 4 represents a substituted or unsubstituted monovalent hydrocarbon group, and X represents a hydrolyzable group) 0 to 50% by weight of organosilane, and 100 parts by weight of organosilane, (B) 1 to 100 parts by weight of a linear polyorganosiloxane containing at least two hydroxyl groups bonded to silicon atoms in the molecule and having a viscosity at 25 ° C of 500 to 200,000 cSt, (C) 0.01 to 10 parts by weight of a hydrolysis catalyst And (D) 50 to 2,000 parts by weight of an organic solvent, a penetrating waterproofing agent composition.