JPH0543840A - Surface-treating agent for coated surface - Google Patents

Abstract

PURPOSE:To prepare the title agent which improves the gloss of a coated surface and enables the surface to retain its gloss and stain resistance for a long term by compounding a specific metal alkoxide with a fluorinated silane compd. CONSTITUTION:The title agent comprises a metal alkoxide of the formula (wherein M is a metal selected from those of the groups III, IV, and V, and is pref. Al, Ga, In, Ti, Zr, Si, Sn, Nb, or Ta, esp. pref. Ti, Zr, or Si; R is a 1-22C satd. or unsatd. aliph. hydrocarbon group provided that n R's may be of the same or different kind; and n is a valency of the metal) and/or a polymer thereof and a fluorinated silane compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for a coated surface, and more particularly to a surface treatment agent for a coated surface containing an alkoxide of a specific metal and / or the polymer and a fluorine-containing silane compound. ..

[0002]

2. Description of the Related Art Car wax and the like have hitherto been widely commercially available as a lustrous wax for painted surfaces. The detailed composition of these polish waxes is unknown due to the know-how of each manufacturer.
A wax (wax) component that forms a film and gives a gloss, a silicone oil component that fluidizes the wax component to impart water repellency to the film, an organic solvent or water as a dispersion medium, a surfactant, an abrasive, etc. are mixed. There is. (Encyclopedia of
Chemical Technology, Edition III Volume 18, 324-325, Kirk
-Othmer, cleaning design, Spring issue (25), 63-80, (1980), rust prevention management, June 9-14, (1985) etc.)

[0003]

Problems to be Solved by the Invention As described above, conventional surface-treating agents for coating surfaces improve the gloss by imparting wax components and silicone oil components to the coating surface, impart water repellency, and It is intended for protection, etc., but since these do not contain a component having a functional group that chemically bonds to the coated surface, the bonding force between the coated surface and the surface treatment agent is weak, and it will not melt away over time. , The sustainability of the effect was insufficient.
The present invention has been made in view of such circumstances, and the coated surface and the surface treatment agent are chemically bonded to each other to improve the gloss of the coated surface, and the gloss retention effect and the antifouling effect are maintained for a long time. It is an object of the present invention to provide a surface treatment agent for a coated surface that can be applied.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a surface treatment agent containing a specific metal alkoxide and a fluorine-containing silane compound as essential components. However, they found that they have an excellent surface treatment effect on the coated surface, and completed the present invention.
The present invention is a surface treatment agent for a coated surface, which contains the following components A and B as essential components. Component A: General formula M (OR) _n ··· (I) (In the formula, M is one selected from the group consisting of metal atoms belonging to groups III, IV and V of the periodic table, R is the same or different, saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms,
n represents a number corresponding to the valence of the metal) and / or the polymer B component: a fluorine-containing silane compound

The present invention will be described in detail below. The component A used in the present invention is represented by the general formula M (OR) _n (wherein M is one selected from the group consisting of metal atoms belonging to groups III, IV and V of the periodic table, R is the same or Different carbon number 1-22
Is a saturated or unsaturated aliphatic hydrocarbon group, n is a number corresponding to the valence of a metal), and / or the polymer. In the metal alkoxide represented by the general formula M (OR) _n , M is group III, group IV, V
Group A metal atom, preferably Al, Ga, In,
Ti, Zr, Si, Sn, Nb and Ta, particularly preferably Ti, Zr and Si. n represents the number corresponding to the valence of these metals. Further, R in the above formula is a same or different saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms, which may be linear or branched, and examples thereof include methyl and ethyl. , Propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, dodecyl, oleyl, stearyl, isostearyl groups and the like. The above M (OR) _n metal alkoxide is
Used alone or as a mixture of two or more kinds.

As the component A used in the present invention, a polymer of a metal alkoxide represented by the above general formula M (OR) _n is also used. In the present invention, the M (OR) _n metal alkoxide and the metal alkoxide polymer are M (O) _n
R) _n metal alkoxides and / or used in the form of said metal alkoxide polymers. It should be noted that at least one metal alkoxide of M (OR) _n is used. Specific examples of these are as follows.

(A) M (OR) _n independent system Al (OR) ₃ , Ga (OR) ₃ , In (OR) ₃ , T
i (OR) ₄ , Zr (OR) ₄ , Sn (OR) ₄ , Si
(OR) ₄ , Nb (OR) ₅ , Ta (OR) _5, etc., (b) Mixed system of M (OR) _n Al (OR) ₃ + Zr (OR) ₄ , Ti (OR) ₄ + S
i (OR) ₄ , Zr (OR) ₄ + Ta (OR) ₅ , Zr
(OR) ₄ + Si (OR) ₄ + Ta (OR) ₅ etc., (c) Polymer of M (OR) _n- single system Titanoxane, zirconoxane, siloxane, Ti—O
-Si skeleton-containing copolymer, Ti-O-Zr skeleton-containing copolymer, Ti-O-Zr-O-Si skeleton-containing copolymer (d) M (OR) _n polymer-mixed system (titanoxane) + (Zirconoxane), (Zirconoxane) + (Siloxane), (Zirconoxane) + (Siloxane) + (Copolymer having Zr—O—Si skeleton)
Etc. (e) Mixed system of M (OR) _n and the polymer Ti (OR) ₄ + (titanoxane), Zr (OR) ₄ +
Si (OR) ₄ + (zirconoxane) + (siloxane), Zr (OR) ₄ + Si (OR) ₄ + (zirconoxane) + (siloxane) + (copolymer having Zr—O—Si skeleton), Ti (OR ) ₄ + siloxane and the like.

The fluorine-containing silane compound used in the present invention is
In particular, those containing a perfluoroalkyl group in the molecule. For _{example, CF 3 -CH 2 CH 2 -} , (CF 3) 2 -
_{CFCH 2 -CH 2 -, CF 3} (CF 2) 3 -CH 2 CH
_{2 -, CF 3 (CF 2} ) 5 -CH 2 CH 2 -, CF 3 (C
_{F 2) 7 -CH 2 CH 2} -, CF 3 (OCF 2) n (OCF
₂ ) Fluorine-containing silane compound having a group such as _m O (CH ₂ ) _p −, and specifically, CF ₃ —CH ₂ CH ₂ —Si.
_{(OCH 3) 3, (CF} 3) 2 -CF CH 2 -CH 2
_{-Si (OCH 3) 3, CF} 3 (CF 2) 3 -CH 2 CH 2
_{-Si (OCH 3) 3, CF} 3 (CF 2) 5 -CH 2 CH 2
_{-Si (OCH 3) 3, CF} 3 (CF 2) 5 -CH 2 CH 2
_{-Si (OC 2 H 5) 3} , CF 3 (CF 2) 7 -CH 2 CH
_{2 -Si (OCH 3) 3,} CF 3 (CF 2) 7 -CH 2 CH
_{2 -Si (OC 2 H 5)} 3, CF 3 (CF 2) 11 -CH 2 C
_{H 2 -Si (OC 2 H 5} ) 3, CF 3 (CF 2) 2 -OCF
_{(CF 3) CF 2 O (} CH 2) 3 Si (OCH 3) 3, C
_{F 3 (OCF 2) 3 -} (OCF 2) 3 O (CH 2) 3 Si (O
CH ₃ ) _{3 and the} like.

The mixing ratio of the metal alkoxide of the component A of the present invention, the metal alkoxide polymer and the fluorine-containing silane compound of the component B is 90 to 5% by weight with respect to 10 to 95% by weight of the metal alkoxide. Further, in consideration of economical efficiency, the fluorine-containing silane compound is 30 to
It is preferably 5%. 10% metal alkoxide
When it is less than 5, the long-term sustainability is insufficient, and when the content of the fluorine-containing silane compound is less than 5%, the water repellency improving effect, the gloss improving effect, the antifouling effect and the like are insufficient. The surface treatment agent for the metal alkoxide, the metal alkoxide polymer and the fluorine-containing silane compound can be used by dissolving in a solvent, and is usually 0.05 to 50% by weight.

As the solvent, hexane, octane,
Hydrocarbons such as petroleum benzine, mineral spirits, process oils; alcohols such as methanol, ethanol, propanol, butanol; acetic acid esters such as methyl acetate, ethyl acetate, butyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Cellosolves such as ethylene glycol monobutyl ether; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane.

In addition to the components A and B, if necessary,
A wax component, a silicone oil component, a surfactant, an abrasive and the like can be blended and used within a range that does not impair the intended performance.

[0012]

The surface-treating agent of the present invention, when applied to a coated surface to a substantially uniform thickness, chemically bonds to the coated surface to improve its gloss, and also has a gloss retention effect and an antifouling effect. It forms a coating film that can last for a long time. Although the mechanism of action is not clear, after the metal alkoxide of the component A, the polymer and the fluorine-containing silane compound of the component B, which are the essential components of the present invention, are applied to the coated surface, the solvent is volatilized, and Due to the water content, the metal alkoxide, the alkoxy group of the polymer and the fluorine-containing silane compound are decomposed and alcohol is produced as a by-product, and a metalloxane bond is generated between the metal alkoxides or between the metal alkoxide and the polymer, or between the fluorine-containing silane compounds, resulting in a high metalloxane bond. A part of the metal alkoxide is polymerized and binds to the resin on the surface of the coating, and at that time, a bulky perfluoroalkyl group is directed toward the surface to form a network, which has gloss and water repellency, and has a long-term antifouling effect. It is believed to form a durable and tough coating.

It should be noted that each of the components A and B alone forms a coating film which is effective as a surface treatment agent, but it is not practically sufficient. That is, the metal alkoxide and the polymer alone are insufficient in the gloss improving effect and the antifouling effect, and the silane compound having a fluorine-containing group alone is extremely slow in curing the coating film, and the long-term sustainability of the effect is sufficiently obtained. I can't. However, by using both together, the synergistic effect is exhibited, and a practically comprehensive coating film is formed. The surface treatment agent of the present invention is useful as a polishing agent having a long-term antifouling property, which is applied to a coated surface of a vehicle, an aircraft, office furniture and the like.

[0014]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. In each example, "part"
Means "parts by weight" unless otherwise specified.

(A) Preparation of surface treatment agent Surface treatment agent (A-1) Ethyl silicate condensate (trade name: ethyl silicate 4
0, made by Tama Chemical KK) 2 parts, tetrahexoxy titanium 1
Parts and C ₈ F ₁₇ C ₂ H ₄ Si- (OCH ₃ ) as fluorine-containing silane compound
₃ 1 part is a hydrocarbon solvent (trade name: Exol D10
0-140, manufactured by Exxon Kagaku KK) at room temperature with stirring for about 1 hour to dissolve, and a surface treatment agent solution (A-1) having a concentration of 4% by weight.
Was prepared.

Surface-treating agent (A-2) Tetraethoxysilane 3 parts, pentatitanoxane butoxide 1.5 parts and C ₈ F ₁₇ C ₂ H ₄ as a fluorinated silane compound.
2 parts of Si-CH ₃ (OCH ₃ ) ₃ was dissolved in a hydrocarbon solvent (described above) with stirring for about 1 hour at room temperature to prepare a surface treatment agent solution (A-2) having a concentration of 6.5% by weight.

Surface-treating agent (A-3) Ethyl silicate condensate (trade name: ethyl silicate 4
0, Tama Kagaku KK) 1.5 parts, tetra (n-butoxy zirconium 1.5 parts) and C ₆ F as a fluorine-containing silane compound.
₁₃ C ₂ H ₄ Si- (OCH ₃ ) ₃ 2 parts was dissolved in a hydrocarbon solvent (described above) at room temperature for about 1 hour with stirring to dissolve a surface treatment agent solution (A-3) having a concentration of 5% by weight. Prepared.

Surface-treating agent (A-4) Penta (ethoxy) silanoxy-penta (n-butoxy) titanoxane 2 parts, tetrabutoxyzirconium 1
Part and fluorine-containing silane compound as C ₄ F ₉ C ₂ H ₄ Si- (OCH ₃ )
₃ 3 parts was dissolved by stirring at room temperature for about one hour in a PSO35 (Chitsuso KK manufactured dimethylpolysiloxane), was prepared concentration of 6% by weight of the surface treatment agent solution (A-4).

Surface treating agents (A-5) to (A-15) and (R-1) to (R-4) In the same manner as in the preparation of (A-1), a metal alkoxide or a polymer thereof, a fluorine-containing compound. A silane compound, a solvent and the like are blended as shown in Table 1 to provide treating agent solutions (A-5) to (A-1).
5) and surface treatment agent solutions of comparative samples (R-1) to (R-3) were prepared. For comparison, a conventional wax was used as a sample (R-4).

[0020]

[Table 101]

[0021]

[Table 102]

The surface treatment agents (A-1) of the present invention described above
(A-15), Examples 1 to 15 using Comparative Samples (R-1) to (R-4), and Comparative Examples 1 to 5,
The following tests were conducted, and the measurement results are shown in Tables 2 and 3.

[0023]

[Table 2]

[0024]

[Table 3] (B) Contamination test 300 x 450 mm JIS K-5400 compliant white and black general-purpose automotive acrylic acrylic melamine resin coated iron plate was polished and scratched using Hanneri compound (KK Wilson), and in use 40 gloss equivalent to that of painted plates
Prepared to ~ 50 degrees. The above-mentioned surface treatment agents (A-1) to (A-11) and (R-1) to (R-4) were applied to the coated plate, dried at a temperature of 25 ° C. for 24 hours, and then washed with a cloth. It was wiped off using a piece to obtain a surface-treated plate. Acetylene black (trade name: XC-550-0.1%, Electrochemical industry
KK) as a hydrocarbon solvent (trade name: Exol D-10)
0-140, manufactured by Exxon Kagaku KK) was sprayed with the contaminated liquid on the surface-treated plate, and the temperature was raised to 70 ° C. for 30 minutes.
The operation of wiping off after standing for 3 minutes was repeated 3 times to treat the soil. Then, the glossiness before and after the stain dyeing treatment was measured using a 20 gloss meter (manufactured by Murakami Color Research Laboratory).

(C) Measurement of contact angle of water droplets Water is dropped from a pipette on the surface-treated plate of the contamination test of the item (b) to generate water droplets, and the contact angle is measured by a contact tank gourmet terminal (CA-). D-1 type, manufactured by Kyowa).

(D) Actual vehicle test Four white-painted cars (manufactured by Nissan Motor Co., Ltd.) were prepared.
Each sample prepared in the item (a) was applied to the table in the same manner as in the item (a), and a running test for 88 days was performed. 25 during this time
It was a rainy day. Before and after the running test and after running, the glossiness after the stain was wiped off was measured using the above-mentioned measuring device.

[0027]

As described above, the surface-treating agent for a coated surface of the present invention improves the gloss of the coated surface by chemically bonding the coated surface and the surface-treating agent, and also has the effect of maintaining the gloss. The antifouling effect can be maintained for a long period of time. The surface treatment agent is applied to the painted surface of vehicles, aircraft, office furniture, etc.,
It is useful as a polish having long-term antifouling properties.

Claims (4)

[Claims] 1. A surface treating agent for a coated surface, which comprises the following components A and B as essential components. Component A: General formula M (OR) _n ··· (I) (In the formula, M is one selected from the group consisting of metal atoms belonging to groups III, IV and V of the periodic table, R is the same or different, saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms,
n represents a number corresponding to the valence of the metal) and / or the polymer B component: a fluorine-containing silane compound 2. M in the general formula (I) is Al, Ga, In, S.
The surface treating agent for a coated surface according to claim 1, which is a metal selected from the group consisting of i, Sn, Ti, Zr, Ta and Nb. 3. The surface treating agent for a coated surface according to claim 1, wherein the fluorine-containing silane compound is a silane compound having a perfluoroalkyl group in the molecule. 4. The component A has the general formula Zr (OR) ₄ , Ti.
A metal alkoxide selected from the group (OR) ₄ , Si (OR) ₄ and Al (OR) ₃ (wherein R represents the same or different saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms). 2) and / or a polymer thereof.