JPH06100853A - Surface treatment agent for building material - Google Patents

Abstract

PURPOSE:To obtain a surface treatment agent having excellent abrasion resistance and curing rate and also excellent water repellency, oil repellency and stainproofness by mixing a specified organosiloxane compound with a specified fluorine compound, a metal alkoxide and a cyclic organosiloxane. CONSTITUTION:This agent is obtained by mixing 100 pts.wt. organosiloxane of formula I (wherein R<1> is 1-5C alkyl; and (n) is 0-5) with 0.5-50 pts.wt. fluoroalkyl-trialkoxysilane monomer of formula II (wherein R<2> is fluoroalkyl; and R<3> is 1-5C alkyl) and/or its oligomer, 1-50 pts.wt. metal alkoxide of formula III (wherein Me is Ti, Zr, Al or B; and R4 is 1-5C alkyl) and 100-2000 pts.wt. cyclic organosiloxane of formula IV (wherein R<5> and R<6> are each H or 1-3C alkyl provided that at least one of them is alkyl; and (n) is 3-7). This agent is applied to the surface of a building material to form a coating film excellent in water repellency, oil repellency and stainproofness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to various building materials such as constructions such as wood, stones and concrete, constructions or construction materials to form a coating film on the surface thereof, and The present invention relates to a surface treatment agent for building materials, which can impart excellent water repellency, oil repellency and antifouling property to the surface.

[0002]

2. Description of the Related Art Conventionally, many building materials have a large water absorption property because their surfaces are porous, and cracks, neutralization phenomena, dirt, etc. due to the intrusion of water such as rainwater and sewage, and the appearance It not only damages the product, but also reduces its durability. Therefore, for the purpose of preventing such a problem, a method of applying a silicon-based water repellent to the surface of a building material to prevent water absorption is generally used. And, these silicon-based water repellents are generally called so-called coating / penetration type waterproofing agents, and are mainly classified into silicone aqueous solution type siliconate type, silicone solution type silicone resin type, and silane type. .

However, among these silicon-based water repellents, the silicone-based ones are strongly alkaline and the substrate is not sufficiently dried.
If it rains within 1 to 2 days after application, it will cause acne.
There are many problems in handling and use, such as the risk of corroding mounting brackets for boards, etc.Also, even after the film is formed, the siloxane chains are gradually cut by the alkali generated from concrete etc. There was a problem that it was lost and its durability was poor. Similar to silicone-based ones, silicone resin-based ones are weak against alkali and cannot be expected to have a long-term water-repellent effect.Moreover, they should not be applied to wet surfaces or within a few hours after application. There was a problem in that white sinter might occur when it came into contact with.

However, silane-based compounds have the general formula RS
i (OR) ₃ [wherein R represents an alkyl group] is a main component of a silane compound having a structural formula, and an alkyl group directly bonded to a silicon atom enhances the water-repellent effect. Has excellent permeability and alkali resistance,
At present, it is the mainstream as a coating / penetration type waterproofing agent. As such a compound, for example, one described in Japanese Examined Patent Publication No. 54-9,639 is known, in which an alkyl silicate is used as a water repellent and a metal carboxylate is used as a hydrolysis catalyst. ing.

However, even with such a silane-based material, the water-repellent effect is not always sufficient,
Therefore, some proposals have been made to improve this point.
For example, in JP-A-3-265,581,
A surface treatment agent containing an organosiloxane compound containing a perfluoroalkyl group bonded to a silicon atom as a main component is disclosed. Although this one has improved its water repellency due to the effect of the perfluoroalkyl group,
On the other hand, since a substituent is introduced into the hydrolyzable silicon compound as the main chain, the number of siloxane bonds (Si-O-bonds) generated by hydrolysis is 3 or less, and the number of siloxane bonds is There is also a problem in use that the dependent bonding force is reduced by that much, there is a problem in terms of abrasion resistance, and that it takes a considerable time to form a strong film.

[0006]

Therefore, the present inventors have conducted extensive studies as to a new surface treating agent for building materials, which has solved various problems in the conventional silane-based water repellent, and as a result, A straight-chain or branched organosiloxane compound as a main component, to which a fluorine-containing alkyltrialkoxysilane monomer and / or oligomer thereof, a metal alkoxide, and a cyclic organosiloxane are blended to simply yield excellent properties. The present invention has been completed by finding that a surface treating agent for building materials having not only water repellency, oil repellency and antifouling property, but also excellent abrasion resistance and curing rate can be obtained. Therefore, the object of the present invention is to solve various problems in conventional silane-based water repellents, and not only have excellent water repellency, oil repellency and antifouling property, but also excellent abrasion resistance. Another object of the present invention is to provide a surface treatment agent for building materials having a curing rate.

[0007]

That is, according to the present invention, the following general formula (1) R ¹ ₃ SiO (R ¹ ₂ SiO) _n SiR ¹ ₃ (1) (wherein R ¹ has ¹ carbon atom) To 5 alkyl groups, and n represents an integer of 0 to 5), and an organosiloxane compound represented by the following general formula (2) R ² Si (OR ³ ) ₃ (2) (provided that In the formula, R ² represents an alkyl group having at least one fluorine atom, and R ³ represents an alkyl group having 1 to 5 carbon atoms) and a fluorine-containing alkyltrialkoxysilane monomer and / or The oligomer and the following general formula (3) Me (OR ⁴ ) ₄ (3) (wherein, Me represents Ti, Zr, Al or B,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms) and a metal alkoxide represented by the following general formula (4)

[Chemical 2] (However, in the formula, R ⁵ and R ⁶ are hydrogen atoms or 1 to 3 carbon atoms.
Of the above-mentioned alkyl groups, at least one of which is the above-mentioned alkyl group, and n represents an integer of 3 to 7), and a surface treatment agent for a building material containing a cyclic organosiloxane.

In the present invention, when the organosiloxane compound represented by the above general formula (1) is applied to the surface of a material to be treated, which is a building material, the organosiloxane compound reacts with moisture on the surface of the material to be treated or in the air. When contacted and hydrolyzed, a strong siloxane bond network structure is generated, thereby protecting the surface of the agent to be treated. Since the organosiloxane compound used in the present invention has a tetravalent hydrolyzable group, its bond is much stronger than that of a conventional silane compound having a trivalent hydrolyzable group. Excellent wear resistance. In this organosiloxane compound, as the alkyl group R ¹ having 1 to 5 carbon atoms in the general formula (1), specifically, a methyl group, an ethyl group, an n-propyl group,
iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, n-hexyl group, iso
-Hexyl group, sec-hexyl group and the like are mentioned, and those having 1 to 4 carbon atoms are preferable from the viewpoint of having appropriate hydrolyzability. Further, in this organosiloxane compound, the repeating number n is usually 0 to 5, preferably 2 to 3, and it is used as a siloxane oligomer. Here, in the case of a monomer, its boiling point is low, and a part or most of it may evaporate at the time of application, and in the case of n = 5 or more, its viscosity becomes too high, which is a building material. It becomes difficult for the treatment material to permeate all the pores.
The organosiloxane compounds represented by the general formula (1) include linear organosiloxanes, branched organosiloxanes and cyclic organosiloxanes, and any of them can be used. It is also possible to use a mixture of two or more kinds of linear organosiloxane, branched organosiloxane, and cyclic organosiloxane.

The fluorine-containing alkyltrialkoxysilane monomer represented by the general formula (2) and / or the oligomer thereof is used as a water repellent, and contains at least one fluorine atom in the formula. An alkyl group R ² having
As, for _{example, CF 3 CH 2 CH 2 -} , C 2 F
_{5 CH 2 CH 2 -, C} 3 F 7 CH 2 CH 2 -, C 4 F
_{9 CH 2 CH 2 -, C} 5 F 11 CH 2 CH 2 -, C 6 F
₁₃ CH ₂ CH ₂ —, C ₈ F ₁₇ CH ₂ CH ₂ —, CF _{3
CH 2 OOCCH 2 CH 2 -,} C 2 F 5 CH 2 OOCC
_{H 2 CH 2 -, C 4} F 9 CH 2 CH 2 OOCCH 2 CH
_{2 -, C 6 F 13 CH} 2 CH 2 OOCCH 2 CH 2 -,
(CF ₃ ) ₂ CFCF ₂ CH ₂ CH ₂ OOCCH ₂ CH
_2- , (CF ₃ ) ₂ CHOOCCH ₂ CH ₂ — are exemplified, and from the viewpoint of water repellency, F is preferably 5 or more, and an alkyl group R ³ having 1 to 5 carbon atoms.
Examples of the alkyl group include those similar to the alkyl group R ¹ in the general formula (1), and those having 1 to 2 carbon atoms are preferable from the viewpoint of imparting appropriate hydrolyzability. Any of these water repellents may be used alone, or may be used as a mixture of two or more kinds. The addition amount is not particularly limited, but if it is too small, the water-repellent effect is weak, and if it is too large, the film strength becomes weak, so 100 parts by weight of the organosiloxane compound represented by the general formula (1) is used. In contrast, usually 0.5 to 50 parts by weight,
It is preferably in the range of 5 to 20 parts by weight.

Further, the metal alkoxide represented by the general formula (3) is used for the purpose of promoting hydrolysis, and the metal atom Me in the formula is Ti or Z.
r, Al or B is preferable, Ti or Zr having 4 hydrolyzable groups and strong bond strength is preferable, and the alkyl group R ⁴ having 1 to 5 carbon atoms is represented by the above general formula. Examples of the same as the alkyl group R ¹ in (1) are exemplified,
From the viewpoint of imparting appropriate hydrolyzability, it preferably has 1 to 4 carbon atoms. Specific examples of the metal alkoxide include Ti (OCH ₃ ) ₄ and Ti.
(OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC
₄ H ₉ ) ₄ , Ti (OC ₅ H ₁₁ ) ₄ , Zr (OCH ₃ )
₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Z
r (O ₄ H ₉ ) ₄ , Zr (OC ₅ H ₁₁ ) ₄ , Al (OC
₃ H ₅ ) ₃ , B (OCH ₃ ) _{3 and the} like. Any of these metal alkoxides may be used alone, or two or more of them may be mixed and used. The amount of the metal alkoxide added is not particularly limited, but if it is too small, the effect is small, and if it is too large, the hydrolysis rate of the coating solution is too fast and the inside of the pores of the material to be treated, which is a building material, is sufficiently high. The water-repellent effect is not sufficiently exhibited before it penetrates to 100 parts by weight. Therefore, it is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the organosiloxane compound represented by the general formula (1). , And more preferably 5 to 40 parts by weight.

The cyclic organosiloxane represented by the general formula (4) is used as a solvent for dissolving and uniformly mixing the compounds represented by the general formulas (1) to (3), and particularly, The surface tension of the entire surface treatment agent according to the present invention is lowered, and it exerts the action of permeating deep into the pores of the material to be treated, which is a building material. Therefore, the cyclic organosiloxane used here is It is preferable that the surface tension is as low as possible. Here, the substituents R ⁵ and R ⁶ in the general formula (4) are each a hydrogen atom or a carbon number 1
~ 3 alkyl groups, at least one of which is an alkyl group, and n represents an integer of 3 to 7,
When the substituents R ⁵ and R ⁶ are both alkyl groups having 1 to 5 carbon atoms and n is an integer of 3 to 7, cyclic organoorganosiloxane compounds represented by the general formula (1) are used. Corresponds to siloxane. Therefore, in such a case, the cyclic organosiloxane functions as the organosiloxane compound represented by the general formula (1) or the cyclic organosiloxane represented by the general formula (4). As preferable examples of the cyclic organosiloxane represented by the general formula (4), specifically,

[Chemical 3] Etc. These cyclic organosiloxanes are
Only one of them can be used alone, or a mixture of two or more can be used. The amount of the cyclic organosiloxane used is usually 100 to 2,000 parts by weight, preferably 200 to 1,000 parts by weight, based on 100 parts by weight of the organosiloxane of the general formula (1).

The surface treating agent for building materials of the present invention is prepared as a coating solution of a uniform solution by mixing the compounds of the above-mentioned general formulas (1) to (4) in a predetermined ratio. To adjust viscosity, surface tension, volatility, etc., if necessary,
Solvents such as alcohols, ketones and glycols, surfactants and the like may be added. The surface treatment agent thus prepared is applied as a coating liquid to the surface of a material to be treated, which is a building material, by a usual coating method such as brush coating, roller coating, or spray coating.

[0013]

The surface treatment agent for building materials of the present invention has four hydrolyzable groups capable of forming a strong network structure when it is applied to the surface of a material to be treated which is a building material and hydrolyzed there. A fluorine-containing alkyltrialkoxysilane monomer having an organosiloxane compound as a main component and having a fluorine substituent excellent in water repellency and / or an oligomer thereof is bound to the inside of the network structure, and at this time, a metal alkoxide is formed. Acts as a catalyst to contribute to the formation of a network structure. The strong siloxane network structure thus formed not only has excellent water repellency, oil repellency and antifouling property, but also acts as a building material due to the action of the cyclic organosiloxane added as a solvent. It penetrates even into the inside of small pores, which at the same time exhibits excellent wear resistance and curing rate.

[0014]

EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples.

Example 1 3 of methyl silicate as an organosiloxane compound
To 4-mer polysiloxane oligomer around the [Tama Chemical Co., Ltd.: MS-51] using 6 parts by weight, CF ₃ (CF ₂₎ repellent as liquid medication to ₇ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ [Toshiba Silicone Co., Ltd .: TSL-8
233] 0.6 part by weight and Ti as a metal alkoxide
2.6 parts by weight of (OC ₄ H ₉ ) ₄ and 50 parts by weight of octamethylcyclotetrasiloxane (KF-994 manufactured by Shin-Etsu Chemical Co., Ltd.) as a cyclic polysiloxane are added respectively, and the remainder is used as isopropyl alcohol. 1
The amount was adjusted to 00 parts by weight, and well stirred using a magnetic stirrer to prepare a uniform solution surface treating agent.

The water repellency of the obtained surface treating agent was evaluated as follows. First, a marble of 5 cm × 5 cm was selected as a material to be treated, the surface was thoroughly wiped, the surface treatment agent was applied with a brush, then left at room temperature for 24 hours, and the surface was wiped off well with a dry cloth. Next, about 0.03 ml of the water-based red ink was dripped on the marble at a total of 16 places at intervals of about 1 cm, and allowed to stand at room temperature for 24 hours, and then wiped off. At this time, the size of the red stain adsorbed on the surface of the marble was measured, and the water repellency of the coating solution was examined and evaluated. Here, the case where the water-based red ink has not soaked at all is marked with ⊚, and the spot with a diameter of about 1 mm or less is 2
○ when it is within the place, 5 stains with a diameter of about 1 mm or less
□ when it is within the place, × when there is a stain with a diameter of about 1 to 5 mm, × when there is a stain with a diameter of about 5 mm or more ×
And evaluated in 5 steps. The results are shown in Table 1.

Example 2 4 of ethyl silicate as an organosiloxane compound
A surface-treating agent was prepared in the same manner as in Example 1 except that a polysiloxane oligomer mainly consisting of a pentamer (ES-40 manufactured by Tama Chemical Industry Co., Ltd.) was used.
Water repellency was evaluated in the same manner as in. The results are shown in Table 1.

Example 3 A surface treating agent was prepared in the same manner as in Example 1 except that Zr (OC ₄ H ₉ ) ₄ was used as the metal alkoxide, and water repellency was evaluated in the same manner as in Example 1. went. The results are shown in Table 1.

Example 4 4 of ethyl silicate as an organosiloxane compound
.About.5 mer mainly polysiloxane oligomer [manufactured by Tama Chemical Industry Co., Ltd .: ES-40] was used, and Zr (OC ₄ H ₉ ) ₄ was used as the metal alkoxide. Prepare a surface treatment agent in the same manner as in 1,
Water repellency was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

Comparative Example 1 A surface treating agent was prepared in the same manner as in Example 1 except that methyltrimethoxysilane was used as a water repellent.
Water repellency was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

Comparative Example 2 Example 1 above except that no metal alkoxide was used.
A surface treating agent was prepared in the same manner as in Example 1 and the water repellency was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 A surface treating agent was prepared in the same manner as in Example 1 except that kerosene was used as a solvent, and water repellency was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0023]

[Table 1]

[0024]

The surface treatment agent for building materials of the present invention not only has excellent water repellency, oil repellency and antifouling property, but also has excellent abrasion resistance and curing rate. , Practically very useful.

Claims (2)

[Claims] 1. The following general formula (1) R ¹ ₃ SiO (R ¹ ₂ SiO) _n SiR ¹ ₃ (1) (wherein, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and n is Represented by the following general formula (2) R ² Si (OR ³ ) ₃ (2) (wherein R ² is at least one). A fluorine-containing alkyltrialkoxysilane monomer and / or oligomer represented by an alkyl group having a fluorine atom, and R ³ represents an alkyl group having 1 to 5 carbon atoms; and the following general formula (3) Me (OR ⁴ ) ₄ (3) (wherein, Me represents Ti, Zr, Al or B,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms) and a metal alkoxide represented by the following general formula (4): (However, in the formula, R ⁵ and R ⁶ are hydrogen atoms or 1 to 3 carbon atoms.
And a cyclic organosiloxane represented by the formula (3), at least one of which is at least the above alkyl group, and n represents an integer of 3 to 7). . 2. The fluorine-containing alkyltrialkoxysilane monomer and / or oligomer thereof represented by the general formula (2) is added to 100 parts by weight of the organosiloxane compound represented by the general formula (1). 0.5 to 50 parts by weight, 1 to 50 parts by weight of the metal alkoxide represented by the general formula (3), and 100 to 2,000 parts by weight of the cyclic organosiloxane represented by the general formula (4). The surface treating agent for a building material according to claim 1, wherein the surface treating agent is contained respectively.