JP2006144019A - Treating agent for obtaining water sliding coat, and method for making water sliding coat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent which is capable of forming a coat by the drying thereof on a substrate and by the wiping work after the drying without needing a heating process, and to provide a coat thereof which is excellent in the water repellency, the water sliding property and the durability. <P>SOLUTION: The treating agent is formed by mixing a straight chain polydimethylsiloxane that has, at the at least one end, two or three of hydrolyzable functional groups and has 30-400 of dimethylsiloxane units [Si(CH<SB>3</SB>)<SB>2</SB>O]; a fluoroalkylsilane that has a hydrolyzable functional group and has 6-12 of fluorocarbon units (CF<SB>2</SB>or CF<SB>3</SB>);and a solution containing at least an organic solvent, an acid and water, with the treating agent being mixed with the above straight chain polydimethylsiloxane of 0.2-3.0 % by weight concentration relative to the total amount of the treating agent, the above fluoroalkylsilane of 0.2-2.0% by weight concentration and the sum total amount of both the above straight chain polydimethylsiloxane and the above fluoroalkylsilane of 0.5-3.5% by weight concentration. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a treatment agent for obtaining a water-slidable film capable of forming a film on a substrate by drying at about room temperature, and a production method for obtaining a water-slidable film.

A phenomenon that water droplets or the like adhere to a window glass or a side mirror of a vehicle or the like and it is difficult to travel in the rain occurs on a daily basis. In order to solve such a problem, means such as forming a film having high water repellency or high water slidability on a substrate such as glass has been taken. However, since the life of the coating is not permanent, the water repellency or water slidability of the coating may not maintain the initial performance during use. In such a case, it is required to recover the water repellency or water slidability by applying a treatment agent on the deteriorated film or on the substrate from which the film has been removed.

In order to satisfy the functions and durability of water repellency and water slidability, it is desirable to heat the treatment agent at 100 ° C. or higher after applying the treatment agent to the base material. When a film is formed by a treatment at about room temperature, it is necessary to devise a treatment agent.

Patent Document 1 discloses a surface treatment agent for vehicle glass having perfluoroalkylsilane, organopolysiloxane, etc., and a film formed by drying at room temperature with the treatment agent is excellent in water repellency and water slidability, It has been shown to suppress judder generation.

However, the water repellency, water slidability and durability of the coating obtained from such a treatment agent vary greatly depending on the concentration and reactivity of perfluoroalkylsilane and organopolysiloxane in the treatment agent. In addition, when such a treatment agent is used, the functional components that give rise to functions such as water repellency and water slidability that were not involved in the formation of the coating after the treatment are dried up as an excess, so that the translucency of the resulting coating is obtained. It adversely affects functions such as water repellency and water slidability. And when removing this surplus by wiping cloth etc., the ease of removal depends on the density | concentration and the reactivity in the processing agent of perfluoroalkylsilane or organopolysiloxane. However, Patent Document 1 does not discuss these points.

Patent Document 2 discloses a treatment agent comprising a silicone having a hydrolyzable functional group at the terminal and a fluoroalkyl group at the other end mixed with a solution containing acid, water, etc. It is shown that the film obtained in this way is excellent in water repellency and water slidability. However, since the treatment agent disclosed in Patent Document 2 requires heating at 100 ° C. or higher after being applied to the base material, it may be necessary to form a coating on a window glass assembled in a vehicle or the like. It is not suitable for recovering the water repellency and water slidability of the film being treated.
JP-A-2-233535 JP 2000-144056 A

The present invention can form a film excellent in water repellency, water slidability and durability by applying a treatment agent without performing a heating step, for example, a film can be formed later on an existing vehicle window, etc. It is another object of the present invention to provide a treating agent that can easily remove excess dry solids by a functional component that causes functions such as water repellency and water slidability that are not involved in the formation of a film after treatment.

That is, the treating agent for obtaining the water-slidable coating film of the present invention has two or three hydrolyzable functional groups at at least one end, and has a dimethylsiloxane unit (Si (CH ₃ )).
₂ O) a linear polydimethylsiloxane having 30 to 400, and a fluoroalkylsilane having a hydrolyzable functional group and having 6 to 12 fluorocarbon units (CF ₂ or CF ₃ ) , And a treatment agent obtained by mixing a solution containing an organic solvent, an acid, and water, and the linear polydimethylsiloxane is 0.2% by weight with respect to the total amount of the treatment agent.
-3.0 wt%, fluoroalkylsilane is 0.2-2.0 wt%, and the total amount of linear polydimethylsiloxane and fluoroalkylsilane is 0.5-3.5 wt% It is characterized by that. (Hereinafter, in this specification, when both linear polydimethylsiloxane and fluoroalkylsilane are shown, it is expressed as “functional component”. Also, when the total amount of linear polydimethylsiloxane and fluoroalkylsilane is shown. , Written as “total amount of functional ingredients”.)

Since the linear polydimethylsiloxane has excellent slidability and has a dimethylsiloxane chain, it improves the slidability of the resulting coating. On the other hand, since the fluoroalkylsilane has a fluoroalkyl chain having excellent durability, the durability of the resulting coating is improved.

The linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one terminal, and the fluoroalkylsilane also has a hydrolyzable functional group. The hydrolyzable functional group is hydrolyzed with an acid and water contained in the treatment agent to form a highly reactive silanol group. Thus, when the treatment agent is applied to the substrate, the surface of the substrate reacts with the silanol groups, and the linear polydimethylsiloxane and the fluoroalkylsilane are firmly bonded to the substrate, resulting in the resulting water-slidable coating. Durability is improved.

Furthermore, the acid and water have an effect of hydrolyzing the hydrolyzable functional group of the linear polydimethylsiloxane or the fluoroalkylsilane to form a silanol group that can be bonded to the substrate.

Furthermore, the processing method for obtaining the water-slidable coating film of the present invention includes a step of applying the treatment agent according to any one of claims 1 to 6 to a substrate, and a step of drying the substrate coated with the treatment agent. And a step of removing unreacted or hydrolyzed or condensed functional components (hereinafter referred to as “surplus”) that were not involved in the formation of the film in a free state after drying.

The treatment agent for obtaining the water slidable coating film of the present invention exhibits excellent water repellency, water slidability and durability by being dried on the substrate after treatment. For this reason, it is optimal as a processing agent for processing to a base material that cannot be heat-treated, such as a window glass and a side mirror assembled in a vehicle or the like. Furthermore, since it is easy to remove the surplus after processing, the work load is small.

The treatment agent for obtaining the water-slidable coating film of the present invention has two or three hydrolyzable functional groups at at least one terminal, and the number of dimethylsiloxane units (Si (CH ₃ ) ₂ O). A linear polydimethylsiloxane having 30 to 400, a fluoroalkylsilane having a hydrolyzable functional group and having 6 to 12 fluorocarbon units (CF ₂ or CF ₃ ), and an organic solvent, acid And a treatment agent obtained by mixing a solution containing water,
The linear polydimethylsiloxane is 0.2 to 3.0% by weight, the fluoroalkylsilane is 0.2 to 2.0% by weight, and the total amount of functional components is based on the total amount of the treatment agent. 0.5 to 3.5 wt% is mixed.

In the linear polydimethylsiloxane used in the treatment agent of the present invention, it is important that the number of dimethylsiloxane units (Si (CH ₃ ) ₂ O) is 30 to 400.

When the number of dimethylsiloxane units of the linear polydimethylsiloxane exceeds 400, the number of hydrolyzable functional groups of the linear polydimethylsiloxane decreases relative to the dimethylsiloxane unit, Reactivity of dimethylsiloxane is reduced. As a result, the resulting coating is weakly bonded to the substrate, and the light resistance and mud-water polishing resistance of the coating is reduced, and the resulting water-slidable coating is rapidly deteriorated.

A substrate having a water-slidable coating produced using the treatment agent of the present invention is often used outdoors, and is often exposed to sunlight. And since there are many opportunities for dust to adhere, muddy water is polished when wiping with a rag or wiper during cleaning. Formation of a film excellent in light resistance and mud water abrasion resistance is very important from a practical viewpoint, and these are particularly important in forming a film on a vehicle window.

On the other hand, when the base material is treated with the treatment agent of the present invention, a functional group in the treatment agent that can be hydrolyzed reacts with a reactive group such as a hydroxyl group represented by a silanol group present on the surface of the base material. By bonding, the functional component is fixed to the substrate. Therefore, when the number of units decreases, the number of dimethylsiloxane units fixed on the substrate decreases. As a result of the study in the present invention, it was found that the muddy water abrasion resistance of the formed film is affected by the number of units. And when the number of units is 30 or more, these characteristics are remarkably improved, and the resulting coating is used for a long time.

Further, it is important that the linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one terminal. When the number of hydrolyzable functional groups at both ends is 1 or less, the reactivity of the polydimethylsiloxane is greatly reduced, and the bond with the substrate is weakened. This is not preferable because the light resistance of the resulting water-slidable coating film is lowered and the coating film is rapidly deteriorated.

Furthermore, it is important that the linear polydimethylsiloxane is mixed in an amount of 0.2 to 3.0% by weight based on the total amount of the treating agent. As a water repellent, perfluoroalkylsilane is generally used as a functional component, but this has a low water slidability and a minimum inclination angle (hereinafter referred to as a tumbling angle) of 25 that allows 50 μl of water droplets to slide down. It is as large as ~ 27 °.

When the water-sliding film is actually used, the falling angle that is an index of water-sliding is around 20 °.
It is experienced that there is a difference in the sliding property or scattering property of the water droplet from the coating. And when a sliding film is used for a vehicle window, this is noticeable.

And when the said linear polydimethylsiloxane is less than 0.2 weight% with respect to the total amount of a processing agent, since the fall angle of the film obtained exceeds 20 degrees, the water slidability of a film will become low.

In addition, after the treatment agent is applied to the substrate and dried, the surplus becomes a dry solid and remains on the substrate. If the concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent exceeds 3.0% by weight, the amount of dried solids increases during the film formation, and this removal process is burdened and takes time. become. This long-time wiping increases the possibility of scratching the coating and increases the risk of adversely affecting the water slidability and durability.

Furthermore, considering the usage environment of the treatment agent, this removal process is often manual wiping, so if the time (load) of the removal process is large, the dry solids can be removed as a result. In many cases, it remains on the film. If the surplus remains, water droplets are caught by the surplus and cannot move smoothly, resulting in a decrease in lubricity. Furthermore, since the surplus remains white and mottled on the surface of the coating, the translucency of the coating is reduced.

The removal process was examined by applying a treatment agent to the front window of a normal passenger car and drying it, followed by manual wiping with a paper towel, cloth, wiper, etc. It was found that fatigue was experienced and removal of the excess could not be performed sufficiently.

As a result of the examination, it was found that when the concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent is 3.0% by weight or less, the treatment agent considering the above points can be obtained. Moreover, it is preferable that the said removal process becomes shorter time, and specifically, it is still better if it is less than 3 minutes. In consideration of this point, the linear polydimethylsiloxane is preferably 2.5% by weight or less based on the total amount of the treatment agent.

As the linear polydimethylsiloxane, polydimethylsiloxane represented by the following general formula [1] is preferably used.

Here, X ¹ and X ² are monovalent hydrolyzable functional groups, respectively, A ¹ and A ²
Are respectively a divalent hydrocarbon group, a — (CH ₂ ) _i —NH—CO—O— group ([i] is an integer of 0 to 9), or oxygen. [N] is an integer of 30 to 400 and represents the number of dimethylsiloxane units. Furthermore, [a] and [b] are each an integer of 0 to 3, and [a
] Or [b] must be 2 or 3.

Further, A ¹ and A ² of the polydimethylsiloxane represented by the general formula [1] are sites that connect a hydrolyzable functional group and a dimethylsiloxane chain that exhibits water repellency and water slidability. Therefore, when the stability of this portion is lowered, the dimethylsiloxane chain easily drops off from the water-slidable coating, and the durability of the coating is reduced. Therefore, A ¹ and A ² of the polydimethylsiloxane represented by the general formula [1] is a divalent hydrocarbon group or oxygen excellent in stability are preferred.

The fluoroalkylsilane used in the treating agent of the present invention has a hydrolyzable functional group, and the number of fluorocarbon units (CF ₂ or CF ₃ ) in the molecule is 6 to 1.
2 having a perfluoroalkyl group (CF ₃ (CF ₂ ) _t-1 —) or a perfluoroalkylene group (— (CF ₂ ) _u —) is used. Fluorocarbon unit (
Increasing the number of CF ₂ or CF ₃ ) increases the light resistance and mud water abrasion resistance of the resulting water-slidable coating. Here, the t and u represent integers.

However, as the number of fluorocarbon units increases, the freezing point of the fluoroalkylsilane rises to room temperature or higher, so that the functional component is easily solidified and difficult to apply, and the fluoroalkylsilane becomes an excess. In some cases, these are more firmly fixed to the surface of the base material, and the load required to remove the surplus is increased.

Therefore, it improves the light resistance and mud water abrasion resistance of the coating film obtained, makes it easy to apply the treatment agent, further facilitates the excess after drying, and is necessary for removing the excess in the front window of ordinary passenger cars. In order to make the time 6 minutes or less, it is important that the number of fluorocarbon units is 6-12.

Furthermore, it is important that the fluoroalkylsilane is mixed in an amount of 0.2 to 2.0% by weight with respect to the total amount of the treatment agent. If it is less than 0.2% by weight, the light resistance and the muddy water abrasion resistance are remarkably lowered. On the other hand, if it exceeds 2.0% by weight, the water slidability is greatly lowered, and the falling angle exceeds 20 °. And in order to obtain higher sliding property (falling angle; 18 degrees or less) and durability, it is preferable to make the mixing amount into 0.5 to 1.6 weight% by weight concentration.

Examples of the fluoroalkylsilane include a fluoroalkylsilane having a hydrolyzable functional group at one end represented by the following general formula [2] and a hydrolyzable functional group represented by the following general formula [3]. The fluoroalkylsilane having is preferably used.

Here, Y ¹ is a monovalent hydrolyzable functional group. Furthermore, [m] is an integer of 6 to 12 and represents the number of fluorocarbon units (CF ₂ or CF ₃ ). Furthermore, [p] is 1
It is an integer of ˜3 and represents the number of hydrolyzable functional groups.

Here, Y ² and Y ³ are each a monovalent hydrolyzable functional group. Furthermore, [m
] Is an integer of 6 to 12 and represents the number of fluorocarbon units. Furthermore, [q] and [r] are integers of 1 to 3, respectively.

As the fluoroalkylsilane, CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) as a fluoroalkyl silane having a hydrolyzable functional group at one end.
₁₁ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si (CH ₃ ) ₂ O
CH ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si
CH 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 (CF 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 ) _1
1 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 (C
F 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 , C
F ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (CH ₃ ) ₂ Cl or the like can be used, and as a fluoroalkylsilane having a hydrolyzable functional group at both ends, (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 (C
F 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 C
_{H 2 Si (OCH 3) 3} , (CH 3 O) 2 CH 3 SiCH 2 CH 2 (CF 2) 10 CH 2 CH 2 SiC
H 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 , (C
_{H 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 S
_{iCH 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 (C
F 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 (C
_{H 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 S
iCH ₃ Cl ₂ , Cl (CH ₃ ) ₂ SiCH ₂ CH ₂ (CF ₂ ) ₁₀ CH ₂ CH ₂ Si (CH ₃ ) ₂ C
l, 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 C
H ₂ Si (CH ₃ ) ₂ Cl, Cl ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ SiCl ₃ , Cl ₂ C
H 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 ₂ CH ₂ Si (CH ₃ ) ₂ Cl or the like can be used.

However, a fluoroalkylsilane having a hydrolyzable functional group at both ends has a tendency to condense easily because it has a hydrolyzable functional group at both ends, which makes it difficult to apply the treatment agent. is there. Furthermore, since it becomes easy to become the condensed surplus when it becomes a surplus, the surplus is firmly fixed to the base material, and it becomes difficult to remove the surplus after drying. Considering this point, it is preferable to use a fluoroalkylsilane having a hydrolyzable functional group only at one end.

Moreover, as a hydrolyzable functional group in the functional component, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butoxy group, a chloro group or an isocyanate group can be used. However, if the reactivity of the hydrolyzable functional group is too high, not only is the handling difficult when preparing the treatment agent, but the pot life of the treatment agent is shortened. On the other hand, if the reactivity is too low, the hydrolysis reaction will not proceed sufficiently, and the amount of silanol groups produced will not be sufficient, so the bond between the substrate and the resulting water-slidable coating will not be sufficient, and the durability of the coating will be reduced. Lower. In view of ease of handling, pot life of the treating agent, and durability of the resulting water slidable coating, the hydrolyzable functional group is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group.

Further, it is important that the total amount of the functional components is mixed in the concentration of 0.5 to 3.5% by weight with respect to the total amount of the processing agent. If it is less than 0.5% by weight, the light resistance and muddy water abrasion resistance of the resulting coating will be reduced. On the other hand, if it exceeds 3.5% by weight, the removability of the excess is reduced,
In the process of removing excess after drying, the manual wiping time using a paper towel, cloth, wiper, etc. exceeds 6 minutes in the front window of a normal passenger car. And in order to make durability of a film higher and to make easy removal of the surplus after application | coating and drying of a processing agent, it is preferable to set it as 0.8 to 3.0 weight%.

In addition, the polydimethylsiloxane may have two or three hydrolyzable functional groups at at least one end, and as such, the hydrolyzable functional group only at one end. Or those having a hydrolyzable functional group at both ends. Those having a reactive group only at one end can be expected to have better fallability since the other end is a highly hydrophobic alkyl group. In addition, the number of silanol groups produced is small and the reactivity is low. For this reason, since there is little production | generation of the excess part which condensed, as a result, there is little production | generation of the dried solid substance which adheres firmly to a film, and there exists a tendency for the removal of the excess part after application | coating and drying to become easy,
It becomes difficult to react with the substrate. Therefore, when using the one having a hydrolyzable functional group only at one end, it is preferable to increase the amount of the polydimethylsiloxane or the fluoroalkylsilane in the treatment agent. The total amount of mixed components is 0.5 to 2.5% by weight of linear polydimethylsiloxane, 0.6 to 1.6% by weight of fluoroalkylsilane, and the total amount of functional components. It is preferable to set it as 1.2 to 3.0 weight%.

On the other hand, those having a hydrolyzable functional group at both ends are highly reactive. For this reason,
It is easy to bond firmly to the substrate, and as a result, a water slidable film with excellent durability can be obtained, but the condensed excess is easily generated, so the removal of the excess after applying and drying the treatment agent is poor. Tend to be. Therefore, when using a functional group having hydrolyzable functional groups at both ends, it is preferable to reduce the amount of the polydimethylsiloxane or the fluoroalkylsilane in the treatment agent, specifically the total amount of the treatment agent. On the other hand, the mixing amount is 0.2 to 2.0% by weight of linear polydimethylsiloxane and 0.5 to 1.4% by weight of fluoroalkylsilane by weight concentration.
Furthermore, the total amount of functional components is preferably 0.8 to 2.5% by weight.

The solvent used for the treating agent can be an organic solvent that dissolves other components (linear polydimethylsiloxane, fluoroalkylsilane, water, acid), and these 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, ethers such as diethyl ether and diisopropyl ether, and mixtures thereof It is preferable. Among them, a mixed solvent of at least one solvent selected from methyl ethyl ketone, ethyl acetate, hexane, diethyl ether and diisopropyl ether and a lower alcohol such as ethyl alcohol or isopropyl alcohol is linear polydimethylsiloxane, fluoroalkylsilane, water. In addition, the solubility of acid and acid is high, and furthermore, the coating property of the processing agent (ease of spreading) and the drying time of the processing agent (working time)
Is particularly preferable since it becomes moderate.

The water used in the treatment agent of the present invention has a molecular number of 1 to 10 times the number of hydrolyzable functional groups of the linear polydimethylsiloxane and the fluoroalkylsilane.
It is preferably 0 times. If it is less than 1 time, the hydrolysis reaction does not proceed, silanol groups are not sufficiently generated, and the durability of the resulting water-slidable coating film is lowered, which is not preferable. On the other hand, if it exceeds 100 times, it becomes difficult to uniformly dissolve the linear polydimethylsiloxane, the fluoroalkylsilane and water in the treatment agent. Further, when the amount of water increases, the reaction rate increases, and as a result, the pot life of the treatment agent is shortened. Therefore, considering the pot life, it is more preferably 50 times or less.

Furthermore, the acid used for the treating agent plays a catalytic role for promoting the hydrolysis reaction of the functional component, and nitric acid, hydrochloric acid, acetic acid, sulfuric acid, and other organic acids can be used. And it mixes so that pH value may become 0-5, preferably 0-2 in the state mixed with the said water.

Next, a preferred method for preparing the treatment agent for obtaining a water-slidable coating will be described. In order to obtain a water slidable coating, a treating agent is added to the mixture of the linear polydimethylsiloxane, the fluoroalkylsilane, and a solvent with water and an acid for causing a hydrolysis reaction, mixed, and then mixed with the linear polydimethylsiloxane. It is obtained by hydrolyzing dimethylsiloxane and the fluoroalkylsilane. Here, the reason why the linear polydimethylsiloxane and the fluoroalkylsilane are mixed first is to mix both components homogeneously in the treating agent. However, acid, water, linear polydimethylsiloxane and fluoroalkylsilane may be mixed simultaneously.

  Next, a method for obtaining a water-slidable film using the obtained treatment agent will be described.

Examples of the application method for applying the coating solution obtained above onto the substrate surface include hand coating, nozzle flow coating method, dipping method, spray method, reverse coating method, flexo method, printing method, flow coating method, and spin coating method. Various coating methods such as a combination thereof can be appropriately employed.

The base material to which the treatment agent is applied is not particularly limited. For example, in the case of a glass base material, a float plate glass or a roll usually used for a window glass for a building or a mirror is used. Plate glass with inorganic transparency such as soda lime glass produced by the luout method can be used. The plate glass can be used both colorless and colored, in combination with other functional films,
The shape of the glass is not particularly limited. In addition to flat glass and bent glass, various glass such as air-cooled tempered glass and chemically tempered 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 coating obtained from the treatment agent of the present invention is excellent in visible light transmission, but can be used even for applications that do not require visible light transmission. May be used.

In addition, since the treatment agent of the present invention does not require heating, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene, polyvinyl chloride, and other plastic substrates can be used.

Furthermore, the base material may be formed by applying a solution to which a silicon compound having four functional groups is added to the base material and solidifying the base material to form a primer layer derived from the silicon compound. good. The primer layer can increase the number of sites for binding to the coating, that is, the number of silanol groups, as compared with the substrate itself. Thus, the water-slidable coating formed using the substrate on which the primer layer is formed can be expected to further improve durability. The primer layer may be a monomolecular layer.

As the silicon compound having four functional groups, tetraisocyanate silane, tetrahalogenated silane, tetramethoxysilane, tetraethoxysilane and the like can be used. And these chemical species are added to a solvent, and the solution for apply | coating to the base-material surface is prepared. Examples of the solvent include alcohols such as lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol, or general organic solvents such as paraffinic hydrocarbons and aromatic hydrocarbons such as n-hexane, toluene, and chlorobenzene. Or mixtures thereof.

In order to adjust the pH of the solution to 0 to 5, an acid such as hydrochloric acid, nitric acid or acetic acid may be introduced, and a small amount of water may be introduced to accelerate the hydrolysis reaction of the chemical species. . In order to efficiently form a primer layer, the chemical species may be added in an amount of 0.5% to 2% by weight, preferably 0.7% to 1.5% by weight, based on the solvent. Preferably 0.9 wt% to 1.
It is preferable to add 2% by weight to prepare the solution.

As a method for applying the coating solution onto the surface of the glass substrate, known means such as a spray coating method, a bar coating method, a roll coating method, a spin coating method, a brush coating method, a dip coating method and the like can be used. Considering the ease of forming the primer layer, the ease of preparing the solution, the number of silanol groups formed, etc., it is preferable to use tetraisocyanate silane as the chemical species.

In order to enhance the adhesion to the substrate, the solution may be fired at 50 to 350 ° C., preferably 100 to 300 ° C. after being applied to the substrate. Then, immediately after the formation of the primer layer, the treatment agent of the present invention may be applied to form a water slidable film. In addition, when the treatment agent of the present invention is applied to the substrate after the substrate on which the primer layer is formed is stored and distributed, silanol groups on the primer layer are present in the organic matter or in the air. It is possible that the primer layer is reactivated by the contact of the acidic solution with the deactivated primer layer or the irradiation of ultraviolet rays, etc., and the primer layer is activated again. It is preferable to do.

Next, the treatment after applying the treatment agent to the substrate will be described. The polydimethylsiloxane and the fluoroalkylsilane are bonded to the substrate by applying a treatment agent to the substrate and then drying it. The drying means may be air-dried and at room temperature, for example, 15 ° C. to 30 ° C., relative humidity 30% to 6%.
It is only necessary to leave it for 5 to 20 minutes in a 0% environment. In order to shorten the drying time, hot air may be blown with a general-purpose dryer or the like.
You may heat at 250 degreeC.

Finally, since the surplus is dried and remains on the film, the slippery film can be formed by wiping the surplus with a paper towel or cloth dampened with an organic solvent and / or a dry paper towel or cloth. A formed substrate is obtained.

In the present invention, the water slidability is evaluated by a method as described in the evaluation method of the example. After dropping 50 μl of pure water on the sample surface, the sample is gradually tilted, and the water droplets move. It is evaluated by measuring the tilt angle at the start. The tilt angle was defined as a sliding angle (°), and the sliding angle was measured in the atmosphere (about 25 ° C.) using a CA-A type manufactured by Kyowa Interface Science.

Examples of the present invention will be described below. The present invention is not limited to these examples. The evaluation method of the water slidable coating is shown below.

    [Evaluation method of water slidable coating]

(1) Contact angle The angle formed by the water droplet and the sample surface when about 2 μl of pure water was placed on the sample surface having the water slidable coating was measured with a contact angle meter. In addition, Kyowa Interface Science CA-X type is used for the contact angle meter,
Measurement was performed in the atmosphere (about 25 ° C.).

(2) Falling angle After holding 50 μl of pure water on the sample surface while holding the sample horizontally, the sample is gradually tilted, and the tilt angle at the time when the water droplet starts to move is defined as the falling angle (°). did. The sliding angle was measured in the atmosphere (about 25 ° C.) using Kyowa Interface Science CA-A type. The initial performance of the tumbling angle is 20 ° or less with respect to the index of water slidability (shown as “◯” in Table 1 or 2).
, 18 ° or less was particularly excellent (indicated as “◎” in Table 1 or Table 2). In addition, the thing over 20 degrees was set as the rejection, and was described as x in Table 1 or Table 2.

(3) Removability of excess parts After applying the treatment agent and air-drying, a transparent sample is wiped with a paper towel (product name: Kim Towel) moistened with isopropyl alcohol after the white residue remains visually. The time required to obtain a transparent sample was measured when producing (a normal automobile front window). Those with an excess removal time (wiping time) of 6 minutes or less were accepted (Table 1).
Or, in Table 2, it is indicated by ○). Furthermore, it was judged that those that were completed within 3 minutes were particularly excellent in the removal of the excess (shown as ◎ in Table 1 or 2). In addition, what took more than 6 minutes for the removal time was rejected, and indicated as x in Table 1.

(4) Muddy water abrasion resistance (ceria abrasiveness)
A cotton cloth impregnated with a ceria suspension (10% by weight) in which glass abrasives Milleak A (T) (Mitsui Mining & Mining) is dispersed in tap water, and the surface of the sample is a strong 1.5 kg / cm ² . Then it was polished. The number of times of polishing (reciprocation) until 70% of the polishing region became hydrophilic was evaluated. here,
Passed 40 times or more (indicated in Table 1 or 2 in Table 2), and passed 50 times or better (in Table 1 or 2)
And 60 times or more were regarded as excellent (indicated as ◎ + in Table 1 or 2). In addition, the thing less than 40 times was made disqualified, and it described with x in Table 1 or Table 2.

(5) Light resistance It evaluated by measuring the contact angle (degree) after irradiating the sample for 2 hours with the powerful UV light of a metal halide lamp. Here, the contact angle of the water drop after the test is 70 ° or more (passed in Table 1), 80 ° or more is good (shown in Table 1 or 2), and 100 ° or more is excellent (
In Table 1 or Table 2). In addition, those less than 70 ° are rejected, and in Table 1, ×
It was written.

Lamp: M0155-L312 made by Eye Graphics
・ Lamp intensity: 1.5kW
Illuminance: The measured value under the following conditions is 128 mW / cm ²
Measuring device: UV intensity meter (Minolta, UM-10)
-Light receiving part: UM-360
(Receiving wavelength range: 310 to 400 nm, peak wavelength: 365 ± 5 nm)
・ Measurement mode: Irradiance measurement

The substrate coated with the water-slidable coating treated with the treatment agent of the present invention is often used outdoors and is exposed to sunlight. In addition, since dust easily adheres, the surface is polished by dust wiping when cleaning, raising or lowering of the glass when used for vehicle glass, and drying or dust containing water when wiping the wiper. Considering this, it is important to improve the light resistance and muddy water abrasion resistance in order to extend the life of the coating.

Example 1
(1) Preparation of processing agent The processing agent was obtained by adding and stirring an acidic aqueous solution to a mixture obtained by mixing linear polydimethylsiloxane and fluoroalkylsilane. FIG. 1 shows the preparation procedure of the treatment agent and the mixing ratio (weight ratio) of each chemical solution. Table 1 shows the sample preparation conditions and the results of evaluation of the resulting products.

First, both terminal trialkoxy type linear polydimethylsiloxane [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₂₅₀ having 250 dimethylsiloxane units.
Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ]; 0.50 g, methyl ethyl ketone; 48.85 g, fluoroalkylsilane having 8 fluorocarbon units [CF ₃
(CF ₂ ) ₇ CH ₂ CH ₂ i (OCH ₃ ) ₃ ]; 0.80 g and isopropyl alcohol;
48.85 g was mixed and stirred for about 5 minutes. Next, 0.5 g of nitric acid aqueous solution (1.0 g) was added, and the mixture was stirred at room temperature for about 2 hours. By the above method, the weight concentration of the mixed linear polydimethylsiloxane (hereinafter referred to as “polydimethylsiloxane concentration”) is 0.5% by weight with respect to the total amount of the processing agent, A treating agent having a weight concentration of the mixed fluoroalkylsilane (hereinafter referred to as “fluoroalkylsilane concentration”) of 0.8% by weight was obtained.

(2) Cleaning glass substrates
The surface of 300 mm × 300 mm × 2 mm thick float glass or the front window of a normal automobile was polished with a polishing liquid, washed with water and dried. The polishing liquid used here was a 2 wt% ceria suspension prepared by mixing glass abrasive Mille A (T) (manufactured by Mitsui Metal Mining) with water.

(3) Formation of water slidable coating agent The treatment agent prepared in (1) above: 1.0 ml (300 mm × 300 mm × 2 mm thickness) or 10 ml (front window) is dropped on a glass substrate, and cotton cloth (trade name; The glass was fully stretched with Bencot) and air-dried for about 5 minutes. Thereafter, the excess remaining in the white mottle was visually wiped with a paper towel moistened with isopropyl alcohol to obtain a transparent sample.

As shown in Table 1, when evaluated in the manner described in [Evaluation method of water slidable coating],
The removability of the excess was very good. In addition, the initial drop angle is 18 °, which shows a good drop drop property. In the ceria polishing test, 50 reciprocations are required to hydrophilize 70%, and in the light resistance test, the contact angle after 2 h irradiation is 85 °. High and durable.

Example 2
Both end trialkoxy type linear polydimethylsiloxane having 400 dimethylsiloxane units [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₄₀₀ Si (
_{CH 3) 2 CH 2 CH 2} Si (OCH 3) 3 ] was the same as in Example 1, except that the catalyst.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 18 °, which shows a good drop-dropping property. In the ceria polishing test, 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is 80 °. High and durable.

Example 3
Both end trialkoxy type linear polydimethylsiloxane having 100 dimethylsiloxane units [(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 ] was the same as in Example 1, except that the catalyst.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial drop angle is 17 °, which indicates a good drop drop property. In the ceria polishing test, 50 reciprocations are required to hydrophilize 70%, and in the light resistance test, the contact angle after 2 h irradiation is 84 °. High and durable.

Example 4
Both end trialkoxy type linear polydimethylsiloxane [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₅₀ Si (CH
₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] was used except that it was the same as Example 1.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial drop angle is 18 °, which shows good drop drop property. In the ceria polishing test, 50 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after the test is as high as 80 °. Excellent durability.

Example 5
Both-terminal dialkoxy type linear polydimethylsiloxane having 250 dimethylsiloxane units [(CH ₃ O) ₂ (H ₃ C) SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} _25
0 Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ] was used, except that the same as Example 1.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle was as good as 16 °, and in the ceria polishing test, 50 reciprocations were required to make 70% hydrophilic, and the durability was excellent. Furthermore, in the light resistance test, the contact angle after 2 h irradiation was 76 °.

Example 6
One-terminal trialkoxy type linear polydimethylsiloxane having 250 dimethylsiloxane units [(CH ₃ ) ₃ SiO {Si (CH ₃ ) ₂ O} ₂₅₀ Si (CH ₃ ) ₂ C
All were the same as Example 1 except that H ₂ CH ₂ Si (OCH ₃ ) ₃ ] was used.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 16 °, which indicates a good water droplet falling property. In the ceria polishing test, 55 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is 80 °. High and durable.

Example 7
All were the same as Example 1 except that the fluoroalkylsilane concentration was 1.6% by weight.

As a result, the physical properties are as shown in Table 1, and the removability of the surplus is very good, and the initial sliding angle is 20 °.
Met. Further, in the ceria polishing test, 55 reciprocations were required to make 70% hydrophilic, and in the light resistance test, the contact angle after the test was as high as 83 ° and the durability was excellent.

Example 8
All were the same as Example 1 except that the fluoroalkylsilane concentration was 0.4 wt%.

As a result, as shown in Table 1, the removal properties of the surplus were very good. The initial falling angle was 18 °, indicating good water droplet falling property. Furthermore, in the ceria polishing test, it was 40 reciprocations to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation was 75 °.

Example 9
Fluoroalkylsilane having 10 fluorocarbon units [CF ₃ (CF ₂ ) ₉
All were the same as Example 1 except that CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] was used.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 17 °, which indicates a good drop-dropping property. In the ceria polishing test, 50 reciprocations are required to hydrophilize 70%, and in the light resistance test, the contact angle after 2 h irradiation is 106 °. High and durable.

Example 10
Fluoroalkylsilane having 6 fluorocarbon units [CF ₃ (CF ₂ ) ₅ C
All were the same as Example 1 except that H ₂ CH ₂ Si (OCH ₃ ) ₃ ] was used.

As a result, the physical properties are as shown in Table 1, and the removability of the surplus is very good, and the initial falling angle is 18 °.
Met. In the ceria polishing test, 45 reciprocations were required to make 70% hydrophilic, and the durability was excellent. In the light resistance test, the contact angle after 2 h irradiation was 74 °.

Example 11
The number of fluorocarbon units is 6, and both terminal trialkoxy type fluoroalkylsilane [(CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH
₃ ) All were the same as Example 1 except that ₃ ] was used.

As a result, as shown in Table 1, the physical properties were excellent in removing the surplus, and the initial sliding angle was 20 °. In the ceria polishing test, 40 reciprocations were required to make 70% hydrophilic. Furthermore, in the light resistance test, the contact angle after 2 h irradiation was as high as 88 °, and the durability was excellent.

Example 12
All were the same as Example 1 except that the polydimethylsiloxane concentration was 1.3% by weight.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 17 °, which indicates a good water droplet falling property. In the ceria polishing test, 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is 82 °. High and durable.

Example 13
The polydimethylsiloxane concentration is 1.0% by weight and the fluoroalkylsilane concentration is 1.6% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is 2.6% by weight with respect to the total amount of the treating agent. Except for the above, all were the same as Example 6.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 18 °, which shows a good drop-dropping property. In the ceria polishing test, 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is 80 °. High and durable.

Example 14
All were the same as Example 6 except that the polydimethylsiloxane concentration was 2.5% by weight.

As a result, the physical properties were good as shown in Table 1. In addition, the initial falling angle is 13 °, which indicates a good water droplet falling property. In the ceria polishing test, 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is 82 °. High and durable.

Example 15
All were the same as Example 1 except that the polydimethylsiloxane concentration was 0.25% by weight.

As a result, as shown in Table 1, the removal properties of the surplus were very good. In addition, the initial falling angle is 18 °, which shows a good water drop falling property. In the ceria polishing test, 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after the test is as high as 82 °. Excellent durability.

Example 16
The polydimethylsiloxane concentration is 1.0% by weight and the fluoroalkylsilane concentration is 1.6% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is 2.6% by weight with respect to the total amount of the treating agent. Except for the above, all were the same as Example 1.

As a result, the physical properties were good as shown in Table 1, and the initial sliding angle was 20 °. In the ceria polishing test, 45 reciprocations were required to make 70% hydrophilic, and in the light resistance test, the contact angle after the test was as high as 81 °, and the durability was excellent.

Example 17
The polydimethylsiloxane concentration is 0.25% by weight, and the fluoroalkylsilane concentration is 0.4.
The weight% was the same as in Example 1 except that the total amount of linear polydimethylsiloxane and fluoroalkylsilane was 0.65% by weight based on the total amount of the treating agent.

As a result, as shown in Table 1, the removal properties of the surplus were very good. The initial falling angle was 18 °, indicating good water droplet falling property. Furthermore, in the ceria polishing test, it was 40 reciprocations to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation was 70 °.

Example 18
The procedure was the same as Example 1 except that a substrate having a primer layer formed thereon was used. The method for forming the primer layer on the substrate will be described below. Tetraisocyanate silane [S
i (NCO) ₄ , manufactured by Matsumoto Pharmaceutical Co., Ltd.] 0.2 g of ethyl acetate [CH ₃ COOC ₂ H ₅ ] 20
to obtain a solution to which 1.0% by weight of tetraisocyanate silane was added. The solution was soaked into a cotton cloth (trade name; Bencott), and the glass substrate that had been ceria-polished with the cotton cloth was wiped off so as not to be applied twice. Then, after drying at room temperature for about 5 minutes, 1 in the furnace
A glass substrate on which a silica film primer layer was formed was obtained by heat treatment at 80 ° C. for 13 minutes (plate temperature of 150 ° C. when leaving the furnace).

Thereafter, the treatment agent was immediately applied and wiped off in the same manner as in Example 1 to obtain a transparent sample. When evaluated in the manner described in [Evaluation Method for High Water-Sliding Coating], as shown in Table 1, the removability of the excess was good. In addition, the initial falling angle is 20 °, indicating a good water drop falling property,
In the ceria polishing test, 70 reciprocations were required to make 70% hydrophilic, and in the light resistance test, the contact angle after irradiation for 2 hours was as high as 108 °, and the durability was excellent. Table 1 shows the production conditions of the sample formed using the base material on which the primer layer is formed and the evaluation result of the resultant product.

Example 19
The heat treatment temperature for obtaining the primer layer is 300 ° C. for 13 minutes (plate temperature 250 ° C. when leaving the furnace)
Example 19 is the same as Example 19. The results show that the initial falling angle is 17 °, which is a good water drop falling property. In the ceria polishing test, 75 reciprocations are required to hydrophilize 70%, and in the light resistance test, the contact angle after 2 h irradiation is 102. ° High and excellent durability.

Example 20
After forming the primer layer, it was left in the atmosphere for 3 hours. Other than that is the same as Example 19. The results show that the initial drop angle is 18 °, which is a good drop drop property. In the ceria polishing test, it takes 65 reciprocations to hydrophilize 70%, and in the light resistance test, the contact angle after 2 h irradiation is 108. ° High and excellent durability.

Example 21
After forming the primer layer, it was left in the atmosphere for 4 days. Thereafter, the base material was added to 0.5 N nitric acid.
Soaked for hours. Other than that is the same as Example 19. As a result, it took 65 reciprocations to hydrophilize 70% in the ceria polishing test, and in the light resistance test, the contact angle after irradiation for 2 h was as high as 106 °, and the durability was excellent.

Example 22
After forming the primer layer, it was left in the atmosphere for 4 days. Thereafter, ultraviolet irradiation was performed using a corona discharge device. Other than that is the same as Example 19. As a result, 65 reciprocations were required to hydrophilize 70% in the ceria polishing test, and in the light resistance test, the contact angle after 2 h irradiation was as high as 98 °, and the durability was excellent.

Example 23
One-terminal trialkoxy type linear polydimethylsiloxane having 30 dimethylsiloxane units [(H ₃ C) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₃₀ Si (CH ₃
) ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ], which is the same as Example 19. As a result, the sliding angle showed a very good value of 15 °, and 70% in the ceria polishing test.
It takes 50 reciprocations to make it hydrophilic, and the contact angle after 2h irradiation is 97 ° in the light resistance test.
It was high and durable.

Example 24
Example 19 was the same as Example 19 except that the heat treatment after application of the solution for obtaining the primer layer was not performed. As a result, in the ceria polishing test, the number of times until hydrophilization was 70% was approximately the same as that of Example 1 in which the primer layer was not formed.

Example 25
Example 19 was the same as Example 19 except that the heat treatment after the primer application was performed at 70 ° C. for 13 minutes (plate temperature at furnace exit: 50 ° C.). As a result, in the ceria polishing test, the number of times until 70% hydrophilicity was achieved was 5
There were 5 round trips.

Example 26
In order to obtain a primer layer, the amount of tetraisocyanate silane added in the coating solution was set to 0.
Example 19 was the same as Example 19 except that the amount was 5% by weight. As a result, in the ceria polishing test, the number of times until 70% hydrophilicity was achieved was 40 reciprocations.

Example 27
After forming the primer layer, it was left in the atmosphere for 4 days. Other than that is the same as Example 19. As a result, in the ceria polishing test, 50 reciprocations were performed to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation was 90 °.

Comparative Example 1
Both-terminal trialkoxy type linear polydimethylsiloxane having 22 dimethylsiloxane units [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₂₂ Si (CH
₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] was used except that it was the same as Example 1.

As a result, as shown in Table 1, 70% of the physical properties became hydrophilic after 35 reciprocations in the ceria polishing test, and the durability was low.

Comparative Example 2
Both end trialkoxy type linear polydimethylsiloxane having 500 dimethylsiloxane units [(CH ₃ O) ₃ SiCH ₂ CH ₂ {Si (CH ₃ ) ₂ O} ₅₀₀ Si (
_{CH 3) 2 CH 2 CH 2} Si (OCH 3) 3 ] was the same as in Example 1, except that the catalyst.

As a result, as shown in Table 1, in the ceria polishing test, 70% of the physical properties became hydrophilic after 35 reciprocations, and in the light resistance test, the contact angle after 2 h irradiation was 63 °, and the durability was low.

Comparative Example 3
All were the same as Example 1 except that the fluoroalkylsilane concentration was 2.5 wt%.

  As a result, the physical properties were as shown in Table 1, and the initial falling angle was 25 ° and the water droplet falling property was low.

Comparative Example 4
All were the same as Example 1 except that the fluoroalkylsilane concentration was 0.1 wt%.

As a result, as shown in Table 1, 70% of the physical properties became hydrophilic after 20 reciprocations in the ceria polishing test. Further, in the light resistance test, the contact angle after 2 h irradiation was 50 °, and the durability was low.

Comparative Example 5
Fluoroalkylsilane having 1 fluorocarbon unit [CF ₃ CH ₂ CH ₂ S
Except for using i (OCH ₃ ) ₃ ], everything was the same as Example 1.

As a result, as shown in Table 1, 70% of the physical properties became hydrophilic after 10 reciprocations in the ceria polishing test. Further, in the light resistance test, the contact angle after irradiation for 2 hours was 65 °, and the durability was low.

Comparative Example 6
All were the same as Example 1 except that the polydimethylsiloxane concentration was 3.5% by weight.

As a result, as shown in Table 1, the physical properties were poor in removal of excess, and a transparent product was not easily obtained.

Comparative Example 7
All were the same as Example 1 except that the polydimethylsiloxane concentration was 0.1% by weight.

  As a result, as shown in Table 1, the initial falling angle was 23 ° and the water droplet falling property was low as shown in Table 1.

Comparative Example 8
The polydimethylsiloxane concentration is 2.0% by weight and the fluoroalkylsilane concentration is 2.0% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is 4.0% by weight with respect to the total amount of the treating agent. Except for the above, all were the same as Example 1.

As a result, as shown in Table 1, the physical properties were poor in removal of excess, and a transparent product was not easily obtained.

Comparative Example 9
The polydimethylsiloxane concentration is 0.2% by weight and the fluoroalkylsilane concentration is 0.2% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is 0.4% by weight with respect to the total amount of the treating agent. Except for the above, all were the same as Example 1.

As a result, as shown in Table 1, the physical properties are 2 to make 70% hydrophilic in the ceria polishing test.
In 5 reciprocations and further in the light resistance test, the contact angle after 2 h irradiation was 55 °, and the durability was low.

Comparative Example 10
All the examples except that both terminal monoalkoxy type linear polydimethylsiloxane [CH ₃ O {Si (CH ₃ ) ₂ O} ₂₅₀ Si (CH ₃ ) ₂ OCH ₃ ] having 250 dimethylsiloxane units was used. Same as 1.

As a result, as shown in Table 1, in the light resistance test, the contact angle after 2 h irradiation was 66 ° and the durability was low as shown in Table 1.

Comparative Example 11
All were the same as in Example 1 except that a trimethyl-blocked linear polydimethylsiloxane [CH ₃ {Si (CH ₃ ) ₂ O} ₂₅₀ Si (CH ₃ ) ₃ ] having 250 dimethylsiloxane units was used. .

As a result, as shown in Table 1, in the light resistance test, the contact angle after 2 h irradiation was 61 ° and the durability was low as shown in Table 1.

FIG. 3 is a diagram showing a procedure for preparing a treatment agent in Example 1.

Claims (9)

A linear polydimethylsiloxane having 2 or 3 hydrolyzable functional groups at at least one end and having 30 to 400 dimethylsiloxane units (Si (CH ₃ ) ₂ O); A treating agent comprising a fluoroalkylsilane having a decomposable functional group and having 6 to 12 fluorocarbon units (CF ₂ or CF ₃ ), and a solution containing an organic solvent, an acid, and water. The linear polydimethylsiloxane is 0.2 to 3.0% by weight and the fluoroalkylsilane is 0.2% by weight with respect to the total amount of the treatment agent.
A treatment for obtaining a water-slidable coating film characterized in that the total amount of the linear polydimethylsiloxane and the fluoroalkylsilane is mixed in an amount of 0.5 to 3.5% by weight. Agent. The treating agent for obtaining a water-slidable coating according to claim 1, wherein the linear polydimethylsiloxane has a hydrolyzable functional group only at one end. The linear polydimethylsiloxane is 0.5 to 2.5% by weight, the fluoroalkylsilane is 0.6 to 1.6% by weight, and the linear polydimethyl is based on the total amount of the treatment agent. The treating agent for obtaining a water-slidable coating according to claim 2, wherein the total amount of siloxane and fluoroalkylsilane is mixed in an amount of 1.2 to 3.0% by weight. The treating agent for obtaining a water-slidable coating according to claim 1, wherein the linear polydimethylsiloxane has hydrolyzable functional groups at both ends. The linear polydimethylsiloxane is 0.2 to 2.0% by weight, the fluoroalkylsilane is 0.5 to 1.4% by weight, and the linear polydimethyl is further added to the total amount of the treatment agent. The treating agent for obtaining a water-slidable coating according to claim 4, wherein the total amount of siloxane and fluoroalkylsilane is mixed in an amount of 0.8 to 2.5% by weight. The hydrolyzable functional group is an alkoxy group, and the treatment agent for obtaining a water-slidable coating film according to any one of claims 1 to 5. A step of applying the treatment agent according to any one of claims 1 to 6 to a substrate, a step of drying the substrate on which the treatment agent is applied, and an unreacted or hydrolyzed state after being dried Alternatively, a method for producing a water-slidable coating, comprising a step of removing condensed linear polydimethylsiloxane and fluoroalkylsilane. The base material is obtained by applying a solution containing a silicon compound having four functional groups to the base material and solidifying the base material to form a primer layer derived from the silicon compound. Item 8. A method for producing a water-slidable coating according to Item 7. 9. The method for producing a water-slidable coating according to claim 8, wherein the silicon compound having four functional groups is tetraisocyanate silane.