JPH07173412A - Water-and oil-repellent transparent coating material - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. which retains an improved water- and oil-repellency for long period of time by compounding a specific metal alkoxide and a fluorinated silane compd. into a solvent. CONSTITUTION:This compsn. is obtd. by compounding 0.1-30wt.% metal alkoxide of the formula, M(OC2H5)n or M(isoOC3H7)n (where M is Si, Al, or Zr; and n is 3 or 4), 0.001-30wt.% fluorinated silane compd. of the formula, R1(CH2)nY (CH2)mSiX (wherein R1 is 7-8C perfluoroalkyl; n and m are each 0-3; Y is CH2, CH2O, NR, CO2, CONR, S, SO3, or SO2NR; R is H or 1-3C alkyl; and X is Cl, Br, OCH3, or OC2H5), and if necessary 0.1-10wt.% cross-linking accelerator and 0.1-5wt.% thickener into an alcohol as the solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to, for example, bathroom materials such as bathtubs and mirrors, textile materials such as work clothes and umbrellas, textile products such as textiles, leather products such as shoes, window glass for vehicles and construction, Further, the present invention relates to a water- and oil-repellent transparent paint which exhibits excellent water- and oil-repellency for a long period of time when applied as a coating film to various materials such as metals, plastics and cement, and its products.

[0002]

2. Description of the Related Art Heretofore, various types of paints have been known which form a coating film on the surface of the above-mentioned various materials to exert a water and oil repellency. Among them, alcohol has a water and oil repellency. A paint prepared by mixing a solution containing a fluorine-containing silane compound in a proportion of 0.1 to 30% by weight with a resin is widely used.

[0003]

However, in the above conventional coating composition, when a coating film is formed, a fluorine-containing silane compound exhibiting a water and oil repellency effect is dispersed in the resin, and a part of the coating film surface is formed. Since only the fluorine-containing silane compound of the above appears, the water- and oil-repellent action cannot be fully exerted, and when exposed to water for a long time, the fluorine-containing silane compound on the surface elutes, and the outermost surface is only resin. Therefore, there is a problem that the water and oil repellency is lowered.

[0004]

Therefore, the present inventors have
From the above viewpoint, the water and oil repellent effect is produced over a long period of time.
Research was conducted on paints capable of forming volatile coating films
As a result, the solvent is preferably alcohol, both of which are total
0.1 to 30% by weight of the general formula M (OC₂H_Five)_nRepresented by
Group alkoxide (where M is Si, Ti, Al, or Zr
And n represents 3 to 4) Desirably silicon tetraeth
Xide, titanium tetraethoxide, aluminum
Riethoxide, and zirconium tetraethoxide,
And the general formula M (isoOC₃H₇)_nThe metal alkoxy represented by
(Where M represents any one of Si, Ti, Al, and Zr, and n is 3 to
4), preferably silicon tetraethoxide isop
Ropoxide, titanium isopropoxide, aluminum
Muisopropoxide, and zirconium isopropoxide
At least one of SID and 0.001 to 30% by weight
General formula Rl (CH₂)_nY (CH₂)_mSiX₃{In the formula, Rl is C7-C8 perfume
Oroalkyl group, n and m are integers from 0 to 3, Y is CH₂, CH
₂O, NR, CO₂, CONR, S, SO₃, SO₂NR (R is H or C1 to C3
Alkyl group), X is Cl, Br, OCH₃, OC₂H_Five} Represents
Fluorine-containing silane compound₈F₁₇SO₂N (CH₃) (C
H₂)₃Si (OCH₃)₃, C₇F₁₅CO₂CH₂CH₂CH₂Si (OCH ₃)₃, Or C
₇F₁₅CONHCH₂CH₂CH₂Si (OCH₃)₃The paint is a mixture of
Used to form a transparent coating film with the same adhesion as before.
And, this transparent coating has an excellent water and oil repellency.
I got the research result that it will be effective for a long time.
It

The present invention was made on the basis of the above-mentioned research results, and the ratio of the solvent to the solvent is the same as that of the whole solvent.
0.1 to 30% by weight, preferably 0.3 to 20% by weight of the general formula M (OC
₂ H ₅ ) n and M (isoOC ₃ H ₇ ) _n (where M is Si, Ti, Al, Zr
And at least one of the metal alkoxides represented by (n represents 3 to 4) and 0.001 to 30.
It is characterized by a water- and oil-repellent transparent coating composition obtained by dissolving a fluorine-containing silane compound in an amount of 0.01% by weight, preferably 0.01 to 20% by weight.

In the water- and oil-repellent transparent coating material of the present invention, the proportion of the metal alkoxide is set to 0.1 to 30% by weight because it is difficult to form a film having good adhesion when the proportion is less than 0.1%. On the other hand, when the proportion exceeds 30% by weight, the viscosity rapidly increases and the film forming operation becomes difficult, so the proportion was set to 0.1 to 30% by weight.

Further, the ratio of the fluorine-containing silane compound is set to 0.001 to 30% by weight. If the ratio is less than 0.001% by weight, the desired excellent water and oil repellency cannot be obtained. If the proportion exceeds 30% by weight, it will be difficult to form a film with good adhesion.
Determined to be% by weight.

Further, in the water-repellent and oil-repellent transparent coating material of the present invention, 0.1 to 10% by weight of a crosslinking accelerator such as hydrochloric acid or nitric acid may be added as an optional component in order to accelerate the hydrolysis. For the purpose of strengthening, a thickener such as acrylic resin or vinyl acetate resin may be contained in a proportion of 0.1 to 5% by weight.

[0009]

EXAMPLES Next, the water and oil repellency effect of the present invention will be specifically described by way of examples. As the metal alkoxide, silicon tetraethoxide (hereinafter referred to as metal alkoxide A), aluminum triisopropoxide (hereinafter referred to as B), zirconium tetraisopropoxide (hereinafter referred to as C), titanium tetraisopropoxide (hereinafter referred to as the same). D) is prepared and C _{8 is} used as a fluorine-containing silane compound.
_{F 17 SO 2 N (CH 3} ) (CH 2) 3 Si (OCH 3) 3 ( hereinafter referred to as fluorine-containing silane compound _{a), C 7 F 15 CO} 2 CH 2 CH 2 CH 2 Si (OCH 3) 3 ( Hereinafter referred to as b), C ₇ F ₁₅ CONHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (hereinafter referred to as c)
Is prepared), and these raw materials are dissolved in an alcohol solution as a solvent at a ratio shown in Table 1 to prepare a water- and oil-repellent transparent paint of the present invention (hereinafter referred to as the present paint)
Adjusted ~ 9. For comparison purposes, conventional water- and oil-repellent transparent coatings (hereinafter referred to as conventional coatings) 1 to 5 prepared by dispersing a fluorine-containing silane compound in an alcohol and a resin at a ratio shown in Table 1 were prepared. With respect to the coating materials 1 to 9 of the present invention and the conventional coating materials 1 to 5, a durability test of the water and oil repellent effect was conducted under the following conditions.

The water- and oil-repellent effect persistence test was carried out by coating the paints as shown in Table 1.
Was coated on the surface of the treated substrate shown in (1) and dried at 100 ° C. for 1 hour to form a transparent coating film having a film thickness of 10 μm, and immersed in running water for 1 day. Before and after soaking in water, 0.2 ml of water drops were placed on the surface of the treated substrate placed horizontally, and the angle formed by the water droplets with the surface of the treated substrate was measured to obtain the surface contact angle with water. Further, 0.2 ml of water droplets are placed on the surface of the treated base material placed horizontally, and the other end is lifted with one end of the treated base material as a fulcrum, at the time when this water droplet rolls off from the plate surface, the critical rolling angle of the water droplet. Was also measured. The results are shown in Table 1.
It was shown to.

[0011]

[Table 1]

In addition, on the surface of the treated substrate placed horizontally,
0.2 ml of silicone oil was placed, and the angle formed by the droplet with the surface of the treated substrate was measured and used as the surface contact angle to the oil. Further, 0.2 ml of silicone oil is placed on the surface of the glass plate placed horizontally, and one end of the treated substrate is used as a fulcrum to lift the other end, and the critical point of the droplet at the time when the droplet rolls off the plate surface. The rolling angle was also measured. The results are shown in Table 2.

[0013]

[Table 2]

[0014]

From the results shown in Tables 1 and 2, the coating materials 1 to 9 of the present invention are transparent and exhibit excellent water and oil repellency, and their excellent water and oil repellency is almost deteriorated. It is possible to form a coating film that can be maintained over a long period of time, whereas the conventional paints 1 to 5 can only form a coating film whose water / oil repellency decreases in a relatively short time. Is clear.

Claims (4)

[Claims] 1. A solvent in a proportion of 0.1 to 3 in total.
0% by weight of the general formula M (OC ₂ H ₅ ) _n and M (isoOC ₃ H ₇ ) _n (however
M represents Si, Ti, Al, or Zr, and n represents 3 to 4), and at least one of the metal alkoxides represented by the following:
Also 0.001 wt% of the general formula _{Rl (CH 2) n Y (} CH 2) m SiX
₃ {wherein Rl is a C7-C8 perfluoroalkyl group, n and
m is an integer of from 0 to 3, Y is _{CH 2, CH 2 O, NR} , CO 2, CONR, S, S
O ₃ , SO ₂ NR (R is H or a C1-C3 alkyl group), X is C
A water- and oil-repellent transparent coating material containing at least one of the fluorine-containing silane compounds represented by l, Br, OCH ₃ , OC ₂ H ₅ }. 2. The metal alkoxide has the general formula M (OC ₂ H ₅ ).
_In the case of _n , silicon tetraethoxide, titanium tetraethoxide, aluminum triethoxide, and zirconium tetraethoxide, in the case of general formula M (isoOC ₃ H ₇ ) _n , silicon tetraethoxide isopropoxide, titanium isopropoxide 2. The water- and oil-repellent transparent coating composition according to claim 1, characterized in that the transparent coating composition comprises aluminum, aluminum isopropoxide, and zirconium isopropoxide. 3. The fluorine-containing silane compound has the chemical formula C₈F₁₇S
O₂N (CH₃) (CH₂)₃Si (OCH₃)₃, C₇F₁₅CO ₂CH₂CH₂CH₂Si (OCH₃)
₃Or C₇F₁₅CONHCH₂CH₂CH₂Si (OCH₃)₃Included foot
The above-mentioned claim 1 which is composed of an elemental silane compound.
Alternatively, the water-repellent and oil-repellent transparent paint described in 2. 4. The water- and oil-repellent transparent paint according to claim 1, wherein the solvent is alcohol.