JP4401907B2 - Easily washable articles for members used around water in a dwelling house and method for producing the same - Google Patents

Description

  The present invention is an easy-to-clean article for glass members, ceramic members, and plastic members used around water such as bathrooms, toilets, kitchens, changing rooms, washstands, etc. The present invention relates to an article having detergency and excellent alkali resistance.

  Articles made by applying a solution containing alkoxysilane such as tetraethoxysilane and fluoroalkylsilane to a base material are known to have water repellency and oil repellency. (For example, patent document 1). However, paying attention to the water repellency and oil repellency of the article, it should be used for a long time when used around water in bathrooms, toilets, kitchens, changing rooms, washstands, etc. Therefore, it is necessary to consider what kind of environment is exposed to actual use. A particularly important factor is resistance to detergents and drugs frequently used in the home.

Around water, articles are placed in an environment where they are in direct contact with water or are frequently exposed to water droplets, and therefore various contaminants, particularly scales, are likely to occur. For this reason, the easy washing | cleaning property with respect to scale is required. Also, there are often occasions where alkaline detergents are used as detergents to remove such contamination. This alkaline detergent may be used directly on the article, or it may be splashed when used on nearby articles. Alkalinity is required.
JP-A-6-93230

  The present invention is an easy-to-clean article for glass members, ceramic members, and plastic members used around water such as bathrooms, toilets, kitchens, changing rooms, and washstands in a house, and has alkali resistance. In particular, an object of the present invention is to provide an article excellent in easy-cleaning against scale.

  That is, the easily washable article of the present invention is an article for a member used around water in a house, and is an article comprising a base material and a film formed on the base material. The coating film comprises silica as a matrix, a fluoroalkylsilane represented by the general formula [A], and a dimethylsilicone represented by the general formula [B], and the content of the fluoroalkylsilane is based on silica. The weight ratio of 0.10 times to 0.30 times, preferably 0.15 times to 0.30 times, the dimethyl silicone is 0.001 times to 0.000 by weight with respect to silica. The amount is 050 times, preferably 0.010 to 0.030 times.

  Since the film configuration is excellent in alkali resistance, it exhibits excellent easy cleaning properties over a long period even in places where alkaline detergents are frequently used. Further, since this film structure is mainly composed of silica as a matrix, the film has a high strength, and has an advantage that the film is hardly damaged even when wiping with a cloth or the like is performed.

ここで、Ｂ^１は-ＣＦ_３基、又は-ＣＨ_２ＣＨ_２Ｓｉ(ＣＨ_３)_{３−ｐ−ｑ}Ｙ^１ _ｑ(Ｏ−)_ｐ基であり、Ｘ^１、Ｙ^１は、それぞれ、１価の加水分解性基又は−ＯＨ基である。さらに、［ｍ］は３〜１２の整数、［ｐ］及び［ｒ］は、それぞれ、１〜３の整数である。さらに、［ｑ］及び［ｓ］は、それぞれ、０〜２の整数であり、［ｐ］と［ｑ］の合計及び［ｒ］と［ｓ］の合計は、それぞれ、３以下である。又、末端の酸素は、他の化学種、又は同一の化学種と結合している状態を示している。

Here, B ¹ is a —CF ₃ group, or —CH ₂ CH ₂ Si (CH ₃ ) _{3 -pq} Y ¹ _q (O—) _p group, and X ¹ and Y ¹ are each monovalent. The hydrolyzable group or —OH group. [M] is an integer of 3 to 12, and [p] and [r] are integers of 1 to 3, respectively. Furthermore, [q] and [s] are each an integer of 0 to 2, and the sum of [p] and [q] and the sum of [r] and [s] are each 3 or less. Further, the oxygen at the terminal indicates a state in which it is bonded to other chemical species or the same chemical species.

ここで、Ａ^１、Ａ^２は、それぞれ、２価の炭化水素基、又は、-(ＣＨ_２)_ｉ-ＮＨ-ＣＯ-Ｏ-基（［ｉ］は０〜９の整数）、若しくは、酸素であり、Ｒ^１、Ｒ^２は、それぞれ、１価の炭化水素基又は水素である。又、［ｎ］は２０００以下の整数、好ましくは２０以上の整数、より好ましくは１０００以下の整数で平均重合度を表す。さらに、［ａ］及び［ｃ］は、それぞれ、０〜３の整数であり、［ａ］と［ｃ］の合計は３以上である。さらに又、［ｂ］及び［ｄ］は、それぞれ、０〜３の整数であり、［ａ］と［ｂ］の合計及び［ｃ］と［ｄ］の合計は、それぞれ、３以下である。又、末端の酸素は、他の化学種、又は同一の化学種と結合している状態を示している。

Here, A ¹ and A ² are each a divalent hydrocarbon group or a — (CH ₂ ) _i —NH—CO—O— group ([i] is an integer of 0 to 9), or oxygen And R ¹ and R ² are each a monovalent hydrocarbon group or hydrogen. [N] represents an average degree of polymerization by an integer of 2000 or less, preferably an integer of 20 or more, more preferably an integer of 1000 or less. Furthermore, [a] and [c] are each an integer of 0 to 3, and the sum of [a] and [c] is 3 or more. Furthermore, [b] and [d] are each an integer of 0 to 3, and the sum of [a] and [b] and the sum of [c] and [d] are each 3 or less. Further, the oxygen at the terminal indicates a state in which it is bonded to other chemical species or the same chemical species.

  The fluoroalkylsilane represented by the general formula [A] has an effect of improving the removal of scale contaminants from the coating and the alkali resistance of the coating, and its content in the coating has both characteristics. Affect. When the content of the fluoroalkylsilane is small, the effect of removing scale contaminants and alkali resistance is reduced. On the other hand, if the content is increased, film repelling occurs and a uniform film cannot be obtained.

  From the above viewpoint, in order to obtain a cleaning article having excellent coating homogeneity, removal of scale contaminants and alkali resistance, the fluoroalkylsilane is 0.10 times by weight to 0.30 by weight with respect to silica. Double amount, more preferably 0.15 times to 0.30 times.

  In the fluoroalkylsilane, [p] and [r] affect the bond strength between the fluoroalkylsilane and silica as a matrix. That is, when [p] and [r] are small, the bond strength between the fluoroalkylsilane and silica as a matrix is not sufficient, and the fluoroalkylsilane may fall off the coating due to wiping work or the like during cleaning. . The portion where the fluoroalkylsilane has dropped off has a large interaction with scale contaminants, and as a result, the removal of scale contaminants on the coating is reduced. In addition, the alkali resistance of the dropped part deteriorates.

  [P] and [r] are each preferably 1 to 3 in order to maintain excellent removal of scale pollutants and alkali resistance over a long period of time, and in particular, [r] is 2 or 3 It is preferable that [S] and [q] are preferably 0 from the viewpoint of the bonding between silica and the fluoroalkylsilane.

  Further, the length of the fluorocarbon chain of the fluoroalkylsilane, that is, the number of [m], also affects the removal of scale contaminants and the alkali resistance. If [m] is small, removal of scale pollutants and alkali resistance tend to decrease. If it is large, it is difficult to obtain a uniform film. Therefore, it is important that the number of [m] is 3 to 12. 7 to 12 is particularly preferable.

  Silica as a matrix has an affinity for water. On the other hand, since the fluoroalkylsilane exhibits a contradictory property of repelling water, in order to obtain a highly uniform (non-uniform) film, the amount of silica and the amount of the fluoroalkylsilane are quantitative. This relationship is important. In order to impart sufficient removal of scale contaminants and alkali resistance to easily washable articles, it was necessary to design a film such as sacrificing the homogeneity of the film. In the present invention, by introducing the dimethyl silicone represented by the general formula [B] into the coating, the present invention succeeded in achieving both high homogeneity, sufficient removal of scale contaminants, and sufficient alkali resistance. .

  That is, in addition to making the quantitative relationship between silica and the fluoroalkylsilane as described above, by making the dimethyl silicone 0.001 to 0.050 times by weight with respect to silica, It is possible to satisfy high homogeneity of the coating, alkali resistance, and sufficient removal of scale contaminants. In addition, the dimethyl silicone also has an effect of removing contaminants. When the amount of dimethylsilicone is less than 0.001 times, the homogeneity of the coating is lowered. On the other hand, when the amount is more than 0.050, compatibility with silica is lowered, film repellency occurs, Homogeneity decreases.

  In the dimethyl silicone, the sum of [a] and [c] affects the bond strength between the dimethyl silicone and silica as a matrix. When the sum of [a] and [c] is small, the bond strength between the dimethyl silicone and the silica as a matrix is not sufficient, and the dimethyl silicone is easily detached from the film by a cleaning operation or the like. The portion where the dimethyl silicone has fallen has a large interaction with the contaminants, and as a result, the removability of the contaminants on the coating is reduced. In order to maintain excellent contaminant removability over a long period of time, it is important that the sum of [a] and [c] is 3 or more. Furthermore, [b] and [d] are preferably set to 0 from the viewpoint of the binding property between the dimethyl silicone and silica.

  In the dimethyl silicone, the average degree of polymerization [n] affects the formation of a uniform and highly durable film. When [n] is less than 20, the effect of making the film uniform is small, and the removal property of contaminants of dimethyl silicone is also low. On the other hand, when [n] is more than 2000, the bond strength between the dimethyl silicone and the silica as a matrix is not sufficient, and the dimethyl silicone is easily detached from the film by a cleaning operation or the like. The portion where the dimethyl silicone has fallen has a large interaction with the contaminants, and as a result, the removability of the contaminants on the coating is reduced. Considering the bond strength between dimethyl silicone and silica as a matrix, [n] is preferably 1000 or less.

  The above-mentioned easily cleanable article for water is represented by a silica sol serving as a matrix, a fluoroalkylsilane represented by the general formula [1] (hereinafter referred to as “reactive fluoroalkylsilane”), and a general formula [2]. A coating solution obtained by mixing with an alkoxy group-terminated dimethylsilicone (hereinafter referred to as “reactive dimethylsilicone”) is applied to a substrate, followed by heat treatment at 200 ° C. to 500 ° C. after coating. Can do.

  In the heat treatment, a polycondensation reaction of the silica sol with the reactive dimethyl silicone and the reactive fluoroalkylsilane proceeds to combine the reactive dimethylsilicone and the reactive fluoroalkylsilane with the silica matrix and simultaneously cure the silica matrix. If the heat treatment temperature is low, the polycondensation reaction tends to be insufficient, and the alkali resistance of the coating tends to decrease. On the other hand, when the heat treatment temperature is high, fluoroalkylsilane and dimethylsilicone are thermally decomposed, so that the removal of scale contaminants and alkali resistance of the coating are lowered. Considering the alkali resistance of the coating and the removal of scale contaminants, the heating temperature after coating is more preferably 250 ° C. to 400 ° C.

ここで、Ｂ^２は-ＣＦ_３基、又は-ＣＨ_２ＣＨ_２Ｓｉ(ＣＨ_３)_３−ｔＹ^２ _ｔ基であり、Ｘ^２、Ｙ^２は、それぞれ、１価の加水分解性基である。さらに、［ｍ］は３〜１２の整数、［ｔ］及び［ｕ］は、それぞれ、１〜３の整数である。

Here, B ² is a —CF ₃ group or a —CH ₂ CH ₂ Si (CH ₃ ) _{3 -t} Y ² _t group, and X ² and Y ² are each a monovalent hydrolyzable group. . Furthermore, [m] is an integer of 3 to 12, and [t] and [u] are integers of 1 to 3, respectively.

ここで、Ａ^１、Ａ^２は、それぞれ、２価の炭化水素基、又は、-(ＣＨ_２)_ｉ-ＮＨ-ＣＯ-Ｏ-基（［ｉ］は０〜９の整数）、若しくは、酸素であり、Ｒ^３及びＲ^４は、それぞれ、１価の炭化水素基を表す。さらに、［ｎ］は２０００以下の整数で平均重合度を表す。さらに、［ｅ］及び［ｆ］は、それぞれ、０〜３の整数であり、［ｅ］と［ｆ］の合計は３以上である。

Here, A ¹ and A ² are each a divalent hydrocarbon group or a — (CH ₂ ) _i —NH—CO—O— group ([i] is an integer of 0 to 9), or oxygen R ³ and R ⁴ each represent a monovalent hydrocarbon group. Furthermore, [n] represents an average degree of polymerization with an integer of 2000 or less. Furthermore, [e] and [f] are each an integer of 0 to 3, and the sum of [e] and [f] is 3 or more.

  The easily-cleanable article of the present invention can easily remove contaminants such as scale contaminants in the wiping operation. And since it is excellent in alkali resistance, it is optimal as a member used around the water in the house where an alkaline cleaning agent is frequently used. Furthermore, since it is possible to wash the article of the present invention with an alkaline cleaning agent, it is easy to maintain the cleanliness of the article, and the article of the present invention is used in bathrooms, toilets, kitchens, changing rooms, washstands, etc. In this case, it is effective for maintaining the cleanliness of the member.

  The easy-to-clean article for members used around water in the dwelling of the present invention is an article composed of a base material and a film formed on the base material, the coating film being silica as a matrix, and the above general It consists of a fluoroalkylsilane represented by the formula [A] and a dimethyl silicone represented by the general formula [B].

  The base material used for the easily cleanable article of the present invention is not particularly limited to glass, plastic, tile, bathroom toilet ceramics, etc., but in the case of a glass base material, for example, a window glass for buildings A plate glass having an inorganic transparency such as a float plate glass usually used for a mirror or a soda lime glass produced by a roll-out method can be used. As the plate glass, both colorless and colored ones can be used, and the combination with other functional films, the shape of the glass and the like are not particularly limited. In addition to flat glass and bent glass, various tempered glass such as air-cooled tempered glass and chemically tempered glass, and netted glass can be used. Furthermore, various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.

  The glass substrate can be used as a single plate, and can also be used as a multilayer glass, a laminated glass, or the like. The film may be formed on one side or both sides of the base material, or may be the whole surface or a part of the base material surface.

  The film thickness is preferably 10 nm to 100 nm. If the film thickness is less than 10 nm, the film is difficult to be uniformly formed on the substrate, and film repellency is likely to occur. On the other hand, if it exceeds 100 nm, it is difficult to obtain a film having excellent transparency.

  The silica as the matrix is preferably prepared from a silica sol formed by advancing hydrolysis and polycondensation reaction of alkoxysilane.

The silica sol is prepared, for example, by mixing a predetermined amount of alkoxysilane (for example, tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ]) and a solvent and stirring (for example, about 30 minutes) to obtain a solution A. The solvent is preferably a lower alcohol such as ethyl alcohol or isopropyl alcohol, or a mixed solvent thereof, but is not limited to alcohols, and ethers and ketones can also be used.

  Separately, an acidic aqueous solution and a solvent as described above are mixed and stirred to obtain a solution B. Next, after mixing the solution A and the solution B, the mixture is stirred at room temperature to proceed hydrolysis and polycondensation reaction of alkoxysilane to obtain a silica sol. The stirring time is preferably 10 minutes to 1 week, and particularly preferably 30 minutes to 3 days, but is not limited to this when stirring is performed at a temperature other than room temperature.

  As described above, hydrolysis of alkoxysilane can be performed by adding a small amount of water and an acid catalyst such as hydrochloric acid, nitric acid, acetic acid, and the hydrolyzate is polycondensed by stirring at room temperature or while heating. A silica sol can be obtained. The method for preparing the silica sol is not limited to the above method, but the method of gradually mixing the alkoxysilane diluted with the solvent and the acidic aqueous solution diluted with the solvent is abrupt. It is preferable because a more uniform reaction can be performed.

  Examples of the alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane, or methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and propyltrisilane. Trialkoxysilanes such as methoxysilane and propyltriethoxysilane can be used. Note that it is preferable to use tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane because the silica matrix bond becomes strong and alkali resistance is improved.

  A coating liquid obtained by mixing the reactive fluoroalkylsilane represented by the general formula [1] and the reactive dimethyl silicone represented by the general formula [2] with a silica sol serving as a matrix as a base material. The easily washable article of the present invention can be manufactured by applying and heating at 200 ° C. to 500 ° C. after application.

Examples of the reactive fluoroalkylsilane represented by the general formula [1] include CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si _{(OCH 3) 3, CF 3} (CF 2) 5 CH 2 CH 2 SiCH 3 (OCH 3) 2, CF 3 ( _{F 2) 5 CH 2 CH 2} Si (CH 3) 2 OCH 3, CF 3 (CF 2) 11 CH 2 CH 2 SiCl 3, CF 3 (CF 2) 11 CH 2 CH 2 SiCH 3 Cl 2, CF 3 ( CF ₂ ) ₁₁ CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl, CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ Cl ₂ , CF ₃ (CF _{2 7} CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl, CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) fluoroalkyl sheet having _{5 CH 2 CH 2 Si (CH} 3) 2 Cl at one end to the hydrolyzable group such as _{N'ya, (CH 3 O) 3 SiCH} 2 CH 2 (CF 2) 12 CH 2 CH 2 Si (OCH 3) 3, (CH 3 O) 2 CH 3 SiCH 2 CH 2 (CF 2) 12 CH 2 CH 2 SiCH ₃ (OCH ₃ ) ₂ , CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₁₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF _{2) 10 CH 2 CH 2 Si} (OCH 3) 3, (CH 3 O) 2 CH 3 SiCH 2 CH 2 (CF 2) 10 CH 2 CH 2 SiCH 3 (OCH 3) 2, CH 3 O (CH 3) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₁₀ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , ( _{CH 3 O) 2 CH 3 SiCH} 2 CH 2 (CF 2) 8 CH 2 CH 2 SiCH 3 (OCH 3) 2, CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₈ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si ( _{OCH 3) 3, (CH 3} O) 2 CH 3 SiCH 2 CH 2 (CF 2) 6 CH 2 CH 2 SiCH 3 (OCH 3) 2, CH 3 O (CH 3) 2 SiCH 2 CH 2 (CF 2) ₆ CH ₂ CH ₂ Si (CH ₃ ) ₂ OCH ₃ , Cl ₃ SiCH ₂ CH ₂ (CF ₂ ) ₁₂ CH ₂ CH ₂ SiCl ₃ , Cl ₂ CH ₃ SiCH ₂ CH ₂ (CF ₂ ) ₁₂ CH ₂ CH ₂ SiCH ₃ Cl ₂ , Cl (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₁₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl, Cl ₃ SiCH ₂ CH ₂ (CF ₂ ) ₁₀ CH ₂ CH ₂ SiCl ₃ , Cl _{2 CH 3 SiCH 2 CH 2 (} CF 2) 10 CH 2 CH 2 SiCH 3 Cl 2, _{l (CH 3) 2 SiCH 2} CH 2 (CF 2) 10 CH 2 CH 2 Si (CH 3) 2 Cl, Cl 3 SiCH 2 CH 2 (CF 2) 8 CH 2 CH 2 SiCl 3, Cl 2 CH 3 SiCH ₂ CH ₂ (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ Cl ₂ , Cl (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₈ CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl, Cl ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ SiCl ₃ , Cl ₂ CH ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ Cl ₂ , Cl (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH A fluoroalkylsilane having hydrolyzable groups at both ends, such as ₂ CH ₂ Si (CH ₃ ) ₂ Cl, can be used. When reactive groups are present on the outermost surface of the coating, the scale contaminants are chemically bonded to the reactive groups and adhere firmly to the coating, so that the removal of scale contaminants decreases. Therefore, in order to obtain a good contaminant removal property, it is preferable to reduce the number of reactive groups present on the outermost surface of the coating. Since the fluoroalkylsilane has a rigid molecule, if one having hydrolyzable groups at both ends is used, there is a possibility that the hydrolyzable group, that is, the reactive group, may come out on the outermost surface of the coating. Therefore, in the present invention, it is preferable to use a fluoroalkylsilane having a hydrolyzable group at one end.

Moreover, examples of the hydrolyzable group represented by X ² or Y ² in the general formula [1] include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group, or a chloro group and an isocyanate group. Can be used.

  Since hydrolysis and polycondensation reactions occur in the hydrolyzable group of the reactive fluoroalkylsilane and the alkoxy group of the reactive dimethylsilicone, the reactive fluoroalkylsilane and the reactive dimethyl are formed when a film is formed. Silicone comes to chemically bond with silica as a matrix, and a film having excellent removal of scale contaminants and excellent alkali resistance can be obtained. At this time, the hydrolyzable group and the alkoxy group which are not chemically bonded to the silica matrix react with the hydrolyzable group of the other reactive fluoroalkylsilane and the alkoxy group of the reactive dimethyl silicone to form a bond. There is no problem.

  Next, the preferable preparation method of a coating liquid is demonstrated. The coating solution is prepared by adding the silica sol to be a silica matrix to a mixture obtained by mixing the reactive fluoroalkylsilane represented by the general formula [1] and the reactive dimethyl silicone represented by the general formula [2]. It can be obtained by mixing, hydrolyzing the reactive fluoroalkylsilane and the reactive dimethylsilicone, and further combining with the silica sol by a polycondensation reaction. Here, the reason why the reactive fluoroalkylsilane and the reactive dimethylsilicone are mixed first is to mix both components in the coating solution uniformly. However, when preparing a coating solution by a simpler procedure, silica sol, reactive fluoroalkylsilane and reactive dimethylsilicone may be mixed simultaneously.

  Solvents used in the coating solution include lower alcohols such as ethyl alcohol and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, toluene, benzene and xylene. It is preferable to use ethers such as diethyl ether, diisopropyl ether, and mixtures thereof.

  Next, as an application method for applying the coating liquid obtained above to the substrate surface, hand coating, nozzle flow coating method, dipping method, spray method, reverse coating method, flexo method, printing method, flow coating method, Various coating formation methods such as spin coating and combinations thereof can be appropriately employed.

  Next, by heat treatment, the polycondensation reaction of the silica sol with the reactive dimethyl silicone and the reactive fluoroalkylsilane proceeds to combine the reactive dimethylsilicone and the reactive fluoroalkylsilane with the silica matrix and simultaneously with the silica. The matrix is cured. If the heat treatment temperature is low, the polycondensation reaction tends to be insufficient, and the alkali resistance of the coating tends to decrease. On the other hand, when the heat treatment temperature is high, fluoroalkylsilane and dimethylsilicone are thermally decomposed, so that the removal of scale contaminants and alkali resistance of the coating are lowered. In order to obtain good removal of scale contaminants and alkali resistance, it is important that the heat treatment temperature is 200 ° C. to 500 ° C., particularly preferably 250 ° C. to 400 ° C.

  Removal of contaminants adhering to the surface of the easily washable article for water (coating surface) can be performed by wiping the article surface (coating surface) with a wiping material such as cotton, synthetic fiber or sponge. At this time, although the wiping material and the article surface may be in a dry state or with water and / or a detergent, the wiping material or article surface with water and / or a detergent is preferred. Moreover, since the coating film of the article of the present invention is excellent in alkali resistance, contaminants can be removed even with a commercially available strong alkaline detergent having a pH of 10 to 14.

  Examples of the present invention will be described below.

Example 1
(1) Preparation of coating solution The coating solution was prepared by adding and mixing silica sol (in this example, expressed as silica sol X) to a mixture obtained by mixing reactive fluoroalkylsilane and reactive dimethyl silicone. Obtained. FIG. 1 shows the procedure for preparing the coating solution and the mixing ratio of each chemical solution.

The silica sol X was prepared by proceeding hydrolysis and polycondensation reaction of alkoxysilane tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ : TEOS]. In FIG. 2, the preparation procedure of silica sol X and the mixing ratio of each component are shown.

  First, TEOS; 312.5 g and a mixed solvent of lower alcohol (mixture consisting of 90 wt% ethyl alcohol and 10 wt% isopropyl alcohol); 450.0 g were mixed and stirred for 30 minutes to obtain Solution A.

  Separately, 60% by weight nitric acid aqueous solution; 7.5 g, distilled water; 210.0 g and a mixed solvent of the same lower alcohol as described above; 20.0 g were mixed and stirred for 30 minutes to obtain Solution B.

Next, solution A and solution B were mixed and stirred at room temperature for about 15 hours to obtain silica sol X.
Sample preparation conditions are shown in Table 1, and the details will be described below.

イソプロピルアルコールで１重量％に希釈したヘンイコサフルオロドデシルトリメトキシシラン〔ＣＦ_３（ＣＦ_２）_９ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、以降「Ｃ１０フルオロアルキルシラン」とする〕溶液；１．１３ｇ、ｎ−ヘキサンで０．２重量％に希釈した平均重合度［ｎ］が３００の反応性ジメチルシリコーン〔（ＣＨ_３Ｏ）_３ＳｉＣＨ_２ＣＨ_２{Ｓｉ（ＣＨ_３）_２Ｏ}_３００Ｓｉ（ＣＨ_３）_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３〕液；０．５３ｇ、メチルエチルケトン；７．００ｇとイソプロピルアルコール；７．００ｇを混合し、約５分間攪拌した。次いで、上記シリカゾルＸ；０．７８ｇを添加し、約１５時間室温で攪拌した。次いで、メチルエチルケトン；２６．１８ｇとイソプロピルアルコール；２６．１８ｇとｎ−ブチルアルコール；０．３５ｇを添加し、３０分間攪拌した。

1. Henicosafluorododecyltrimethoxysilane [CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , hereinafter referred to as “C10 fluoroalkylsilane”] solution diluted to 1% by weight with isopropyl alcohol; Reactive dimethyl silicone [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₃₀₀ Si with an average polymerization degree [n] of 300 diluted with 13 g of n-hexane to 0.2% by weight CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] solution; 0.53 g, methyl ethyl ketone; 7.00 g and isopropyl alcohol; 7.00 g were mixed and stirred for about 5 minutes. Next, 0.78 g of the silica sol X was added and stirred at room temperature for about 15 hours. Next, methyl ethyl ketone; 26.18 g and isopropyl alcohol; 26.18 g and n-butyl alcohol; 0.35 g were added and stirred for 30 minutes.

By the above method, it has the polycondensate of the alkoxysilane which will be 0.1 weight% with respect to a coating liquid when converted into a silica, and fluoroalkylsilane is 0.000 by weight with respect to the silica as a matrix after coating. A coating solution was obtained which was 16 times the amount and dimethyl silicone was 0.015 times the amount by weight.
(2) Preparation of base material The surface of 600 mm × 900 mm × 5 mm thick float glass is polished with a suspension obtained by mixing 1% glass abrasive Milleak A (T) (Mitsui Mining & Mining) with water. Then, it was washed with water and dried, and this was used as a substrate for applying the coating solution.
(3) Formation of coating film The coating solution prepared in (1) above is applied onto the substrate prepared in (2) above by spin coating, heat-treated at 350 ° C. for 10 minutes, cooled to room temperature, and An easy-to-clean article was obtained.

The obtained article was evaluated according to the following evaluation methods (a) to (c). As shown in Table 2, the evaluation results showed excellent removal of scale contaminants and alkali resistance.
(A) Removal of scale contaminants Samples are cut to a size of 150 mm x 75 mm and attached to a sunshine weather meter (model number: WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd.) at an angle of 90 °. While always irradiating, it was allowed to stand for 500 hours under the condition of spraying tap water for 12 minutes at intervals of 48 minutes, and scale was adhered. Here, tap water was used as it was without passing through the ion exchange membrane. Next, five reciprocations were wiped with a load of 120 g / cm ² using a 100% cotton cloth wiped with water on the sample surface to which scale contaminants adhered. After wiping, visual observation was performed, and a sample in which removal of scale contaminants was confirmed was used as a sample having excellent contaminant removal properties. The main purpose of this test is to evaluate the removal of scale contaminants.

The main cause of scale is soluble silicate contained in tap water. The soluble silicate deposits and solidifies when it adheres to the article and dries. The solidified product is visually confirmed, and is recognized as scale contamination. Considering the formation mechanism of the scale dirt, it is judged that the article from which the scale contaminants are removed in the pollutant removal test has sufficient characteristics as an easy-to-clean article excellent in scale dirt removal. it can.
(B) Alkali resistance A 1.0 N NaOH aqueous solution was brought into contact with the coating surface of the sample for 2 h. Thereafter, the sample surface was washed with water, and then a dirt soil was adhered to the sample surface in accordance with the procedure described in “(a) Removability of scale contaminants”. Finally, using a 100% cotton wipes containing water, wipe the area where the NaOH aqueous solution was in contact with the load of 240 g / cm ² 5 times, and after wiping, visually observe to confirm the removal of scale contaminants. The obtained sample was a sample excellent in alkali resistance.
(C) Film thickness The film thickness of the easily washable article for water circumference was measured with a surf coder (manufactured by Kosaka Laboratory, ET4000A).

実施例２
反応性フルオロアルキルシランにヘプタデカフルオロデシルトリメトキシシラン〔ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、以降「Ｃ８フルオロアルキルシラン」とする〕を用いた以外はすべて実施例１と同じとした。結果、得られた物品は、表２に示すとおり、優れた汚染物の除去性と耐アルカリ性を示した。

Example 2
All examples except that heptadecafluorodecyltrimethoxysilane [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , hereinafter referred to as “C8 fluoroalkylsilane”] was used as the reactive fluoroalkylsilane. Same as 1. As a result, as shown in Table 2, the obtained article exhibited excellent contaminant removal and alkali resistance.

Example 3
All were the same as Example 1 except that the weight ratio of fluoroalkylsilane to silica as a matrix was 0.19 times. As a result, as shown in Table 2, the obtained article exhibited excellent removal of scale contaminants and alkali resistance.

Example 4
All were the same as Example 1 except that the weight ratio of fluoroalkylsilane to silica as a matrix was 0.13 times the amount. As a result, as shown in Table 2, the obtained article exhibited excellent removal of scale contaminants and alkali resistance.

Example 5
Reactive dimethyl silicone [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₁₀₀ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3 with an} average degree of polymerization [n] of 100 ] Was used in the same manner as in Example 1. As a result, as shown in Table 2, the obtained article exhibited excellent removal of scale contaminants and alkali resistance.

Comparative Example 1
All were the same as Example 1 except that the fluoroalkylsilane with respect to silica as a matrix was 0.07 times by weight. As a result, as shown in Table 2, the obtained article had low alkali resistance.

Comparative Example 2
Reactive dimethyl silicone [(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₂₅₀₀ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si ( All were the same as in Example 1 except that CH ₃ ) (OCH ₃ ) ₂ ] was used. As a result, as shown in Table 2, the obtained article had low alkali resistance.

Comparative Example 3
All were the same as Example 2 except that dimethyl silicone with respect to silica as a matrix was 0.0001 times by weight. As a result, as shown in Table 2, a uniform film was not obtained.

Comparative Example 4
Example 2 was the same as Example 2 in which the amount of dimethyl silicone relative to silica as the matrix was 0.1 times the weight ratio. As a result, as shown in Table 2, a uniform film was not obtained.

Comparative Example 5
All were the same as Example 2 except that the fluoroalkylsilane with respect to silica as a matrix was 0.40 times by weight. As a result, as shown in Table 2, a uniform film was not obtained.

Comparative Example 6
The heat treatment temperature was the same as Example 1 except that the heat treatment temperature was 100 ° C. As a result, as shown in Table 2, the alkali resistance was low.

It is a figure which shows the process for obtaining the coating liquid in Example 1. FIG. 2 is a diagram showing a process for obtaining silica sol X. FIG.

Claims (7)

An article comprising a substrate and a coating formed on the substrate, wherein the coating is represented by silica as a matrix, a fluoroalkylsilane represented by the general formula [A], and a general formula [B]. The fluoroalkylsilane content is 0.10 to 0.30 times by weight with respect to silica, and the dimethylsilicone content is 0.001 by weight with respect to silica. A washable article for members used around water in a dwelling having excellent alkali resistance, characterized in that the amount is double to 0.050.

Here, B ¹ is a —CF ₃ group, or —CH ₂ CH ₂ Si (CH ₃ ) _{3 -pq} Y ¹ _q (O—) _p group, and X ¹ and Y ¹ are each monovalent. The hydrolyzable group or —OH group. [M] is an integer of 3 to 12, and [p] and [r] are integers of 1 to 3, respectively. Furthermore, [q] and [s] are each an integer of 0 to 2, and the sum of [p] and [q] and the sum of [r] and [s] are each 3 or less. Further, the oxygen at the terminal indicates a state in which it is bonded to other chemical species or the same chemical species.

Here, A ¹ and A ² are each a divalent hydrocarbon group or a — (CH ₂ ) _i —NH—CO—O— group ([i] is an integer of 0 to 9), or oxygen And R ¹ and R ² are each a monovalent hydrocarbon group or hydrogen. Furthermore, [n] represents an average degree of polymerization with an integer of 2000 or less. Furthermore, [a] and [c] are each an integer of 0 to 3, and the sum of [a] and [c] is 3 or more. Furthermore, [b] and [d] are each an integer of 0 to 3, and the sum of [a] and [b] and the sum of [c] and [d] are each 3 or less. Further, the oxygen at the terminal indicates a state in which it is bonded to other chemical species or the same chemical species.
The easily washable article according to claim 1, wherein [r] of the fluoroalkylsilane represented by the general formula [A] is 2 or 3.
The content of the fluoroalkylsilane represented by the general formula [A] is 0.15 to 0.30 times by weight with respect to silica. Easy-to-clean goods.
The easily-cleanable article according to any one of claims 1 to 3, wherein [m] of the fluoroalkylsilane represented by the general formula [A] is 7 to 12.
The easily washable article according to any one of claims 1 to 4, wherein the average degree of polymerization [n] of the dimethyl silicone represented by the general formula [B] is 20 to 1000.
The content of the dimethyl silicone represented by the general formula [B] is 0.010 times to 0.030 times by weight with respect to silica. The easily washable article as described in 1.
After applying a coating solution obtained by mixing a silica sol serving as a matrix with a fluoroalkylsilane represented by the general formula [1] and an alkoxy-terminated dimethyl silicone represented by the general formula [2] on a substrate The method for producing an easily-cleanable article according to any one of claims 1 to 6, wherein a heat treatment at 200 ° C to 500 ° C is performed.

Here, B ² is a —CF ₃ group or a —CH ₂ CH ₂ Si (CH ₃ ) _{3 -t} Y ² _t group, and X ² and Y ² are each a monovalent hydrolyzable group. . Furthermore, [m] is an integer of 3 to 12, and [t] and [u] are integers of 1 to 3, respectively.

Here, A ¹ and A ² are each a divalent hydrocarbon group or a — (CH ₂ ) _i —NH—CO—O— group ([i] is an integer of 0 to 9), or oxygen R ³ and R ⁴ each represent a monovalent hydrocarbon group. Furthermore, [n] represents an average degree of polymerization with an integer of 2000 or less. Furthermore, [e] and [f] are each an integer of 0 to 3, and the sum of [e] and [f] is 3 or more.

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