JPH05140509A - Surface treating agent for coated surface - Google Patents

Abstract

PURPOSE:To obtain the subject agent, containing a reactional product prepared by reacting a metallic alkoxide with a fluorine-containing alkoxysilane and having metalloxane bonds, and having excellent effects on improvement and retention of the gloss, antifouling, etc. CONSTITUTION:The objective surface treating agent contains a reactional product, obtained by thermally reacting (A) a metallic alkoxide expressed by formula I [M is at least one metal selected from Al, Ga, In, Si, Sn, Nb and Ta; R is 1-22C saturated or unsaturated aliphatic hydrocarbon group; (n) is a number corresponding to the valence of the metal] and/or its polymer with (B) a fluorine-containing alkoxy compound expressed by formula II [Rf is fluorine- containing (alkoxy)alkyl which may have a polyperfluoroalkyl ether structure; R<1> is same as R; R<2> is lower alkyl; (m) is 0 or 1] in the presence of a catalyst in an organic solvent at <=100 deg.C and having metalloxane bonds. This surface treating agent is capable of chemically binding to a coated surface and sustaining gloss retaining and antifouling effects for a long period.

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 coated surfaces, and more particularly, a reaction having a metalloxane bond obtained by reacting an alkoxide of a specific metal and / or the polymer with a fluorine-containing silane compound. The present invention relates to a surface treatment agent for a coated surface containing a product.

[0002]

2. Description of the Related Art Car wax and the like have hitherto been widely marketed as a wax for polishing a coated surface. 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), Antirust Control, June 9-14, (1985) etc.)

[0003]

Problems to be Solved by the Invention Conventional surface-treating agents for coated surfaces are, as described above, improved in gloss due to adhesion of wax component or silicone oil component to coated surface, imparting water repellency, and coated surface. 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 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a reaction product having a metalloxane bond obtained by reacting a specific metal alkoxide with a fluorine-containing silane compound is obtained. The present invention has been completed by finding that the surface treatment agent contained as a component has excellent effects such as improvement in gloss, gloss retention, and antifouling.

The present invention is a surface treatment agent for a coated surface containing a reaction product having a metalloxane bond obtained by the reaction of the following components A and B. A component: General formula M (OR) _n ··· [1] (In the formula, M is at least one metal selected from the group consisting of Al, Ga, In, Si, Sn, Nb and Ta, R
Is the same or different type of saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, and n is the number corresponding to the valence of the metal)
And a polymer of these metal alkoxides B component: General formula RfSi (R ² ) _m (OR ¹ ) _3-m [2] (wherein Rf is polyperfluoro) Represents a fluorine-containing alkyl group which may have an alkyl ether structure or a fluorine-containing alkoxyalkyl group, R ¹ represents the same or different saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms,
R ² represents a lower alkyl group, and m represents 0 or 1. )
At least one kind of fluorine-containing alkoxysilane compound represented by

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 (where M is A
at least one metal selected from the group consisting of 1, Ga, In, Si, Sn, Nb and Ta, 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 a polymer of these metal alkoxides. In the metal alkoxide represented by the general formula M (OR) _n , M is Al, Ga, In, Si, Sn,
Nb and Ta. 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 metal alkoxide represented by M (OR) _n is used alone or in 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. The degree of polymerization of the polymer is usually about 2 to 20, and when the degree of polymerization exceeds 20, the reactivity of the alkoxy group is lowered, and the viscosity of the obtained polymer is increased to deteriorate the film forming property. In the present invention, the M (OR) _n of the metal alkoxide, M (OR) _n metal alkoxide and /
Alternatively, it can be used in the form of the metal alkoxide polymer. Specific examples of these are as follows.

(A) M (OR) _n independent system Al (OR) ₃ , Ga (OR) ₃ , In (OR) ₃ , S
i (OR) ₄ , Sn (OR) ₄ , Nb (OR) ₅ , Ta
(OR) _5th grade,

(B) Mixed system of M (OR) _n Al (OR) ₃ + Si (OR) ₄ , Nb (OR) ₅ + S
i (OR) ₄ , Ta (OR) ₅ , Si (OR) ₄ + Ta
(OR) _5th grade,

(C) M (OR) _n polymer-alone type siloxane, a copolymer having a Si--O--Si structure,
Copolymer having Sn-O-Si structure, Al-OA
copolymer having l structure, copolymer having Si-O-Al structure, copolymer having Al-O-In structure, copolymer having Sn-O-In structure, Nb-O
And a copolymer having a Ta structure.

The component B fluorine-containing alkoxysilane compound used in the present invention contains a fluorine-containing alkyl group or a fluorine-containing alkoxyalkyl group which may have a polyperfluoroalkyl ether structure in the molecule.
As the polyperfluoroalkyl ether structure, O-
_{CF 2 -O, O-CF 2} -CF 2 -O, O-CF 2 -C
_{F 2 -CF 2 -O, O-} CF 2 -CF (CF 3) -O,
_{O-CF (CF 3) -CF} 2 -O, O-CF (CF 3)
_{-CF (CF 3) -O, O} -C (CF 3) 2 -CF 2 -
_{O, O-CF 2 -C (} CF 3) 2 -O, O-C (C
_{F 3) 2 -C (CF 3} ) 2 -O, and the like can be exemplified.

As such a fluorine-containing alkyl group,
For _{example, CF 3 -CH 2 CH 2 -} , (CF 3) 2 -CF
_{CH 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) p (OCF
_{2) q O (CH 2)} r - in the fluorine-containing alkoxysilane compound having a group such as (wherein, p, q, r are 1, 2, 3
Indicates a natural number such as. ), And more specifically, CF _{3
-CH 2 CH 2 -Si (OCH 3} ) 3, (CF 3) 2 C
_{F-CH 2 -CH 2 -Si (} OCH 3) 3, CF 3 - (C
_{F 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, C
_{F 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 CH 2 -Si (OCH
_{3) 3, CF 3 - (} CF 2) 7 -CH 2 CH 2 -Si (CH
_{3) (OC 2 H 5)} 2, CF 3 - (CF 2) 2 -OCH 2 C
_{H 2 -Si (OC 2 H 5} ) 3, CF 3 - (CF 2) 2 -O-
_{CF (CF 3) CF 2 O-} (CH 2) 3 -Si (OC
_{H 3) 3, CF 3 O-} (CF 2) 3 -O- (CF 2) 3 -O-
_{(CH 2) 3 -Si (OCH} 3) it is ₃ and the like.

The reaction product having a metalloxane bond in the present invention is produced by the reaction of the above-mentioned component and the B component.
It is a compound having a -Si-OM- (M is the above) bond.

The compound having a metalloxane bond in the present invention is usually prepared by adding the above components A and B to an organic solvent in the presence of an acid such as hydrochloric acid, nitric acid, sulfuric acid or an alkali catalyst such as sodium hydroxide or potassium hydroxide. By heating at a temperature of 100 ° C. or lower, for example, according to the following reaction formula. R _f C ₂ H ₄ Si (OR ₁ ) ₃ + M (OR ₂ ) _n + H ₂ O → R _f C ₂ H ₄ Si (OR ₁ ) ₂ OM (OR ₂ ) _n-1 + HOR ₁ + HOR ₂ (wherein R _f is a perfluoroalkyl group, R ₁ and R ₂ are alkyl groups, M is the above, and n is the number corresponding to the valence of the metal.) In that case, the number of metal atoms of the component A to be reacted and The ratio of the number of silicon atoms of the B component is arbitrary, but it is preferable that the number of metal atoms of the A component is 100 to the number of silicon atoms of the B component.
1 to 200.

Although the structures of the compounds having a metalloxane bond to be produced are complex and diversified, examples of predicted structures of the expected products are as shown in the following general formulas [3] and [4]. .. (In the formula, R and R ¹ have the same meanings as described above, w is an integer from 1 to 14, and t is 0 to 2
Each represents an integer up to 0. )

[Chemical 1]

[0016]

[Chemical 2]

The surface treating agent containing the reaction product having a metalloxane bond as a component in the present invention is produced by dissolving the component in an organic solvent or dispersing it in water, and the concentration of the main component is usually 0.05 to 50% by weight. %. When the concentration of the main component is 0.05% by weight or less, the effect of water repellency decreases. Further, if it is 50% by weight or more, the effect is not further enhanced even if the concentration is further increased.

Solvents for dissolving the above components in organic solvents include hydrocarbons such as hexane, octane, petroleum resin, mineral spirits and process oils; alcohols such as methanol, ethanol, propanol and butanol; methyl acetate, Acetic acid esters such as ethyl acetate and butyl acetate; ethylene glycol monomethyl ether,
Cellosolves such as ethylene glycol monoethyl ether and 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 reaction product having a metalloxane bond, which is the reaction product of the A component and the B component, if desired, a wax component, a silicone oil component, a surfactant, a polishing agent, etc. can be used to obtain desired performance. Can be used by mixing within a range that does not impair

When a surface treating agent containing a reaction product having a metalloxane bond in the present invention as a component is applied to a coated surface, the coating method may be brush coating, roller coating, spray coating, dipping method or the like. Either method can be used.

[0021]

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. The mechanism of action is not clear, but the compound having a metalloxane bond obtained by the reaction of the A component and the B component, which are essential components of the present invention, is applied to the coated surface and then the metal is evaporated with the evaporation of the solvent. The alkoxide and / or the alkoxy group which is a part of the compound having a metalloxane bond, which is a reaction product of the polymer and the fluorine-containing silane compound, is decomposed to bond with the resin on the coating surface while alcohol is produced as a by-product. ,
It is considered that a bulky perfluoroalkyl group is directed toward the surface to form a network, which has gloss and water repellency, and forms a tough coating film that has a long-lasting antifouling effect.

The surface treatment agent of the present invention is useful as a polish agent having a long-term antifouling property to be applied to the painted surface of vehicles, aircraft, office furniture and the like.

[0023]

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" is
Unless otherwise specified, it means "part by weight".

(I) Synthesis of compound having metalloxane bond As a fluorine-containing alkylsilane compound, C ₈ F ₁₇ C ₂ H
Charge 568 g of ₄ Si (OCH ₃ ) ₃ into a round bottom flask,
To this, 4.6 g of ethanol as a solvent and 1.0 g of 0.1N hydrochloric acid as a catalyst were added and stirred, and 36 g of water was gradually added dropwise. After stirring for 2 hours, 208 g of tetraethoxysilane was added dropwise and stirring was continued for another 2 hours. Then, alcohol and solvent by-produced under reduced pressure at 20-40 mmHg and a bath temperature of 60 ° C. were distilled off to obtain 714 g of a slightly viscous transparent liquid (A-1). As a result of IR analysis, this product had absorption derived from Si—O—Si bond at 1150 Kaiser. Also, by heating at 900 ℃, S
As a result of measuring the content of iO ₂ , it was 8.29% (theoretical value 8.38%). As a result of the above, this product was presumed to have the following structure (1).

[0025]

[Chemical 3]

Similarly, the metal alkoxide or the metal alkoxide polymer thereof and the fluorine-containing alkylsilane compound are reacted in the amounts shown in Table 1 to give a reaction product (A-2) having a metalloxane bond as described above. ~
(A-7) was obtained.

[0027]

[Table 1]

(Ii) Preparation of surface treatment agent 6 g of (A-1) synthesized in (i) was added with 25 g of PSO35 (dimethylpolysiloxane, manufactured by Chitso KK) and Exole.
D100-140 (hydrocarbon solvent, Exxon Chemical KK) 70g
To prepare a surface treatment agent (F-1) of the present invention.
Similarly, the reaction products (A-2) to (A-7) having a metalloxane bond obtained above are dissolved in a solvent, and the surface treatment agents (F-1) to (F-7 of the present invention are dissolved. ) Was prepared. The contents of these preparations are shown in Table 2.

[0029]

[Table 2]

As a comparative sample, a surface treating agent (R-1) was prepared in which a mixture of a metal alkoxide and a fluorine-containing alkylsilane was dissolved in a solvent. For comparison, a conventional wax was used as a sample (R-2).

The above-mentioned surface treatment agents (F-1) of the present invention
(F-7), Comparative Samples (R-1), (R-2) Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to the following tests, and the measurement results are shown. The results are shown in Tables 3 and 4.

[0032]

[Table 3]

[0033]

[Table 4]

(Iii) Test method <Staining test> 300 × 450 mm white and black coated iron plates of acrylic melamine resin for general automobiles according to JIS K-5400 were ground with a Hanneri compound (manufactured by KK Wilson). The surface was scratched, and the gloss was adjusted to 40 to 50 degrees, which is equivalent to that of the coated plate in use. On the coated plate, the surface treatment agents (F-1) to (F-7), (R-1),
(R-2) was applied, dried at a temperature of 25 ° C. for 24 hours, and then wiped with a piece of cloth to obtain a surface-treated plate.
Acetylene black (trade name: XC-550-0.1%,
Denki Kagaku KK) in a hydrocarbon solvent (trade name: Exxol D-100-140, Exxon Kagaku KK) is dispersed in a contaminated liquid and sprayed onto the surface-treated plate at a temperature of 70 ° C. After being left for 3 minutes for 30 minutes, the operation of wiping was repeated 3 times to treat the stain. Then, the glossiness before and after the stain treatment was 20 gloss meter (manufactured by Murakami Color Research Laboratory).
Was measured.

<Measurement of Contact Angle of Water Droplet> Water was dropped by a pipette on the same surface-treated plate used in the above contamination test to generate water droplets, and the contact angle was measured by the contact tan gourmet-taper.
(CA-D-1 type, manufactured by Kyowa).

<Actual vehicle test> White painted vehicle (manufactured by Nissan Motor Co., Ltd.)
Four units were prepared, and each of the samples prepared in the item (i) was applied to three of them in the same manner as in the item (i), and a running test for 88 days was performed. During this period, it was a rainy day for 25 days. 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. Further, the water repellency after removing the stain was examined.

[0037]

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 (2)

[Claims] 1. A surface treating agent for a coated surface, which comprises a reaction product having a metalloxane bond obtained by reacting the following components A and B: A component: General formula M (OR) _n ... [1] (In the formula, M is at least one metal selected from the group consisting of Al, Ga, In, Si, Sn, Nb, and Ta, R
Is the same or different type of saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, and n is the number corresponding to the valence of the metal)
And a polymer of these metal alkoxides B component: general formula RfSi (R ² ) _m (OR ¹ ) _3-m [2] (wherein Rf is polyperoxide) Represents a fluorine-containing alkyl group or a fluorine-containing alkoxyalkyl group which may have a fluoroalkyl ether structure, R ¹ represents the same or different C 1-22 saturated or unsaturated aliphatic hydrocarbon group, R 1 ² represents a lower alkyl group, and m represents 0 or 1.) At least one fluorine-containing alkoxysilane compound represented by 2. A fluorine-containing alkoxysilane compound in which the Rf group in the general formula [2] is a fluorine-containing alkyl group having a carbon number of 3 to 16 as the component B.
Surface treatment agent for the painted surface described.