JP2621427C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to durability, such as weather resistance, stain resistance, water resistance, and frost resistance, treated with a water- and oil-repellent agent comprising a fluorine-containing silane compound, and mold resistance. To building materials with excellent properties. More specifically, the present invention relates to a water- and oil-repellent cement joint material, an ALC plate, a slate plate, a calcium silicate plate, a slate, a cement molding, a cement mortar, a concrete base, and a paint applied to these. [Conventional technology and problems] In general, building base materials, such as ALC boards, cement mortar surfaces, concrete surfaces,
The slate plate and the silica plate have a high water absorption rate, and are easily stained and stained by water absorption. In particular, ALC plates, slate plates, and the like are often coated on a design or for protection of a substrate because the strength is reduced by water absorption, and are rarely used without being coated. If the durability of the coating film on the coated surface is insufficient, deterioration, peeling, blistering, etc., occur, and not only the coating film but also the underlayer is chipped, dropped off, and weakened. [Problems to be Solved by the Invention] Water causes any of the causes of the deterioration of building materials as described above, and in many cases, deterioration occurs through water. Therefore, if water repellency is imparted to a building material, it is possible to obtain a material that can be used in places where durability is required without changing the components of the material itself. [Means for Solving the Problems] The present invention relates to a compound represented by the general formula R _f (CH ₂ ) _n Y (CH ₂ ) _m SiX ₃ (I) wherein R _f is a C _1-20 perfluoroalkyl group, n and m is an integer of 0 to 3, Y is _{-CH 2 -, - CH 2 O} -, - NR -, - CO 2 -, - CON
R -, - S -, - SO 3 -, - SO 2 NR- (R is H or an alkyl group C _{1 to 5),} X is Cl, Br, OC
H ₃ , OC ₂ H ₅ ] and a water / oil repellent treated building material treated with a water / oil repellent comprising a fluorinated silane compound. The building materials targeted in the present invention are many building materials such as cement-based jointing materials, ALC plates, slate plates, calcium silicate plates, cement-based moldings, cement mortars, concrete bases, and materials coated with these. Is included. In the present invention, the fluorine-containing silane compound which is the main component of the water / oil repellent is a compound represented by the general formula (I), and is preferably a general formula C ₅ F ₁₇ SO ₂ NR (CH ₂ ) ₃ SiX ₃ (II) ( Where R
Alkyl group, X of H or C _{1 to 5} is a fluorine-containing silane compound represented Cl, Br, with _{OCH 3, OC 2 H 5)} . The compound represented by the general formula (II) has high compatibility with a solvent due to a linear sulfonyl group and a side chain alkyl group, and has high uniformity of a coating film when applied to a building material. Further, the perfluoroalkyl group is uniformly oriented on the outer surface, exhibits excellent hydrophobicity, and has a function of preventing permeation of water with a small amount. In the present invention, the coating amount of the fluorine-containing silane compound represented by the general formula (I) or (II) is preferably in the range of 0.001 to 20% by weight. If it is 0.001% by weight or less, the effect of water / oil repellency is small, and if it is 20% by weight, the effect is saturated and the treatment agent is wasted. The fluorine-containing silane compound used in the present invention is usually used as a solution having a dilution concentration of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, which is applied by diluting with a solvent. Even when the concentration of the fluorinated silane coupling agent is 0.01% by weight or less, sufficient water repellency and oil repellency can be obtained by coating several times. If the content is more than 20% by weight, uneven coating may occur or a long time is required for drying. When applied to a building material having a high water absorption rate, for example, an inorganic material, it is preferable to repeat the recoating in order to impart a better water absorption prevention effect. As the solvent, organic solvents such as halogenated hydrocarbons, alcohols, ethers and the like are preferable, and those which are anhydrous or to which a small amount of an aqueous solution of an amine or an acid is added as necessary are used. The amine used here may be any of primary, secondary and tertiary amines, but primary amines are particularly effective. In an aqueous solution of these amines or acids, a polar group present near the surface of the material (for example, a hydroxyl group, a hydroxyl group, a trihalogenosilyl group or a trialkoxysilyl group of a fluorinated silane compound) is hydrolyzed by water to form a trihydroxyl group. Hydrogen bond or dehydration-condensation with a carboxyl group or the like to form a chemical bond and exhibit a strong adsorption action. In the present invention, a method of treating a building material with a water / oil repellent comprising a fluorine-containing silane compound is performed by applying a solution of the fluorine-containing silane compound to the surface of the material or by immersing the material in the solution and then drying. . [Effects of the Invention] Architectural materials surface-treated with the fluorine-containing silane compound according to the present invention have fungicidal properties,
Excellent in stain resistance, water resistance, frost damage resistance, efflorescence resistance, etc. Particularly, a fluorine-containing silane compound represented by the formula (II) having a sulfonyl group and an alkyl group in a side chain exhibits excellent properties. EXAMPLES Examples of the present invention will be described below. Example 1 100 parts by weight of cement, 300 parts by weight of sand, water as a joint material for ceramic tiles and porcelain tiles
60 parts by weight and 0.2 parts by weight of methylcellulose are kneaded and mixed in a concrete block (30
× 30 × 5cm) with a thickness of 5mm and after curing for 2 weeks in wet air, fluorinated silane compound C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₃ Si (OCH ₃ ) ₃ with ethanol It was diluted to 5%, applied and dried to obtain a test specimen. The lower 5 cm of the test specimen was immersed in water, and the occurrence of mold and moss was observed at a humidity of 95% and a room temperature of 35 ° C. As a result, no mold or moss was generated even after 3 months. Comparative Example 1 Using the cement base prepared in Example 1 as a silane compound, CH ₃ Si (OCH ₃ ) ₃ was diluted to 5% with ethanol, applied, dried, and tested under the same conditions as in Example 1 to obtain 3 months. Later mold developed. Example 2 40 parts by weight of an acrylic emulsion (EC720 manufactured by Dainippon Ink and Chemicals, Inc.), 25 parts by weight of titanium oxide, 0.2 parts by weight of sodium oleate, 0.3 parts by weight of methylcellulose, water
An emulsion paint was prepared by mixing 35 parts by weight, this paint was applied to a slate plate of 150 × 50 × 3 mm, dried, and dried to obtain a fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (CH _{2 2} ) ₃ Si (OC
H ₃ ) ₃ was diluted to 0.1% with ethanol and applied once to obtain a test sample. The surface and side surfaces of the test specimen were sealed and exposed outdoors to observe the coating surface for blistering, peeling, dirt, and the like. As a result, no change such as blistering, peeling, and dirt on the painted surface was observed even after one year. Comparative Example 2 CH ₃ CONHC ₃ H ₆ Si (OCH ₃ ) ₃ as a silane compound was diluted to 5% with ethanol, applied to the painted surface prepared in Example 2, dried, and dried under the same conditions as in Example 2. When exposed outdoors for 1 year, there was no blistering or peeling of the painted surface, but it was significantly contaminated. Example 3 (Reference Example) A fluorine-containing silane compound represented by C ₇ F ₁₅ —COO—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was diluted to 5% with nitranol on the painted surface prepared in Example 2. After coating and drying, the coated surface was exposed outdoors for one year under the same conditions as in Example 2, but no blistering or peeling of the painted surface was observed.
Slightly contaminated. Example 4 20 parts by weight of colloidal silica (Snowtex C manufactured by Nissan Chemical Industries, Ltd.), titanium oxide
10 parts by weight, 20 parts by weight of calcium carbonate, 0.2 parts by weight of sodium oleate, 0.4 parts by weight of methylcellulose, 50 parts by weight of water, 1.0 part by weight of red iron oxide were mixed to prepare a silica-based paint, and this paint was 150 × 150 Apply to a × 3 mm slate plate and after drying, fluorinated silane compound C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ Si (OCH ₃ ) ₃ with ethanol at 5%
And applied once to obtain a test specimen. The back and side surfaces of the test body were sealed, and the lower half was immersed in water to observe blistering and peeling of the painted surface. As a result, there was no change such as blistering or peeling of the coating film even after 3 months, and there was almost no stain on the boundary surface. Comparative Example 3 A silane compound was applied to the painted surface prepared in Example 4. After diluting, drying and half-immersing in water under the same conditions as in Example 4, the film peeled off near the boundary surface with water after 3 months. Example 5 An ALC plate (150 × 40 × 40 mm) was entirely immersed and impregnated in a 10% ethanol solution of a fluorine-containing silane compound C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ . After drying, the specimen was obtained. The specimen was completely immersed in water and subjected to a freeze-thaw test at -20 ° C. for 2 hours and 30 ° C. for 2 hours, two cycles a day, to observe cracks, chipping and the like of the specimen.
As a result, no change such as cracking or chipping was observed in 20 cycles, and partial chipping occurred in 50 cycles. Comparative Example 4 A liquid obtained by diluting a fluorine-containing silane compound represented by C ₈ F ₁₇ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Si (OCH ₃ ) ₃ to 10% with ethanol using the ALC plate used in Example 5 After immersion in impregnation,
After drying and conducting a test under the same conditions as in Example 5, no change such as cracking was observed in 20 cycles of freezing and thawing, but some cracks occurred in 40 cycles, and fracture occurred in 50 cycles. Comparative Example 5 The ALC plate used in Example 5 was completely immersed in a 10% ethanol solution of the silane compound C ₃ H ₇ Si (OCH ₃ ) ₃ , and the same test as in Example 5 was performed. Chipped and destroyed in 30 cycles. Example 6 Fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ S was placed on a slate plate (300 × 300 × 5 mm).
A 10% ethanol solution of i (OCl) ₃ was applied once, dried, and subjected to a water permeability test according to JISA6910. As a result, even after 24 hours, the water absorption was 0 and did not change. Comparative Example 6 The same test as in Example 6 was performed on the same slate plate as that used in Example 6 without performing the treatment with the fluorine-containing silane compound.
Crossed. Example 7 100 parts by weight of cement, 200 parts by weight of sand, and 40 parts by weight of water were kneaded to prepare a cement molded body of 200 × 100 × 10 mm, which was cured at room temperature for one day, and then a fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (
A 5% ethanol solution of CH ₃ ) (CH ₂ ) ₃ Si (OCH ₃ ) ₃ is applied once, dried, sealed on the back side, and observed at the temperature of 5 ° C. and 95% humidity for the self-phenomena on the surface. As a result, it was not observed after one month. Comparative Example 7 The same test as in Example 7 was performed on the cement molded article prepared in Example 7 without performing treatment with the fluorine-containing silane compound. As a result, the surface became white one week later, and a efflorescence phenomenon was observed.

Claims (1)

[Claims] 1. A cement-based joint material, an ALC board, a slate board, a calcium silicate board, a cement-based molded product, a cement mortar, or a building material that is a concrete base, and has a general formula R _f (CH ₂ ) _n Y (CH ₂ ) _m SiX ₃ (I) wherein R _f is a C _1-20 perfluoroalkyl group, n and m are integers of 0 to 3, Y is —SO ₂ NR— (R is H or an alkyl group of C _1-8 ) ), X is a water / oil repellent treated building material treated with a water / oil repellent comprising a fluorine-containing silane compound represented by Cl, Br, OCH ₃ or OC ₂ H ₅ ].