JPH05125083A - Production of surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain a surface-treating agent, improving the lusters of the coating surfaces by chemical combination with coating surfaces and capable of maintaining the effects for long periods by reacting a specific metal alkoxide with a specified fluorine-containing alkylsilane compound. CONSTITUTION:A metal alkoxide of formula M(OR)4 (M is Ti, Zr; R is 1-10C alkyl) or its polymer is reacted with a fluorine-containing alkylsilane compound of formula I or II (Rf is 3-20C fluorine-containing alkyl which may have a perfluoroalkyl ether structure; R' is 1-22C aliphatic hydrocarbon; R'' is 1-4C alkyl) to obtain a compound containing an M-O-Si bond, e.g. a compound of formula III. The reaction is preferably performed by a method comprising heating a compound of formula I or II in the presence of an acid or alkali catalyst at 40-70 deg.C and subsequently condensing the synthesized silanol with a metal alkoxide of the formula M(OR)4 or its polymer at 40-70 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a titanate- or zirconate-modified silane-based surface treatment agent,
More specifically, it relates to a method for producing a surface treating agent containing a novel reaction product of a Ti alkoxide, a Zr alkoxide or a polymer thereof and a fluorine-containing alkylsilane compound as an active ingredient. The surface treatment agent according to the present invention is a coated surface,
It has excellent wettability with metal surface and inorganic surface, chemical resistance, and stain resistance, so it can be widely used in the fields where wax, silicone, fluorinated silicone, and fluororesin have been conventionally used. I can.

[0002]

2. Description of the Related Art As a wax for polishing a coated surface, a wax such as a wax has been widely commercially available. Regarding the composition of these lustrous waxes, the details are unknown because each manufacturer has the know-how, but the typical component is a wax that forms a film and gives a luster.
It is known that a silicone oil component that fluidizes the components and the wax component to impart water repellency to the coating, an organic solvent or water as a dispersion medium, a surfactant, and an abrasive are blended. (Encyclopedia of Chemical Technology
, Vol. 18, Vol. 18, 324-325, Kirk-Othmer, Cleaning Design,
Spring issue (25), 63-80, (1980), rust prevention management, June 9-14, (198
(See 5) 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 period of time. It is an object of the present invention to propose a production method capable of easily obtaining a surface treatment agent which can be maintained in high yield.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, after hydrolyzing a fluorine-containing alkylsilane compound in the presence of an acid or alkali catalyst to obtain a silanol derivative, Ti alkoxide, Z
By reacting r-alkoxides or their polymers in the presence of an acid or alkali catalyst, they have excellent effects such as improved gloss, gloss retention, and antifouling. A compound with -MO-Si- bond is efficient and simple. The present invention has been completed by finding out that it can be obtained.

The present invention is characterized by reacting the following A component with a silanol derivative of B component: -MO-Si-
A method for producing a surface treatment agent for a painted surface, which contains a compound having a bond. Component A: General formula M (OR) ₄・ ・ ・ ・ ・ ・ ・ ・ [1] (In the formula, M or Ti or Zr is shown, and R is the same or different and has 1 to 10 carbon atoms. Which represents an alkyl group) or a polymer thereof, and B component: a fluorine-containing alkylsilane compound represented by the following general formula [2] or [3] RfSi (OR ′) ₃ ... ··· [2] RfSi (R ″) (OR ′) ₂ ··· [3] (In the formula, the Rf group may have a perfluoroalkyl ether structure, and has 3 to 20 carbon atoms. Is a fluorine-containing alkyl group, R'is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, which is the same or different, and R "is 1 carbon atom.
~ 4 alkyl groups are shown)

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) ₄ (wherein M and R
Has the same meaning as above. ) Is a metal alkoxide or a polymer thereof. The alkyl group of the alkoxy group of these Ti alkoxides or Zr alkoxides is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, decyl group and the like.

In the present invention, the above metal alkoxides can be used alone or in a mixed system. Examples of the Ti alkoxide or Zr alkoxide used include:
You can list the following: Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (O-iC ₃ H ₇ ) ₄ , Ti
(OC ₄ H ₉ ) ₄ , Ti (OC ₅ H ₁₁ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti (OC ₂ H ₅ ) ₂ (OC ₈
H ₁₇ ) ₂ , Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₂ H ₅ )
₂ (OC ₈ H ₁₇ ) ₂ , etc.

As the component A used in the present invention, a hydrolyzed polymer represented by the above general formula M (OR) ₄ is also used. Specific examples of these include the following.

(C ₃ H ₇ O) ₃ TiO- [Ti (OC ₃ H ₇ ) ₂ O-] ₂ -Ti (OC ₃ H ₇ )
₃ ,, (C ₄ H ₉ O) ₃ TiO- [Ti (OC ₄ H ₉ ) ₂ O-] ₄ -Ti (OC ₄ H ₉ ) ₃ , (iC _{3
H 7 O) 3 TiO- [Ti} (O-iC 3 H 7) 2 O-] 7 -Ti (O-iC 3 H 7) 3, (C 4 H 9 O) 3 Ti
O- [Ti (OC ₄ H ₉ ) ₂ O-] ₁₀ -Ti (OC ₄ H ₉ ) ₃ , (C ₃ H ₇ O) ₃ ZrO- [Zr (OC ₃ H
_{7) 2 O-] 2 -Zr (} OC 3 H 7) 3, (C 4 H 9 O) 3 ZrO- [Zr (OC 4 H 9) 2 O-] 4 -
Zr (OC ₄ H ₉ ) ₃ , etc.

The fluorine-containing alkylsilane compound used in the present invention has a perfluoroalkyl structure (C _n
F _{2n + 1} ) is included, and examples thereof include compounds represented by the following general formula [4] or [5]. _{C n F 2n + 1 (CH} 2) m Si (OR ') 3 ········ [4] _{C n F 2n + 1 (CH} 2) m Si (R ") (OR') 2 · ··· [5] (In the formula, n represents an integer of 1 to 14, m represents an integer of 2 to 6, and R ′ and R ″ have the same meanings as described above.) the manner, CF ₃ -CH ₂ CH ₂ -S
_{i (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) 11 -CH 2 CH 2
_{-Si (OC 2 H 5) 3} , CF 3 (CF 2) 3 -CH 2 CH
_{2 -Si (CH 3) (OCH} 3) 2, CF 3 (CF 2) 7 -
_{CH 2 CH 2 -Si (CH 3} ) (OCH 3) 2, CF
_{3 (CF 2) 8 -CH 2} CH 2 -Si (CH 3) (OC 2
_{H 5) 2, CF 3 (} CF 2) 8 -CH 2 CH 2 -Si (C 2
H ₅ ) (OC ₂ H ₅ ) ₂ , and the like.

As the fluorine-containing alkylsilane compound of the present invention, one having a perfluoroalkyl ether structure in the molecule can be used. Specific examples thereof include compounds represented by the following general formulas [6] and [7]. _{C p F 2p + 1 O (} C p F 2p O) r (CH 2) m Si (OR ') 3 ··· (6) _{C p F 2p + 1 O (} C p F 2p O) r (CH 2 ) _m Si (R ″) (OR ′) ₂ [7] (where m is an integer from 2 to 6, p is an integer from 1 to 4 and r is an integer from 1 to 10, and R 'and R "are as defined supra.) examples of specific _{compounds, CF 3 O (CF 2 O} ) 6 -CH 2 CH 2 -Si
_{(OC 2 H 5) 3,} CF 3 O (C 3 F 6 O) 4 -CH 2 C
_{H 2 -Si (OCH 3) 3} , CF 3 O (C 3 F 6 O)
_{2 (CF 2 O) 3 -CH} 2 CH 2 -Si (OCH 3) 3,
_{CF 3 O (C 3 F 6} O) 8 -CH 2 CH 2 -Si (OC
_{H 3) 3, CF 3 O} (C 4 F 9 O) 5 -CH 2 CH 2 -S
_{i (OCH 3) 3, CF} 3 O (C 4 F 9 O) 5 -CH 2 C
_{H 2 -Si (CH 3) (} OC 2 H 5) 2, CF 3 O (C 3
_{F 6 O) 4 -CH 2 CH} 2 -Si (C 2 H 5) (OC
H ₃ ) ₂ and the like.

The compound having a -MO-Si- bond in the present invention can be synthesized by reacting the above-mentioned components A and B.

The method for producing a compound having a -MO-Si- bond in the present invention comprises the following silanols prepared by heating the above-mentioned component B, an alkoxysilane, in the presence of an acid or alkali catalyst at a temperature of 100 ° C or lower. (8), (9),
After obtaining (10), (11), (12), (13) and the like, a compound having a -MO-Si- bond can be produced by a condensation reaction of silanol and a metal alkoxide or a polymer thereof.

C _n F _{2n + 1} (CH ₂ ) _m Si (OR ') ₂ OH (8) C _n F _{2n + 1} (CH ₂ ) _m Si (OR') (OH) ₂ ... _{(9) C n F 2n +} 1 (CH 2) m Si (R ") (OR ') OH ··· (10) C p F 2p + 1 O (C p F 2p O) r (CH 2) m _{Si (OR ') 2 OH ···} (11) C p F 2p + 1 O (C p F 2p O) r (CH 2) m Si (OR') (OH) 2 ··· (12) C p F _{2p + 1} O (C _p F _2p O) _r (CH ₂ ) _m Si (R ″) (OR ′) OH (13)

(A) Synthesis of silanol Silanol is a compound in which at least one of the alkoxy groups in the molecule of the above-mentioned fluorine-containing alkylsilane compound is hydrolyzed to a hydroxyl group. For example, it is synthesized according to the following reaction formula. be able to. _{C n F 2n + 1 (CH} 2) m Si (OR ') 3 + H 2 O → C n F 2n + 1 (CH 2) m Si (OR') 2 OH + R'OH C n F 2n + 1 (CH 2 _{) m Si (OR ') 3} + 2H 2 O → C n F 2n + 1 (CH 2) m Si (OR') (OH) 2 + 2R'OH C n F 2n + 1 (CH 2) m Si (R " ) (OR ′) ₂ + H ₂ O → C _n F _{2n + 1} (CH ₂ ) _m Si (R ″) (OR ′) OH + R′OH C _p F _{2p + 1} O (C _p F _2p O) _r (CH ₂ ) _m Si (OR ') ₃ + H ₂ O → C _p F _{2p + 1} O (C _p F _2p O) _r (CH ₂ ) _m Si (OR') ₂ OH + R'OH C _p F _{2p + 1} O ( _{C p F 2p O) r (} CH 2) m Si (OR ') 3 + 2H 2 O → C p F 2p + 1 O (C p F 2p O) r (CH 2) m Si (OR') (OH) _{2 + 2R'OH C p F 2p +} 1 O (C p F 2p O) r (CH 2) m Si (R ") (OR ') 2 + H 2 O → C p F _{2p + 1} O (C _p F _2p O) _r (CH ₂ ) _m Si (R ″) (OR ′) OH + R′OH (where n, m, p, r, R ′ and R ″ are Represents the same meaning as out.)

In the above-mentioned synthesis of silanol, the catalyst is
When the catalyst is an acid, the pH of the system is adjusted to 2 to 7, and when it is an alkali, the pH is adjusted to 7 to 13. When the pH in the reaction system becomes 2 or less or 13 or more, a siloxane polymer is produced, the reaction product gels, the viscosity increases, and finally it solidifies and cannot be used.

The acid used as a catalyst is hydrochloric acid,
Examples thereof include protic acids such as sulfuric acid, phosphoric acid, nitric acid, and acetic acid. Further, examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

In the above silanol synthesis reaction, the amount of water used is such that the molar ratio of H ₂ O / Si is from 0.1 / 1 to
It is within the range of 3/1, preferably within the range of 0.5 / 1 to 2/1. When the H ₂ O / Si molar ratio is 0.1 / 1 or less, the silanol production yield is poor, and when it is 3/1 or more, water remains in the reaction system, resulting in metal alkoxide. (Or its polymer),
Water causes a side reaction with the metal alkoxide (or its polymer), and the yield of the target compound having an M-O-Si- bond is significantly reduced.

The reaction temperature is 20 ° C to 90 ° C, preferably 4 ° C.
It is 0 ° C to 70 ° C. When the reaction temperature exceeds 90 ° C,
The reaction product gels. On the other hand, at 20 ° C or lower, the progress of the hydrolysis reaction is significantly delayed.

The above silanol can be synthesized usually without a solvent, but an organic solvent such as alcohols can also be used. The obtained silanol can be used in the next reaction without isolation.

(B) Production of Compound Having -MO-Si- Bond-The compound having a MO-Si- bond is the above silanol and T.
It can be prepared by dealcoholation reaction with i alkoxide, Zr alkoxide or a polymer thereof. The synthesis of the compound having a -MO-Si- bond can be performed continuously with the reaction of silanol. The reaction is performed subsequent to the synthesis of the silanol. Usually, silanol can be used for the next reaction without isolation. In this reaction, an acid or alkali catalyst is required, but when it is carried out without isolating silanol, the catalyst used for the synthesis of silanol remains in the system, so it is particularly necessary to add it. Absent.

The amount of metal alkoxide used in the reaction is Si / M (molar ratio) = 0.5 / 1 to 3/1, preferably 1/1 to 2/1. Si / M (molar ratio) is 3
In the case of / 1 or more, unreacted silanol remains in the system, and the yield of the target compound having a -MO-Si- bond decreases. If it is 0.5 / 1 or less, a compound having a -MO-Si- bond having good water repellency cannot be obtained.

The reaction temperature is 20 ° C to 90 ° C, preferably
It is 40 ° C to 70 ° C. When the temperature is 90 ° C. or higher, the reaction product gels and the yield of the desired product is lowered.

After completion of the reaction, the byproduct is distilled off under reduced pressure (usually 20 to 80 mmHg), whereby the desired product can be obtained easily and efficiently.

The compounds having —MO—Si— bonds produced are complex and diversified, and it is difficult to identify the products. However, this presumed condensation reaction is, for example, as follows.

C _n F _{2n + 1} (CH ₂ ) _m Si (OR ') ₂ OH + M (OR) ₄ → C _n F _{2n + 1} (CH ₂ ) _m Si (OR') ₂ O-M (OR) ₃ C _n F _{2n + 1} (CH ₂ ) _m Si (OR ') (OH) ₂ + 2M (OR) ₄ → C _n F _{2n + 1} (CH ₂ ) _m Si (OR')-(O-M (OR) ₃ ) ₂ C _n F _{2n + 1} (CH ₂ ) _m Si (R ″) (OR ′) OH + M (OR) ₄ → C _n F _{2n + 1} (CH ₂ ) _m Si (R ″) (OR ′) O _{-M (OR) 3 C p F} 2p + 1 O (C p F 2p O) r (CH 2) m Si (OR ') 2 OH + M (OR) 4 → C p F 2p + 1 O (C p F _{2p O) r (CH 2)} m Si (OR ') 2 O-M (OR) 3 C p F 2p + 1 O (C p F 2p O) r (CH 2) m Si (OR') (OH) _{2 + 2M (OR) 4 →} C p F 2p + 1 O (C p F 2p O) r (CH 2) m Si (OR ') - - (OM (OR) 3 _{2 C p F 2p + 1 O} (C p F 2p O) r (CH 2) m Si (R ") (OR ') OH + M (OR) 4 → ( wherein, n, m, R, R ' and R "has the same meaning as described above.)

Further, as an example of the compound having a —MO—Si— bond, the following general formula is given.

[9], [10], etc. can be mentioned.

[0028]

[Chemical 1]

[0029]

[Chemical 2]

The surface treating agent containing a compound having a -MO-Si- bond as a component in the present invention is this -MO-Si.
It is produced by dissolving a compound having a bond 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 weight or less, the effect of water repellency decreases. Further, if it is 50% by weight or more, the effect does not increase even if the concentration further increases.

Solvents for dissolving the above components in organic solvents include hexane, octane, petroleum benzine, mineral spirits, hydrocarbons such as kerosene, and silicone oil.

Further, it is a reaction product of the A component and the B component.
In addition to the compound having a -MO-Si- bond, an abrasive or the like can be blended and used within a range that does not impair the intended performance, if necessary.

When a surface treatment agent containing a compound having a --MO--Si bond as a component in the present invention 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.

[0034]

The surface-treating agent of the present invention, when applied to a coated surface in 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 —MO—Si bond, which is obtained by reacting the A component and the B component, which are essential components of the present invention, is applied to the coated surface and then the solvent evaporates. Along with this, the reaction product of a metal alkoxide and a fluorine-containing alkylsilane compound is decomposed by an alkoxy group, which is a part of the compound having a -MO-Si bond, and by-product of alcohol, is bonded to the resin on the coating surface, At that time, the bulky perfluoroalkyl group is directed to the surface to form a network,
It is considered to form a tough coating film that has gloss and water repellency and maintains the antifouling effect for a long period of time.

The surface treating agent of the present invention is useful as a polishing agent having a long-term antifouling property to be applied to a painted surface of a vehicle or the like.

[0036]

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) Synthesis of Compound Having -Si-O-Ti- Bond (1) As a fluorine-containing alkylsilane compound, C ₈ F ₁₇ C ₂ H ₄ Si (OC
H _{3) 3} was charged with 56.8g round bottom flask, ethanol thereto as a solvent - 0.1 N hydrochloric acid 1g Le 4.6 g, as a catalyst
Was added and stirred, to which 3.6 g of water was gradually added dropwise. After stirring for 2 hours, 56.4 g of tetrakis (2-ethylhexoxy) titanium was added dropwise and stirring was continued for 2 hours. Subsequently, alcohols by-produced at a bath temperature of 60 ° C. and alcohol of the solvent were removed under reduced pressure at a bath temperature of 60 ° C. to obtain 98.8 g of a slightly viscous transparent liquid (A-1). As a result of IR analysis, this product had absorption derived from Si—O—Ti bond at 935 Kaiser. The content of SiO ₂ + TiO ₂ was measured by heating at 900 ° C. and found to be 14.1% (theoretical value 14.2%). In addition, as a result of elemental analysis, C
It was 43.0%, H6.5%, O9.9%, F32.9%. (Theoretical value C43.7%, H6.2%, O9.7%, F32.7%) As a result of the above, the following structure [11] was estimated as an expected formula of this product.

[0038]

[Chemical 3]

(B) Synthesis of compound having -Si-O-Ti- bond (2) C ₉ F ₁₉ C ₂ H ₄ Si (OC) as fluorine-containing alkylsilane compound
618 g of ₂ H ₅ ) ₃ was charged into a round bottom flask, 46 g of ethanol as a solvent and 10 g of 0.1N sulfuric acid as a catalyst were added thereto and stirred, and 18 g of water was gradually added dropwise thereto. After stirring for 2 hours, 284 g of tetraisopropoxy titanium was added dropwise.
The stirring was continued for 2 hours. Subsequently, alcohol by-produced at 20-40 mmHg under reduced pressure and a bath temperature of 60 ° C. and alcohol as a solvent were expelled to obtain 856 g of a slightly viscous transparent liquid (A-2). As a result of IR analysis, this product showed Si at 935 Kaiser.
It had absorption derived from the -O-Ti bond. Also, 900
As a result of measuring the content of SiO ₂ + TiO ₂ by heating at ℃, 16.1
% (Theoretical value 16.4%). Also, as a result of elemental analysis,
It was C 33.2%, H4.5%, O11.4%, and F42.0%. (Theoretical values C33.6%, H4.1%, O11.2%, F42.2%) As a result, the following structure [12] was estimated as the expected formula of this product.

[0040]

[Chemical 4]

(C) Synthesis of Compound Having -Si-O-Ti- Bond (3) As a fluorine-containing alkylsilane compound, CF ₃ C ₂ H ₄
A round bottom flask was charged with 218 g of Si (OCH ₃ ) ₃ and 46 g of ethanol as a solvent and 0.1N sulfuric acid as a catalyst were added to the flask.
18 g was added and stirred, and 18 g of water was gradually added dropwise thereto. After stirring for 2 hours, 424 g of dipropoxydi (2-ethylhexoxy) titanium was added dropwise and stirring was continued for 2 hours. Subsequently, the alcohols by-produced and the solvent alcohol were distilled off under reduced pressure at 20 to 40 mmHg and a bath temperature of 60 ° C. to obtain 568 g of a slightly viscous transparent liquid (A-3). This is IR
As a result of the analysis, 935 Kaiser had absorption derived from Si—O—Ti bond. Also, by heating at 900 ° C, SiO ₂ +
As a result of measuring the content of TiO ₂ , it was 24.9% (theoretical value 2
4.6%). In addition, as a result of elemental analysis, C 50.1%, H 9.5%,
O was 16.7% and F was 10.3%. (Theoretical value C50.7%, H
As a result of 9.0%, O16.9%, F10.0%) or more, the following structure [13] was estimated as an expected formula of this compound.

[0042]

[Chemical 5]

(D) Synthesis of Compound Having -Si-O-Ti- Bond (4) As a fluorine-containing alkylsilane compound, CF ₃ C ₂ H ₄
Si (OCH ₃ ) ₃ 218 g was charged into a round bottom flask, 46 g of ethanol as a solvent and 10 g of 0.2N sodium hydroxide ethanol solution as a catalyst were added and stirred, and 18 g of water was gradually added dropwise to this. did. After stirring for 2 hours, 284 g of tetraisopropoxy titanium was added dropwise and stirring was continued for 2 hours. Then, by-produced alcohol and by-product alcohol were distilled off under reduced pressure at 20 to 40 mmHg and a bath temperature of 60 ° C. to obtain 766 g of a slightly viscous transparent liquid (A-4). As a result of IR analysis, this product had absorption derived from Si—O—Ti bond at 935 Kaiser. In addition, as a result of elemental analysis, C 3
It was 7.3%, H7.1%, O20.8%, F14.6%. (Theoretical values C37.6%, H6.8%, O20.9%, F14.9%) As a result of the above, the following structure [14] was estimated as an expected formula of this product.

[0044]

[Chemical 6]

(E) Synthesis of Compound Having -Si-O-Ti- Bond (5) 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, 46 g of ethanol as a solvent and 10 g of 0.4N hydrochloric acid as a catalyst were added and stirred, and 18 g of water was gradually added dropwise thereto. After stirring for 2 hours, tetraisopropoxy titanium
142 g was added dropwise and stirring was continued for 2 hours. Then under reduced pressure 20
-40 mmHg, alcohol by-produced at a bath temperature of 60 ° C and solvent alcohol were distilled off to give a slightly viscous transparent liquid (A-
5) 636 g was obtained. As a result of IR analysis, this product shows 935
Kaiser had absorption derived from the -Si-O-Ti bond.
In addition, as a result of elemental analysis, C 28.0%, H 2.7%, O 10.1%,
F5 was 1.3%. (Theoretical value C28.3%, H2.7%, O1
0.1%, F51.0%) Also, by heating at 900 ℃, SiO ₂ + T
The iO ₂ content was measured and found to be 15.9% (theoretical value 15.
7%). As a result of the above, the following structure [15], for example, was estimated as the expected formula of this product.

[0046]

[Chemical 7]

Production examples of the present invention (A-
1) to (A-8) are summarized in Table 1.

[Table 1]

(G) Preparation of Surface Treatment Agent 5 g of (A-1) synthesized in (a) was dissolved in 25 g of PSO35 (dimethylpolysiloxane, manufactured by Chisso KK) and 70 g of Exsol D100-140 (manufactured by Exxon Chemical KK). The surface treatment agent (F-1) was prepared. Similarly,
As shown in Table 2, compounds having a -MO-Si- bond (A-
1) to (A-8) were mixed or emulsified in a solvent or the like to prepare surface treatment agents (F-2) to (F-10).

For comparison, a surface treatment agent example (R-1) in the case of mixing a Ti alkoxide and a fluorine-containing alkylsilane mixture in a solvent was prepared. For comparison, a conventional wax was used as a sample (R-2).

[0050]

[Table 2]

The surface treatment agents (F-1) of the present invention described above.
(F-10), Comparative samples (R-1) and (R-2) were used to perform the following tests on Examples 1 to 10 and Comparative Examples 1 and 2, and the measurement results are shown. As reference examples, shown in Tables 3 and 4.

(H) Contamination test 300 x 450 mm white and black general-purpose automobile acrylic acrylic melamine resin coated iron plate was ground and scratched using Hanneri compound (KK Wilson) , Gloss level of 40, which is equivalent to that of the coated plate in use
Prepared to ~ 50 degrees. The above-mentioned surface treatment agents (F-1) to (F-10), (R-1) and (R-2) were each applied to this coated plate and dried at a temperature of 25 ° C for 24 hours, and then a cloth It was wiped off using a piece to obtain a surface-treated plate. Acetylene black (trade name: XC-550-0.1%, manufactured by Denki Kagaku Kogyo KK) is used as a hydrocarbon solvent (trade name: EXZOL D-1).
00-140, manufactured by Exxon Chemical Co., Ltd.), the contaminated liquid is sprayed on the surface-treated plate, and the temperature is 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 treatment was measured using a 20 gloss meter (manufactured by Murakami Color Research Laboratory).

(I) Measurement of Contact Angle of Water Droplet Water was dropped by a pipette onto the surface-treated plate used in the contamination test of the item (b) to generate a water droplet, and the contact angle was measured by a contact tan gourmet terminal (CA-). D-1 type, manufactured by Kyowa).

(J) 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. In addition, the water repellency and antifouling property after removing the stains were observed.

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

As described above, the surface treating agent of the present invention is an efficient and simple method for hydrolyzing a fluorine-containing alkylsilane compound into a silanol derivative and then conducting a condensation reaction with a metal alkoxide or a polymer thereof. Can be manufactured. The surface-treating agent of the present invention is capable of chemically bonding the coated surface and the surface-treating agent, improving the gloss of the coated surface, and maintaining the gloss retaining effect and the antifouling effect for a long period of time. Further, the surface treatment agent of the present invention is applied as a polish agent having long-term antifouling property by applying it to the coated surface of vehicles, plastics, wood, metals, inorganic substances (marble, glass), indoor and outdoor building materials, etc. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09G 1/00 A 6917-4H

Claims (2)

[Claims] 1. A method for producing a compound having a —MO—Si— bond, which comprises reacting the following components A and B: Component A: General formula M (OR) ₄ ... [1] (In the formula, M represents Ti or Zr, and R is the same or different carbon number 1 to 1). 10 represents an alkyl group) or its polymer B component: Fluorine-containing alkylsilane compound RfSi (OR ') ₃ represented by the following general formula [2] or [3]: -[2] RfSi (R ") (OR ') ₂ ... [3] (In the formula, the Rf group may have a perfluoroalkyl ether structure and has 3 to 20 carbon atoms. Represents a fluorine-containing alkyl group, R ′ represents the same or different saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ″ represents 1 carbon atom
~ 4 alkyl groups are shown. ) 2. The method for producing a compound having a —MO—Si— bond according to claim 1, wherein the fluorine-containing alkylsilane compound which is the B component represented by the general formula [2] or [3] is acid or After hydrolyzing in the presence of an alkali catalyst to form a silanol derivative with at least one OR 'group in the molecule of the compound of the general formula [2] or [3] as a hydroxyl group, a metal alkoxide of the general formula [1] is obtained. Alternatively, a method for producing a compound having a -MO-Si- bond, which comprises reacting the polymer.