JP2621427B2 - Water- and oil-repellent building materials - 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 damage 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-based joint material, an ALC plate, a slate plate, a calcium silicate plate, a slate plate, a cement-based molded product, a cement mortar, a concrete base, and a paint applied to these.

[Conventional technology and problems]

Generally, architectural base materials, for example, ALC board, cement mortar surface, concrete surface, slate surface, and silica plate have a high water absorption rate, and tend to be stained and stained by water absorption. Especially ALC
Plates, slate plates, etc., are often coated for design or substrate protection, because their strength is reduced by water absorption, and are rarely used in final coating. 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]

All of the above-mentioned causes of deterioration of building materials are mediated by water, and in many cases, deterioration occurs via 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 problem]

The present invention has the general formula _{R f (CH 2) n Y} (CH 2) m SiX 3 (I) [ perfluoroalkyl group wherein R _f is _{C 1 to 20,} n and m
Is an integer of 0 to 3, Y is _{-CH 2 -, - CH 2 O} -, - NR -, - C
O ₂ —, —CONR—, —S—, —SO ₃ —, SO ₂ NR— (R is H or a C _1-8 alkyl group), X is Cl, Br, OCH ₃ , OC ₂ H
₅ ] A water- and oil-repellent-treated building material treated with a water- and oil-repellent agent comprising a fluorine-containing silane compound represented by the following formula:

The building materials targeted in the present invention include many building materials such as cement joint fillers, ALC boards, slate boards, calcium silicate boards, cement 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 ₈ F ₁₇ SO ₂ NR (CH ₂ ) ₃ SiX ₃ (II) ( Where R
The alkyl group of H or _{C 1 to 5,} X is Cl, Br, 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 diluted with a solvent and applied at a dilution concentration of 0.01 to 20% by weight, preferably 0.1 to 10% by weight. Even when the concentration of the fluorine-containing silane coupling agent is 0.01% by weight or less, a sufficient water repellency and oil repellency effect can be obtained by performing recoating several times. If the content is more than 20% by weight, uneven coating may occur,
Requires a long time to dry. 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 (for example, a hydroxyl group, a hydroxyl group, or the like) existing in the vicinity of the surface of the material by the trihalogenosyl group or trialkoxysilyl group of the fluorine-containing silane compound being hydrolyzed by water to form a trihydroxyl group Hydrogen bonding or dehydration condensation with a carboxyl group or the like to form a chemical bond and exhibit strong adsorption.

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. .

〔The invention's effect〕

The architectural material surface-treated with the fluorine-containing silane compound according to the present invention is mildew-resistant, stain-resistant, water-resistant, frost-resistant,
Excellent whitening resistance. 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.

〔Example〕

 Hereinafter, examples of the present invention will be described.

Example 1 Cement 100 was used as a joint material for ceramic tiles and porcelain tiles.
Parts by weight, sand 300 parts by weight, water 60 parts by weight, methylcellulose
0.2 parts by weight are kneaded, and concrete block (30 × 30
× 5 cm) with a thickness of 5 mm, and after curing for 2 weeks in wet air, the fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₃ Si (OC
H _{3) 3} and is applied by diluting to 5% with ethanol dried to obtain a test body. Immerse 5 cm under the test piece in water and humidify 95
%, Mold and moss were observed at room temperature of 35 ° C. As a result, no mold or moss was generated even after 3 months.

Comparative Example 1 CH ₃ Si (OCH ₃ ) ₃ was diluted to 5% with ethanol using the cement substrate prepared in Example 1 as a silane compound, and dried, and then tested under the same conditions as in Example 1 for 3 months. Later mold developed.

Example 2 Acrylic emulsion (manufactured by Dainippon Ink and Chemicals, Inc.)
EC720) 40 parts by weight, titanium oxide 25 parts by weight, sodium oleate 0.2 parts by weight, methylcellulose 0.3 parts by weight, water 35
The emulsion-based paint was prepared by mixing parts by weight, and this paint was applied to a 150 × 50 × 3 mm slate plate, dried, and dried to obtain a fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₃ Si (OCH 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 C was used as a silane compound on the painted surface prepared in Example 2.
ONHC ₃ H ₆ Si (OCH ₃ ) ₃ was diluted to 5% with ethanol, applied, dried, and exposed outdoors for one year under the same conditions as in Example 2. When the painted surface was blistered, peeled, etc. It was not, but heavily contaminated.

Example 3 C ₇ F ₁₅ -COO-CH ₂ CH ₂ CH ₂ S was applied to the painted surface prepared in Example 2.
The fluorine-containing silane compound represented by i (OCH ₃ ) ₃ was diluted to 5% with ethanol, applied, dried, and exposed outdoors for one year under the same conditions as in Example 2. Although not seen, it was only slightly contaminated.

Example 4 20 parts by weight of colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.), 10 parts by weight of titanium oxide, and 20 parts by weight of calcium carbonate
Parts by weight, 0.2 parts by weight of sodium oleate, 0.4 parts by weight of methylcellulose, 50 parts by weight of water, and 1.0 part by weight of red iron oxide were mixed to prepare a silica-based paint, and this paint was 150 × 150 ×
Was applied to 3mm slate system, after drying the fluorine-containing silane compound _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2) 3 Si (OCH 3) 3 Ethanol 5% once diluted coating To make a test body. 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. Was diluted to 5% with ethanol, dried and immersed halfway in water under the same conditions as in Example 4, and peeled off near the boundary surface with water three months later.

Example 5 An ALC plate (150 × 40 × 40 mm) was coated with a fluorine-containing silane compound C ₈ F
_The entire surface was immersed in a 10% ethanol solution of ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , impregnated, and dried to obtain a test specimen. 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, it breaks in 20 cycles,
No change such as chipping was observed, and partial chipping occurred in 50 cycles.

Comparative Example 4 The ALC plate used in Example 5 was replaced with C ₈ F ₁₇ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
A fluorine-containing silane compound represented by Si (OCH ₃ ) ₃ was immersed in a solution diluted to 10% with ethanol, impregnated, dried, and tested under the same conditions as in Example 5.
No change such as cracking was observed in 20 cycles, but 40
Some cracks occurred in the cycle, and fractured in 50 cycles.

Comparative Example 5 The ALC plate used in Example 5 was replaced with a silane compound C ₃ H ₇ Si (OC
H ₃₎ fully immersed in ₃ of 10% ethanol solution, Example 5
When the same test was performed, chipping occurred in 20 cycles of freezing and thawing, and fracture occurred in 30 cycles.

Example 6 A 10% ethanol solution of a fluorine-containing silane compound C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ Si (OCl) ₃ was applied once to a slate plate (300 × 300 × 5 mm). After drying, a water permeability test was performed 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, and the water absorption exceeded 30 cc in 1 hour.

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 (CH ₃ )
A 5% ethanol solution of (CH ₂ ) ₃ Si (OCH ₃ ) ₃ was applied once, dried and sealed on the back side surface, and the surface was observed for the self-phenomena at 5 ° C. and 95% humidity. It has not been seen for more than a month.

Comparative Example 7 The same test as in Example 7 was carried out on the cement molded body prepared in Example 7 without treatment with the fluorine-containing silane compound. As a result, the surface became white one week later, and a efflorescence phenomenon was observed.

Claims (4)

(57) [Claims] 1. A compound of 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 are integers of 0 to 3, Y is —CH ₂ —, —CH ₂ O—, —NR
_{-, - CO 2 -, -} CONR -, - S -, - SO 3 -, SO 2 NR-
(R is H or a C _1-8 alkyl group), X is Cl, Br,
OCH ₃ , OC ₂ H ₅ ], a water- and oil-repellent treated building material treated with a water- and oil-repellent agent comprising a fluorinated silane compound. 2. The water- and oil-repellent building material according to claim 1, wherein the building material is a cement joint material, an ALC plate, a slate plate, a calcium silicate plate, a cement molding, a cement mortar, or a concrete base. . 3. The water- and oil-repellent-treated building material according to claim 1, wherein the water- and oil-repellent is attached in an amount of 0.001 to 20% by weight. 4. 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 are integers of 0 to 3, Y is —CH ₂ —, —CH ₂ O—, —NR
_{-, - CO 2 -, -} CONR -, - S -, - SO 3 -, SO 2 NR-
(R is H or a C _1-8 alkyl group), X is Cl, Br,
A paint for imparting water and oil repellency to building materials, characterized by containing a fluorine-containing silane compound represented by OCH ₃ or OC ₂ H ₅ ].