JP2009160550A - Low-friction film-covered article, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-friction film-covered article excellent in operability of a wiper such as to suppress generation of chattering, and to provide a low-friction film-covered article manufacturing method capable of efficiently manufacturing the low-friction film-covered article. <P>SOLUTION: The low-friction film-covered article comprises a substrate and a low-friction film formed on the substrate. The low-friction film is formed on a side to be in contact with a wiping member. The low-friction film mainly contains silicon oxide. As measuring conditions of the dynamic friction coefficient between the surface of the low-friction film and the wiping member, when assuming the speed of moving the wiping member on the surface of the low-friction film is 50 cm/min, the dynamic friction coefficient in a wet state is ≤0.30. The low-friction film coated article manufacturing method is also disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a low-friction coating-coated article formed by forming a low-friction coating on the surface of a substrate such as glass and a method for producing the same.

Conventionally, the improvement of the wiper operation in the glass for automobiles is mainly due to the improvement of the wiper (see, for example, Patent Documents 1 and 2), and there has been almost no improvement in the window glass.
On the other hand, as the technology for imparting water repellency to automotive glass has become widespread, the water-repellent glass plate has a lower wiper operation than a normal glass plate (hydrophilic glass plate). Due to the problem of judder (also called chatter), a water-repellent glass plate that improves the wiper operation has been proposed (see, for example, Patent Documents 3 and 4).
Although many improvements have been made with respect to water-repellent glass plates, there have been few examples of glass plates having hydrophilicity for improving the wiper operation and wettability between hydrophilicity and water-repellency. This is considered to be because even if the treatment for increasing the hydrophilicity is performed on the normally hydrophilic glass plate, it is difficult for the user to realize the effect as the water repellent treatment.

  While wipers such as Patent Documents 1 and 2 are proposed, in recent years, flat wipers have begun to be used for improving the design of the wiper. In many cases, the flat wiper employs a structure in which the flat wiper is pressed against the window glass only at the central portion, and the wiper operation tends to be lower than that of the conventional product. Accordingly, in the case of a flat wiper, even if it is a hydrophilic glass plate, the wiper operability may be lower than that of a conventional wiper.

  As described above, there is a demand for a glass plate with high wiper operability in which the generation of judder is suppressed even when the wiper configuration is changed, but no effective glass plate has been found at present.

Japanese Patent Application Laid-Open No. 6-262943 JP-A-8-268234 JP 2004-306010 A WO2007 / 018184

  The present invention aims to solve the above problems. That is, an object of the present invention is to provide a low-friction coating-coated article that has excellent wiper operability, such as generation of judder. It is another object of the present invention to provide a method for producing a low-friction coating-coated article that can efficiently produce the low-friction coating-coated article of the present invention.

  As a result of intensive studies to achieve the above object, the present inventor has conceived the present invention described below and found out that the above problems can be solved.

That is, the present invention
(1) It has a base material and a low-friction film formed on the base material, and the low-friction film is formed on the side in contact with the wiping member, and the low-friction film is silicon oxide As a measurement condition of the dynamic friction coefficient between the surface of the low friction coating and the wiping member, the speed at which the wiping member moves on the surface of the low friction coating is 50 cm / min. A low-friction coated article having a coefficient of dynamic friction in a wet state of 0.30 or less,
(2) The low-friction coating-coated article according to (1), wherein a contact angle of water on the surface of the low-friction coating is 80 ° or less,
(3) The low-friction coated article according to (1) or (2), wherein the absolute value of the difference in dynamic friction coefficient between the dry state and the wet state is 0.30 or less,
(4) The contact angle of water is 20 ° or less, (2) or (3) according to the low friction film-coated article,
(5) The low-friction coated article according to any one of (1) to (4), wherein organic substances are removed from the surface of the low-friction coating by surface treatment,
(6) The low-friction coating-coated article according to (5), wherein the water contact angle is 10 ° or less,
(7) The low-friction coating-coated article according to (5) or (6), wherein the surface treatment is a plasma jet treatment,
(8) (A) (B) chlorosilyl group-containing compound and (C) colloidal silica are dissolved in a solvent containing alcohol and / or water, and (B) the chloro group of the chlorosilyl group-containing compound is converted to an alkoxyl group or a hydroxyl group. A replacement coating solution is prepared, and the coating solution is applied to a substrate under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). A method for producing a low-friction coating-coated article that is dried under conditions of 40 ° C. and absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA),
(9) An undercoat coating solution in which (B) a chlorosilyl group-containing compound is dissolved in a solvent containing (A) alcohol and / or water, and (B) the chloro group of the chlorosilyl group-containing compound is replaced with an alkoxyl group or a hydroxyl group. And (D) an upper layer coating liquid is prepared by dissolving (B) a chlorosilyl group-containing compound in a silicone solvent, and a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / The undercoat layer coating solution is applied to the substrate under the conditions of kg (DA) and dried under the conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). As a result, a base layer is formed on the surface of the base material, and under the conditions of the temperature of 10 to 40 ° C. and the absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). The upper layer coating solution on the ground layer Coated, using a solvent used in the production of the upper strata coating liquid washed off the upper strata coating liquid excess of the substrate surface, temperature of 10 to 40 ° C., absolute humidity 1 × 10 ^-3 ~18 × 10 ^{- It is} allowed to stand for 1 second or more under the condition of ³ kg / kg (DA), and then the silicone solvent on the surface of the substrate is washed away with alcohol, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ^{− A} method for producing a low-friction coating-coated article that is dried under conditions of ³ kg / kg (DA);
(10) (E) A chlorosilyl group-containing compound is dissolved in a hydrocarbon solvent to prepare a coating solution, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg. Under the condition of (DA), the coating liquid is applied to the base material, and the excess coating liquid on the surface of the base material is washed away using the (E) hydrocarbon solvent used in the preparation of the coating liquid. Let stand for at least 1 second under conditions of 40 ° C. and absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), and wash away the (E) hydrocarbon solvent on the substrate surface with alcohol, A method for producing a low-friction coating-coated article that is dried under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA),
(11) (F) Silicon alkoxide and / or its hydrolyzate 0.01-2 mass% (silica conversion), (G) fluoroalkyl group-containing silane compound 0.00001-0.15 mass% (silica conversion), (H) an acid and (I) a coating solution containing 0 to 20% by mass of water and having an acid concentration of 0.001 to 3 N, or (B) a chlorosilyl group-containing compound and (G) a fluoroalkyl group A coating solution in which a silane compound is dissolved in (A) a solvent containing alcohol and / or moisture, and the chloro group of the (B) chlorosilyl group-containing compound is substituted with an alkoxyl group or a hydroxyl group, a temperature of 10 to 40 ° C., It was applied to the substrate under conditions of absolute humidity 4.5 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), temperature 10 to 40 ° C., and absolute humidity 4.5 × 10 ⁻³ to 18 × 10 ^{−. A} method for producing a low-friction coating-coated article in which a hydrophilic coating is formed by applying a surface treatment to remove the water-repellent component on the surface after drying under conditions of ³ kg / kg (DA),
(12) The method for producing a low-friction film-coated article according to (11), wherein the surface treatment is a plasma jet treatment.

  ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of judder can be suppressed and the low friction coating-coated article excellent in the operativity of a wiper can be provided. Moreover, the manufacturing method of the low-friction coating-coated article which can manufacture the low-friction coating-coated article of this invention efficiently can be provided.

[Low friction coating coated article]
The low-friction coating-coated article of the present invention has a substrate and a low-friction coating formed on the substrate. The low-friction film is formed on the side in contact with the wiping member (for example, a wiper) and contains silicon oxide as a main component.
Examples of the wiping member include a windshield wiper, a weather strip of an openable / closable window (for example, a door window and a roof) of a vehicle, and a wiper used for cleaning a building window. For the contact portion of the wiping member with the low friction coating, rubber, sponge-like resin, and cloth-like material can be used. In the following description, rubber used for a wiper (simply referred to as wiper rubber) is used.

  The low friction coating according to the present invention preferably has a water contact angle of 80 ° or less. By setting it to 80 ° or less, it has hydrophilicity or intermediate wettability between hydrophilicity and water repellency. Since hydrophilicity and water repellency largely depend on the user's preference, if the contact angle is 80 ° or less, the user's choice can be met.

  The glass plate used for the window is installed vertically or at an angle enough to be attached to the automobile. In such an installation state, water droplets adhering to the surface of the glass plate due to rain or the like are connected to surrounding water droplets while flowing and flow down when the glass plate surface is hydrophilic. As the water changes from hydrophilic to water-repellent, the water droplets do not spread and tend to stop in place, and as rain falls, they overlap with other water droplets and flow down. When the water repellency increases, it slides down with its own weight and wind force leaving the shape of the water droplets.

Since water droplets spread in the form of a film on the film of the hydrophilic glass plate, a film of water is formed almost entirely between the film and the wiper rubber at the initial stage of rainfall. Therefore, the period during which there is a portion where there is a water droplet and a portion where there is no water droplet is very short, and in a state where the water droplet adheres to such an extent that the user operates the wiper, the surface of the coating is in a wet state at the beginning of the wiper operation. It is considered to be. In this case, if the dynamic friction coefficient in the wet state is low, a good wiper operation can be obtained.
Such a contact angle is more preferably 20 ° or less, further preferably 10 ° or less, and particularly preferably 5 ° or less. As will be described later, the contact angle of water when the organic substance is removed from the surface of the low friction coating by surface treatment (for example, plasma jet treatment) is preferably 10 ° or less.

  Further, the coefficient of dynamic friction in the wet state is essential to be 0.30 or less and preferably 0.20 or less when the speed at which the wiper rubber moves on the surface of the glass plate coating is 50 cm / min. .

  Water droplets adhering to the coating on the glass plate with low hydrophilicity do not spread in the form of a film and tend to stop in place, so that the wiper stretches the droplet between the coating and the wiper rubber in the early rainy season. There are parts with and without water droplets. Therefore, the period in which there is a portion with and without water droplets is longer than when the hydrophilicity is high, and in the state where the attachment of water droplets proceeds to the extent that the user operates the wiper, in the initial stage of the wiper operation, The surface of the coating is considered to be in a state where a wet state and a dry state (or a state close thereto) are mixed. In this case, if the absolute value of the difference in the dynamic friction coefficient between the wet state and the dry state is small in addition to the low dynamic friction coefficient in the wet state, a better wiper operation can be obtained even at the initial stage of the wiper operation. The absolute value of the difference between the dynamic friction coefficients is preferably 0.30 or less, more preferably 0.20 or less, and still more preferably 0.10 or less.

  Although it does not specifically limit as a base material used for the low-friction coating-coated article of this invention, A transparent glass plate, a resin plate, a resin film, etc. can be used suitably. The thickness of the substrate is appropriately selected according to the application and is not particularly limited, but is usually about 0.01 to 10 mm.

  There are various methods for measuring the dynamic friction coefficient, and there is no particular limitation. For example, the coated article in a dry state (also referred to as a Dry state) and a wet state (also referred to as a Wet state) using, for example, the following friction coefficient measurement method The dynamic friction coefficient between the coating and the wiper rubber can be measured.

  FIG. 3 is a schematic diagram for explaining a measurement method when a flat glass plate is used as a substrate. FIG. 3 shows a case where the dynamic friction coefficient of the surface of the flat glass plate (11) is measured. Hereinafter, the measurement method will be specifically described in the case of the coated article (1) in which the film (12) is formed on the glass plate (11).

  First, the wiper rubber test body (2) to which the wiper rubber (21) is attached is manufactured as follows. Two wiper rubbers (for example, “Part No. 85214-22420”, Toyota Motor Corp., cut into a length of 10 cm with a gap of 10 cm in the vicinity of the center of the lower surface of the 15 × 15 cm plate-like body (22). Affix the replacement parts with double-sided tape so that they are parallel. Here, the reason why the two wiper rubbers are used in parallel is to stabilize the wiper rubber specimen (2). Then, a weight (23) is placed on the center of the upper surface side of the plate-like body (22) such as a glass plate so that the total load including the plate-like body and the wiper rubber is 400 g (20 gf / cm). . Usually, since the tip of the wiper rubber has a triangular shape and is flexible, it is difficult to accurately measure the contact area between the wiper rubber (21) and the coating (12). In such a case, it is effective to express the force applied to the wiper rubber by the weight applied per unit length by using the length instead of the area of the wiper rubber contacting the low friction coating.

  For the measurement of the dynamic friction coefficient in the dry state, the wiper rubber specimen (2) produced as described above is placed on the coating (12) on the surface of the coated article (1) having a size of 30 × 30 cm, and pulled. Connect to the measuring device (4) by means of the tool (3). The wiper rubber (21) is pulled horizontally in a direction perpendicular to the length direction of the wiper rubber (21) at a speed of 50 cm / min. While pulling the wiper rubber specimen (2), the tensile force is measured by an autograph (“DSS-10T”, manufactured by Shimadzu Corporation) which is a measuring device (4). From the measured value when the tensile force is stabilized, the dynamic friction coefficient (total load / tensile force) in a dry state is obtained.

  Next, the dynamic friction coefficient in a wet state will be described. In this measurement, sufficient water droplets are sprayed on the coating film (12) by spraying (not shown), the wiper rubber specimen (2) is placed on the coating film (12), and the wiper rubber (21) is moved in the traveling direction side. Then, water is sprayed and water is sufficiently accumulated at the contact portion between the wiper rubber (21) and the coating (12). Other conditions are the same as in the dry state.

  Although the case where the coefficient of dynamic friction of a coated article having a film formed on a flat glass plate is measured has been described above, a curved glass plate (curved glass plate) is generally used as a window glass of an automobile. The shape and hardness of the wiper rubber are devised so that the wiper rubber can contact the surface of the curved glass plate without any gap.

FIG. 4 shows a schematic diagram in the case of measuring the dynamic friction coefficient of the film-covered article (1) in which the film (12) is formed on such a curved glass plate (13).
Place the curved glass plate (13) on a stand (not shown) so that the place (measurement point) where you want to measure is the apex, and place the measuring device (4) so that the pulling tool is horizontal To do. The mark (1) is marked on the place where the vertex of the coated article (1) is known (for example, the side surface of the table) and the wiper rubber specimen (2) (for example, the side surface of the plate-like body (22)) corresponding to the vertex A center mark (24) is added. As shown in FIG. 4, it becomes easy to confirm if, for example, triangular marks (24a) and (24b) are arranged so that the vertices face each other.
The wiper rubber specimen (2) is pulled to a position closer to the measurement position (4) than the apex position, and measurement is performed. The determination when the wiper rubber specimen (2) reaches the apex position can be made by matching the two center marks. By measuring the distance from the start of towing to the apex position and comparing with the result of the measuring device (4), the measurement result when the wiper rubber specimen (2) reaches the apex position is obtained, and the dynamic friction coefficient is calculated. Can be calculated.
Thus, by determining the dynamic friction coefficient at the apex position of the low-friction coated article (1), the dynamic friction coefficient can be measured even for a curved low-friction coated article.

  The low-friction coating-coated article of the present invention as described above can be used for, for example, an automobile or a windshield of a train that uses a wiper as a wiping member. In this case, the low-friction coating of the low-friction coating-coated article is provided on the side in contact with the wiper.

[Production Method of Low Friction Coated Coated Article]
(First manufacturing method)
In the first method for producing a low-friction coating-coated article of the present invention, (B) a chlorosilyl group-containing compound and (C) colloidal silica are first dissolved in a solvent containing (A) alcohol and / or water. B) A coating solution in which the chloro group of the chlorosilyl group-containing compound is substituted with an alkoxyl group or a hydroxyl group is prepared.

Here, the (B) chlorosilyl group-containing compound is a compound having at least one chlorosilyl group in the molecule, and the chlorosilyl group, a group represented by -SiCl _n X _{3-n, n} is 1 2, or 3, X is hydrogen, or an alkyl group, an alkoxyl group, or an acyloxy group each having 1 to 10 carbon atoms.
Among them, a compound having at least two chlorines is preferable, and at least two hydrogens in silane Si _n H _{2n + 2} (where n is an integer of 1 to 5) are substituted with chlorine to obtain other hydrogens. Is preferably a chlorosilane substituted with an alkyl group, an alkoxyl group, or an acyloxy group, a partially hydrolyzed product thereof, or a polycondensed product thereof.
Specifically, tetrachlorosilane (SiCl ₄ ), trichlorosilane (SiHCl ₃ ), trichloromonomethylsilane (Si (CH ₃ ) Cl ₃ ), dichlorosilane (SiH ₂ Cl ₂ ), and Cl— (SiCl ₂ O) _n -SiCl ₃ (n is an integer of from 1 to 10), and the like. Among these, it can use individually or in combination. The most preferred chlorosilyl group-containing compound is tetrachlorosilane.

(A) The solvent containing alcohol and / or water is used to cause the dehydrochlorination reaction by substituting the chloro group of the (B) chlorosilyl group-containing compound with an alkoxyl group or a hydroxyl group. For example, an alcohol-based hydrophilic solvent and a ketone-based hydrophilic solvent are preferably used.
Among these, alcohols are preferable, and chain saturated monohydric alcohols having 3 or less carbon atoms such as methanol, ethanol, 1-propanol, and 2-propanol are particularly preferable because of their high evaporation rate at room temperature. Examples of ketone-based hydrophilic solvents include acetone and methyl ethyl ketone.
Note that the solvent does not necessarily include alcohol as long as the solvent includes water necessary to cause the dehydrochlorination reaction. Furthermore, the solvent does not need to be composed of only a hydrophilic solvent, and may contain a non-aqueous solvent such as hydrocarbon or fluorine.

  Colloidal silica is a sol in which ultrafine particles of silica with a particle size of 1 to 100 μm are dispersed in water or an alcohol-based dispersion medium, or a dry powder from which a dispersing group has been removed, but commercially available products can be used. It is. Examples of the sol include water-dispersed silica gels such as Nissan Chemical's Snowtex OL, Snowtex O, and Snowtex OUP, as well as organic solvent-dispersed silica gels such as Nissan Chemical's MIBK-ST and XBA-ST, Examples include Catalyst SI-80P (silica gel) manufactured by Catalytic Chemicals.

Next, this coating solution was applied to the substrate under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), and the temperature was 10 to 40 ° C. and the absolute humidity. A low friction coating film is formed on the surface of the substrate by drying under conditions of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), and the low friction coating coated article of the present invention is manufactured. To do.

In preparing the coating liquid, the amount of (C) colloidal silica can be adjusted in order to adjust the surface roughness of the low friction coating.
When it is necessary to increase the hydrophilicity of the low-friction coating, it is highly hydrophilic (for example, the contact angle is 10 ° or less) by applying a surface treatment to remove organic components on the surface. Articles can be manufactured.

(Second manufacturing method)
In the second method for producing a low-friction coating-coated article of the present invention, a coating having a two-layer structure is coated on the surface of the substrate by two coatings (hereinafter referred to as a two-coat type). A coating liquid that is directly applied to the substrate is used as a base layer coating liquid, and a film coated thereby is used as a base layer. The coating liquid applied on the base layer is used as the upper layer coating liquid, and the film coated thereby is used as the upper layer.
The underlayer and the upper layer may have different surface states and properties. For example, when the underlayer is hydrophilic, a film having water repellency or an intermediate wettability between hydrophilicity and water repellency can be formed on the hydrophilic film.

First, (B) a chlorosilyl group-containing compound is dissolved in a solvent containing alcohol and / or water, and (B) the chloro group of the chlorosilyl group-containing compound is replaced with an alkoxyl group or a hydroxyl group to prepare an undercoat coating solution To do. This undercoat layer coating liquid is a coating liquid when (C) colloidal silica is not added to the coating liquid of the first production method.
(D) Dissolve the (B) chlorosilyl group-containing compound in a silicone-based solvent to prepare an upper layer coating solution.

Here, examples of the (D) silicone solvent include decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.
In particular, among these solvents, those having high volatility are preferable, and specifically, those having a vapor pressure at 25 ° C. of 500 Pa or more, and more preferably 1000 Pa or more are preferable.

Next, under the conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), the base layer coating solution is applied to the substrate, and the temperature is 10 to 40 ° C. An undercoat layer is formed on the surface of the substrate by drying under conditions of a humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA).

Next, an upper layer coating solution is applied on the base layer of the base material under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), and immediately the upper layer Wash off the excess upper layer coating solution on the surface of the substrate using the solvent used for the preparation of the coating solution, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). Under the condition, the substrate surface is left wet with this solvent for 1 second or longer. Thereafter, the silicone solvent on the substrate surface is washed away with an alcohol such as ethanol, and dried under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). A low-friction coating film is formed on the surface of the substrate to produce the low-friction coating-coated article of the present invention.

In preparing the undercoat layer coating liquid and / or the upper layer coating liquid, (C) colloidal silica can be added as necessary to adjust the surface roughness of the low friction coating.
When it is necessary to increase the hydrophilicity of the low-friction coating, it is highly hydrophilic (for example, the contact angle is 10 ° or less) by applying a surface treatment to remove organic components on the surface. Articles can be manufactured.

(Third production method)
In the third method for producing a low-friction coating-coated article of the present invention, first, a coating liquid is prepared by dissolving (B) a chlorosilyl group-containing compound in (E) a hydrocarbon solvent. Then, the temperature 10 to 40 ° C., under the conditions of absolute humidity ^{1 × 10 -3 ~18 × 10 -3} kg / kg (DA), and coating the coating solution on the substrate was immediately used in the preparation of the coating liquid ( E) The excess coating liquid on the substrate surface is washed away using a hydrocarbon solvent, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA) for 1 second. As described above, the substrate surface is left wet with this solvent. Then, the (E) hydrocarbon solvent on the substrate surface is washed away with an alcohol such as ethanol and dried under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). By doing so, a low-friction coating film is formed on the surface of the substrate to produce the low-friction coating-coated article of the present invention.

  Here, examples of the hydrocarbon solvent (E) include normal paraffins such as n-butane, n-heptane, n-octane and n-nonane; isoparaffins such as isobutane and isopentane. In particular, among these solvents, those having high volatility are preferable, and specifically, those having a vapor pressure at 25 ° C. of 500 Pa or more, and more preferably 1000 Pa or more are preferable.

In preparation of the coating liquid, (C) colloidal silica can be added as necessary to adjust the surface roughness of the low friction coating.
When it is necessary to increase the hydrophilicity of the low-friction coating, surface treatment is performed to remove organic components on the surface, resulting in a low-friction coating with a surface contact angle of 10 ° or less, and excellent hydrophilicity. In addition, a low-friction coated article can be produced.

In the first to third production methods, a preferable temperature range in coating, standing, and drying is 15 to 35 ° C., and a preferable absolute humidity range is 2 × 10 ^{−3 to} 12 × 10 ^−3. kg / kg (DA).

(Fourth manufacturing method)
In the fourth method for producing a low-friction coating-coated article of the present invention, first, (F) silicon alkoxide and / or a hydrolyzate thereof 0.01 to 2% by mass (in terms of silica), (G) containing a fluoroalkyl group A coating liquid containing 0.00001 to 0.15% by mass of silane compound (in terms of silica), (H) acid, and (I) 0 to 20% by mass of water, and having an acid concentration of 0.001 to 3N, or (B) a chlorosilyl group-containing compound and (G) a fluoroalkyl group-containing silane compound are dissolved in a solvent containing (A) alcohol and / or water, and (B) the chloro group of the chlorosilyl group-containing compound is converted into an alkoxyl group or A coating solution substituted with hydroxyl groups is prepared. Thereafter, any one of the above coating solutions was applied to the substrate under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 4.5 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). Drying is performed under the conditions of ° C. and absolute humidity of 4.5 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA) to form a water-repellent coating on the surface of the substrate. The formed water-repellent coating is divided into a base layer on the substrate surface and a water-repellent component on the base layer. The formed water-repellent coating is subjected to a surface treatment for removing the water-repellent component on the surface to form a low-friction coating, and the low-friction coating-coated article of the present invention can be produced.

  The fourth production method is characterized in that when a low-friction film is formed on a substrate, a water-repellent film is once formed under specific conditions and a surface treatment is performed to remove the water-repellent component on the surface. . By removing the water-repellent component of the water-repellent coating formed as described above by surface treatment, the surface contact angle becomes a low-friction coating of 10 ° or less, and the wet dynamic friction coefficient is 0.30 or less. The low-friction coating-coated article of the present invention can be produced efficiently.

  Next, the material of the coating when the water repellent coating has a fluoroalkyl group will be described in detail. Various materials can be used as the material for forming the water-repellent coating, but in the present invention, the following materials can be preferably used.

  Examples of the silicon alkoxide as component (F) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Among these, those having a relatively small molecular weight, for example, tetraalkoxysilane composed of an alkoxyl group having 3 or less carbon atoms are preferably used because they tend to be dense films. These tetraalkoxysilane polymers may have an average degree of polymerization of 5 or less. In addition, as described in detail later, the content of the component (F) in the coating liquid is preferably 0.01 to 2% by mass, and more preferably 0.01 to 0.6% by mass in terms of silica.

As the fluoroalkyl group-containing silane compound as component (G), a silane compound containing a fluoroalkyl group and containing a hydrolyzable group such as an alkoxyl group, an acyloxy group, or a chlorine group is preferably used. Examples thereof include compounds represented by the following chemical formula (I).
_{CF 3 - (CF 2) n} -R-SiX p Y 3-p ··· (I)
Here, n is an integer of 0 to 12, preferably an integer of 3 to 12, and R is a divalent organic group having 2 to 10 carbon atoms (for example, a methylene group, an ethylene group, etc.), or a silicon atom and an oxygen atom. A group containing X, a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms (for example, an alkyl group, a cycloalkyl group, an allyl group) or a derivative thereof; p is 0, 1 or 2, Y is an alkoxyl group having 1 to 4 carbon atoms, an acyloxy group, or a halogen atom.

More _{specifically, C 6 F 13 CH 2 CH} 2 Si (OCH 3) 3, C 7 F 15 CH 2 CH 2 Si (OCH 3) 3, C 8 F 17 CH 2 CH 2 Si (OCH 3) 3 _{, C 9 F 19 CH 2 CH} 2 Si (OCH 3) 3, C 10 F 21 CH 2 CH 2 Si (OCH 3) 3, C 6 F 13 CH 2 CH 2 SiCl 3, C 7 F 15 CH 2 CH 2 SiCl ₃ , C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ , C ₉ F ₁₉ CH ₂ CH ₂ SiCl ₃ , C ₁₀ F ₂₁ CH ₂ CH ₂ SiCl ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₃ ) ( _{OCH 3) 2, C 8 F} 17 CH 2 CH 2 Si (OC 2 H5) 3, C 8 F 17 CH 2 CH 2 Si (OCOCH 3) 3, (CF 3) 2 CF (CF 2) 8 CH 2 CH such as ₂ Si (OCH _{3) 3} can be mentioned. among _{them, C 8 F 17 CH 2 CH} 2 Si (OCH 3) 3 ( Heputadekafuru B _{decyltrimethoxysilane), C 8 F 17 CH 2} CH 2 Si (CH 3) (OCH 3) 2 ( heptadecafluorodecyl _{methyldimethoxysilane), C 8 F 17 CH 2} CH 2 SiCl 3 ( heptadecafluorodecyl Trichlorosilane) and C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₃ ) Cl ₂ (heptadecafluorodecylmethyldichlorosilane) are preferred, and heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltrichlorosilane are particularly preferably used. . These can be used alone or in combination of a plurality of substances.
In addition, 0.00001-0.15 mass% is preferable in conversion of a silica, and, as for content of (B) component in a coating liquid in full detail later, 0.0001-0.03 mass% is more preferable.

As the acid as component (H), volatile acids such as hydrochloric acid, hydrofluoric acid, nitric acid, and acetic acid are preferable from the viewpoint that they are volatilized by drying at room temperature and do not remain in the film. Among them, hydrochloric acid is highly volatile. The water-repellent film thus obtained has a relatively good appearance, exhibits high durability, and is relatively safe when handled. The concentration (acid concentration) of the component (H) in the coating solution is preferably 0.001 to 3 N, more preferably 0.01 to 1 N, as will be described in detail later.
Moreover, since water which is (I) component melt | dissolves an acid, it is contained as needed and refined water is usually used. In addition, as described in detail later, the content of the component (I) in the coating liquid is preferably in the range of 0 to 20% by mass, more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass.

  It is convenient in handling that the component (F) and the component (G) are used by dissolving in a solvent when preparing a coating composition. As the solvent, various solvents can be used, for example, hydrocarbons such as hexane, toluene, and cyclohexane; halogenated hydrocarbons such as methyl chloride, carbon tetrachloride, and trichloroethylene; acetone, methyl ethyl ketone, and the like. Organic solvents such as ketones; nitrogen-containing compounds such as diethylamine; alcohols; esters such as ethyl acetate can be used. Among these, an alcohol solvent in which an acid is easily dissolved is preferably used, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, butyl alcohol, amyl alcohol, and the like. A chain saturated monohydric alcohol having 3 or less carbon atoms such as methanol, ethanol, 1-propanol and 2-propanol is more preferably used because of its high evaporation rate at room temperature.

  In addition to (F) silicon alkoxide, (G) fluoroalkyl group-containing silane compound and (H) acid, the coating liquid in the present invention includes, for example, a small amount of methyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane). , Methyltripropoxysilane, methyltributoxysilane, etc.) can be contained in an amount of 50% by mass or less of the silicon alkoxide content in terms of silica.

In the present invention, the inside of the coating solution containing silicon alkoxide, fluoroalkyl group-containing silane compound, acid, solvent and water (including those for dissolving the acid, impurities in the solvent, and those entering from the humidity of the atmosphere) Thus, during the preparation, during storage and after application, hydrolysis reaction represented by the following formula (II) occurs between the silicon alkoxide and water using the acid as a catalyst.
(-Si-OR) + (H 2 O) → (-Si-OH) + (ROH) ··· (II)
In the formula, R is an alkyl group.

In addition, silanol groups (—Si—OH) generated by the hydrolysis reaction undergo a dehydration condensation reaction to form a siloxane bond (—Si—O—Si—) as shown in the following formula (III).
(—Si—OH) + (— Si—OH) → (—Si—O—Si —) + (H ₂ O) (III)
Whether or not the alkoxyl group of the silicon alkoxide undergoes a hydrolysis reaction in the coating liquid containing silicon alkoxide, fluoroalkyl group-containing silane compound, acid, solvent and water, as well as the same. Whether or not the silanol groups (—Si—OH) subjected to the decomposition reaction undergo a dehydration condensation reaction as shown in the above formula (III) in the coating solution depends on the acid concentration of the solution, the silicon alkoxide or the hydrolyzate thereof. It depends greatly on the concentration and water content. Specifically, the above reaction hardly occurs when the acid concentration of the solution is in the range of 0.001 N to 3 N, and the above reaction hardly occurs as the concentration and water content of the silicon alkoxide or its hydrolyzate are lower.

  In the present invention, the silicon alkoxide in the coating liquid suppresses the dehydration condensation reaction and keeps the monomer as much as possible, and when the coating liquid is applied to the substrate surface and dried, the above formula (II), formula Since the reaction (III) is caused to form a siloxane bond, a dense film can be formed at room temperature. When silicon alkoxide is hydrolyzed and polycondensed in a solution as in the prior art, polymer bonds occur when the solution is applied to the surface of the substrate and dried, which makes it easy to create gaps. It was necessary to perform baking and curing in order to obtain a dense film instead of a film. Therefore, in this invention, it is preferable that the silicon alkoxide or its hydrolyzate in a coating liquid is a monomer or a polymer less than a 20-mer. However, when the total of the monomer, the hydrolyzate, and the polymer less than 20 mer accounts for 80% by mass or more based on the entire silicon alkoxide, the polymer including 20 mer or more may be contained. There is no problem.

  In the present invention, the concentration of the acid catalyst in the coating solution is maintained at 0.001 to 3 N, preferably 0.01 to 1 N. As a result, the hydrolysis reaction of the remaining alkoxyl group of the above formula (II) and the dehydration condensation reaction of the above formula (III) are less likely to occur in the coating liquid before coating, and abruptly immediately after the coating liquid is applied. These reactions proceed.

  The concentration of the silicon alkoxide or the hydrolyzate thereof in the coating solution is as low as possible, coupled with the acid concentration of the coating solution, and the hydrolysis reaction of the remaining alkoxyl groups of the above formula (II), and The dehydration condensation reaction of formula (III) is preferable because it hardly occurs in the coating solution before coating. However, if this concentration is too low, the thickness of the water-repellent film becomes too small, for example, the film thickness becomes less than 5 nm, and the ability to prevent the diffusion of the alkali component when the substrate contains an alkali component is reduced. The durability performance tends to be inferior. On the other hand, if the concentration of silicon alkoxide or its hydrolyzate exceeds 2% by mass, the thickness of the water-repellent film obtained exceeds 200 nm, and the water-repellent film is easily damaged and does not become a strong film. Therefore, the preferable range of the concentration of the silicon alkoxide or the hydrolyzate thereof in the coating liquid (including the polymer less than 20-mer) is 0.01 to 2% by mass in terms of silica, and the more preferable range is 0.01-0.6% by mass.

  If the thickness of the water repellent coating is too large as described above, the film hardness tends to decrease, and if it is too small, the durability of the film tends to decrease. Therefore, the film thickness of the water repellent coating is preferably 5 to 200 nm, more preferably 5 to 100 nm, and still more preferably 5 to 50 nm.

  If the concentration of the fluoroalkyl group-containing silane compound in the coating solution is too low, the water repellency is reduced. If the concentration is too high, the hardness of the film decreases. Therefore, the preferred concentration range of the fluoroalkyl group-containing silane compound in the coating solution is silica. In conversion, it is 0.00001 to 0.15 mass%, more preferably 0.0001 to 0.03 mass%. In addition, the ratio of the content (mass converted to silica) of the fluoroalkyl group-containing silane compound to the silicon alkoxide content (mass converted to silica) in the coating solution is the silica in the coated and dried water-repellent film. Almost corresponds to the content of the fluoroalkyl group.

  The value of [fluoroalkyl group-containing silane compound amount (silica conversion)] / [silicon alkoxide or its hydrolyzate amount (silica conversion)] in the coating liquid is 0.0005 to 0.5. It is preferably 0.0005 to 0.3, more preferably 0.0005 to 0.05.

  If a large amount of water is present in the coating solution, the hydrolysis reaction of the hydrolyzate of silicon alkoxide is promoted in the coating solution before application, and a dehydration condensation reaction is likely to occur. In this case, unevenness of the film thickness is likely to occur, so that the concentration of water in the coating solution is preferably as small as possible. Therefore, the concentration of water in the coating liquid is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and most preferably 0 to 5% by mass. Thus, by maintaining the concentration of water in the coating solution, the above formula (in combination with the maintenance of the acid concentration of the coating solution and the concentration of the silicon alkoxide (or its hydrolyzate) in the coating solution) The hydrolysis reaction of the remaining alkoxyl group of II) and the dehydration condensation reaction of the above formula (III) are less likely to occur in the coating solution before coating. Even if the concentration of water in the coating liquid is zero, the hydrolysis reaction is not hindered because moisture in the air is absorbed by the coating film after being applied to the substrate. However, when alcohol is used as a solvent, the alcohol originally contains some water, and since the acid is often added in the form of an aqueous solution, the concentration of water in the coating solution is usually It becomes 0.1 mass% or more.

  The coating liquid according to the present invention contains acid and water so that the mass ratio of acid / water is preferably 0.002 or more, more preferably 0.02 or more. This is because the hydrolysis reaction of the remaining alkoxyl group of the above formula (II) and the dehydration condensation reaction of the formula (III) are less likely to occur in the coating solution before coating. When a solution in which a silicon alkoxide, a fluoroalkyl group-containing silane compound, and an acid are dissolved in the above-described solvent is stirred, in the solution, the silicon alkoxide mainly forms a hydrolyzate by the reaction of the above formula (II), and A part of the hydrolyzate undergoes a dehydration condensation reaction by the reaction of the formula (III). Thus, a coating solution is prepared, and in this coating solution, silicon alkoxide is present in the form of a monomer (including a hydrolyzate) or a polymer of less than 20 mer. When the coating liquid is applied to the substrate, the specific surface area of the liquid that has been applied to the film increases, so the solvent in the film evaporates rapidly, and the coating film of silicon alkoxide and its hydrolyzate The intermediate concentration suddenly increases, and the hydrolysis and dehydration condensation reactions (including the further condensation polymerization of the polymer less than the 20-mer) that have been suppressed up to abruptly occur and siloxane bonds (. O-Si ...) is generated in the coating film, and as a result, the bond between the base material and the base layer constituting the water-repellent film is strengthened, and the main component is silica having a film thickness of 5 to 200 nm. A highly dense film is formed. Thus, in the present invention, the reactivity at the time of film formation is high, and the reaction is performed at room temperature to form a very dense film, and subsequent baking is not necessary. In the case where many siloxane bonds by dehydration condensation reaction are already present in the coating liquid before coating as in the prior art and a polymer having a polymerization degree of 20 or more is contained, the resulting water-repellent film contains siloxane. Bonds exist, but not so many siloxane bonds that connect the substrate surface and the water-repellent coating, so the bond between the substrate surface and the water-repellent coating is not so strong. And in order to strengthen this coupling | bonding, in a prior art, higher temperature baking is required.

  As another material for forming the water-repellent coating, (B) a chlorosilyl group-containing compound and (G) a fluoroalkyl group-containing silane compound are dissolved in a solvent containing (A) alcohol and / or moisture, and (B) It is also possible to use a solution in which the chloro group of the chlorosilyl group-containing compound is substituted with an alkoxyl group or a hydroxyl group and the silicon alkoxide or a hydrolyzate thereof is a monomer or a polymer of 19-mer or less.

(B) In the case of forming a water-repellent coating using a chlorosilyl group-containing compound, a solution obtained by dissolving (B) a chlorosilyl group-containing compound and a fluoroalkyl group-containing silane compound in a hydrophilic solvent is used as a base material, for example, a glass substrate. Apply to the surface. At that time, various chemical reactions occur between the —OH group on the substrate surface and the fluoroalkyl group-containing silane compound, (B) chlorosilyl group-containing compound, and hydrophilic solvent in the applied film.
That is, as described in detail below, a chlorosilyl group reacts in solution, during its preparation, during storage and during film formation, and changes to a siloxane bond (—Si—O—Si—). Part of the changed siloxane bond forms a siloxane bond with the fluoroalkyl group-containing silane compound, and the other part forms a siloxane bond with the substrate surface.

For example, when an alcohol solvent is used as the solvent, the chlorosilyl group-containing compound in the solution forms an alkoxide by a dehydrochlorination reaction with the alcohol solvent as shown in the following formula (IV). In addition, the chlorosilyl group-containing compound undergoes a hydrolysis reaction with moisture contained in a trace amount in an alcohol solvent or atmosphere, and hydrogen chloride is removed as shown in Formula (V) (dehydrochlorination reaction). At this time, silanol (..Si-OH) is generated. In the formula, R is an alkyl group.
(..Si-Cl) + (ROH) → (.. Si-OR) + (HCl) (IV)
(·· Si-Cl) + (H ₂ O) → (·· Si-OH) + (HCl) (V)
Hydrochloric acid generated by the formulas (IV) and (V) in an alcohol solvent acts as a catalyst for the reaction of the above formula (II), and a part of (..Si-OR) further generates silanol.
And a part of silanol produced | generated by Formula (V) and said Formula (II) reacts like following formula (VI), and forms a siloxane bond (-Si-O-Si-). Further, a part of the generated silanol undergoes a dehydration condensation reaction as shown in the above formula (III) to form a siloxane bond.

(..Si-Cl) + (.. Si-OH) .fwdarw. (.. Si-O-Si ..) + (HCl)
... (VI)

The reactivity of the chloro group of the chlorosilyl group-containing compound is extremely high. For this reason, the chlorosilyl group-containing compound in the alcohol solvent reacts with most of the chloro group, and (..Si-OR), (..Si-OH), (..Si-O-Si ..), It has changed to (HCl). That is, in the above-mentioned solution, hydrochloric acid is also contained in the alcohol solvent in addition to the silicon alkoxide or a hydrolyzate thereof and the fluoroalkyl group-containing silane compound. Even when the solvent is a non-alcohol hydrophilic solvent, the chloro group reacts with moisture inevitably contained in the hydrophilic solvent, as shown in formula (V) and formula (III) ( (Si-OH), (..Si-O-Si ..), (HCl).
Therefore, since the chloro group with extremely high reactivity hardly remains, the pot life of the solution can be lengthened. Furthermore, since it becomes difficult to be affected by the humidity of the atmosphere during the work, the management thereof becomes easy.

In order to set the surface roughness (Ra) to 0.5 to 3.0 nm, the coating and drying conditions are specified. Specifically, the coating and drying temperatures are 10 to 40 ° C., respectively, and the absolute humidity is 4.5 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), respectively. Preferably, the coating and drying temperatures are each 15 to 35 ° C., and the absolute humidity is 5 × 10 ^{−3 to} 12 × 10 ⁻³ kg / kg (DA), respectively.
In addition, absolute humidity means the humidity which represented the quantity of the water vapor | steam contained in air with the mass ratio per 1 kg of dry air here. [Kg / kg (DA)] is used as a unit to indicate that 1 kg of this dry air is used as a reference.

  Next, in order to impart hydrophilicity with a surface contact angle of 10 ° or less, a surface treatment for selectively removing the water-repellent component constituting the water-repellent coating and the fluoroalkyl group of the underlayer is applied. Examples of the surface treatment method include plasma jet treatment, UV treatment, ozone treatment, and baking treatment. In consideration of workability, plasma jet treatment is preferable. If the contact angle is 10 ° or less, some fluoroalkyl groups may remain.

  By the plasma jet treatment, the bond between the alkyl group and Si in the perfluoroalkylsilane or the like that exhibits the water repellency function can be decomposed, and the water repellency function can be lost.

  The plasma jet treatment can be realized by relatively moving the plasma jet irradiation gun along the surface of the water repellent coating. Since the movement of the plasma jet irradiation gun can be realized without difficulty, the intended treatment can be easily performed even if the water repellent coating has a curved surface.

  The plasma jet treatment is performed by using a plasma jet irradiation gun. The plasma jet irradiation gun is set to operate with an output power of about 0.5 kw, for example, and is arranged 5 to 15 mm away from the processing object. It is preferable to do. By setting the distance between the plasma jet irradiation gun and the surface of the object to be processed to be 5 to 15 mm, a plasma jet flow having a stable output can be generated.

  Moreover, it is preferable to set so that it may move at a conversion speed of 1 to 60 mm / sec in parallel with the surface of the processing object in each pass of the processing. Here, the “converted speed” is a speed obtained by dividing the speed of the plasma jet irradiation gun that moves parallel to the surface of the object to be processed by the number of times of processing with the plasma jet of the object to be processed. The lower limit value of the conversion speed is more preferably 10 mm / sec or more, and further preferably 20 mm / sec or more. The upper limit value is more preferably 50 mm / sec or less, and further preferably 40 mm / sec or less.

  For details of the apparatus and method for performing the plasma jet treatment, for example, paragraphs 0034 to 0041 and FIGS. 1 to 5B of JP-T-2003-509321 and paragraphs 0033 to 0040 of JP-A-2002-187740 and FIG. Reference can be made to FIG. In practice, the treatment can be performed using a commercially available product.

The surface treatment as described above is performed to produce the low-friction coating-coated article of the present invention.
In preparation of the coating liquid, (C) colloidal silica can be added as necessary to adjust the surface roughness of the low friction coating.

The fourth production method of the present invention can be used as a method for producing a low-friction film-coated article having water repellency, except for a surface treatment for removing a water-repellent component. The surface treatment does not have to be performed immediately after the production of the low-friction coating-coated article having water repellency, and can be performed on what has been used or stored as the low-friction coating-coated article having water repellency.
When the low-friction coated article is a vehicle window glass, water repellency or hydrophilicity is selected according to the user's preference. According to the fourth manufacturing method of the present invention, a window glass having such different characteristics is firstly prepared by using a common coating liquid and a low friction coating film-coated glass plate having water repellency by a common facility (hereinafter referred to as “glass pane”). Manufactured simply as a water-repellent glass plate). Thereafter, a surface treatment is performed on the water-repellent glass plate to obtain a hydrophilic low-friction coating-coated glass plate (hereinafter simply referred to as a hydrophilic glass plate).
Many vehicle users tend to select a water-repellent glass plate that does not require the wiper to operate during high-speed running. Therefore, manufacturing the window glass as a water-repellent glass plate and manufacturing the hydrophilic glass plate by surface treatment as necessary is effective in terms of manufacturing cost and inventory management.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
Below, the measuring method of each physical-property value in each Example and a comparative example is shown.

[Measuring method]
(Procedure 1) According to the following (Measurement Method 1), the contact angle of water on the surface of the sample glass was measured.
(Procedure 2) 2 mL of ethanol was placed on a Bencot (“LINTFREE AZ-8”, manufactured by Asahi Kasei Co., Ltd.), and the surface of the obtained sample glass was rubbed 10 times, and then wiped dry with a new Bencot 10 times. And the contact angle and sliding angle of the sample glass surface were measured.
(Procedure 3) Compared with the previous measurement result, (Procedure 2) was repeated until the measured value was stabilized. This is intended to remove excess water repellent when the sample glass surface is dirty and the sample glass is water repellent.
(Procedure 4) When the contact angle and the sliding angle were stabilized, the surface roughness and the dynamic friction coefficient were measured according to the following (Measurement Method 3) and (Measurement Method 4).
Each measured value obtained by the above procedure was used as the initial measured value.

(Measuring method 1) Measurement of contact angle The contact angle of a 3 microliter water droplet was measured by the sessile drop method using the contact angle measuring machine ("CA-V150 type | mold", Kyowa Interface Science company make). The larger the contact angle value, the better the static water repellency.

(Measurement Method 2) Measurement of Surface Roughness (Ra) Using an atomic force microscope (“SPI3700”, manufactured by SII Nanotechnology Inc.), the surface shape is measured in the cyclic contact mode, and the arithmetic average roughness The value of Ra was calculated. The cantilever used was “SI-DF20” made of silicon, the measurement area of the sample is a square of 1 μm × 1 μm, the number of measurement points is 512 × 256 points, the scanning speed is 1.02 Hz, the correction by the low-pass filter, and the leveling of the measurement data Correction was performed and surface roughness (Ra) was calculated. Note that the leveling correction of the measurement data was performed by obtaining and fitting a curved surface by least square approximation, correcting the inclination of the data, and further removing distortion in the Z-axis direction.

(Measuring method 3) Measurement of dynamic friction coefficient The dynamic friction coefficient was measured by the method in which a water-repellent coating was formed on a flat glass plate described in the specification text. As the wiper rubber, “Part No. 85214-22420” (replacement part of Toyota Motor Corporation) was used.

[Example 1 and Example 6]
As a base material, a glass plate whose surface to be coated was washed with celico was prepared.
98.9 g of ethanol (manufactured by Kanto Chemical) as an alcohol solvent, 0.4 g of tetrachlorosilane (manufactured by Shin-Etsu Silicone) as a chlorosilyl group-containing compound, and colloidal silica having a particle diameter of 40 to 50 mm (Snowtex OL: manufactured by Nissan Chemical Co., Ltd.) 0 0.7 g was added and stirred for 30 minutes to prepare a coating solution. This coating solution was applied to the surface of a glass plate that had been cleaned with celico using a flow coating method at a temperature of 20 ° C. and a relative humidity of 30% RH (absolute humidity 4.3 × 10 ⁻³ kg / kg (DA)). The glass plate was coated with the low friction coating film of Example 6 by drying for about 30 minutes under the same conditions.
The contact angle and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Example 6, and the results are shown in Table 1 below.
The low-friction coating-coated glass plate of Example 1 was obtained by subjecting the coating of the low-friction coating-coated glass plate of Example 6 to plasma jet treatment, which will be described later, which is a surface treatment for removing organic components on the surface. . The surface roughness, contact angle, and dynamic friction coefficient of the coating on the side of the low friction coating coated glass of Example 1 were measured, and the results are shown in Table 1.

For the plasma jet treatment, a plasma treatment apparatus (PJ-1: manufactured by Corotech) was used under the following conditions.
・ Output: 0.5kW
・ Distance between head and workpiece: 8mm
・ Conversion head feed speed: 20mm / sec
・ Flow velocity of plasma jet: about 7m / sec

[Example 2 and Example 7]
As a base material, a glass plate whose surface to be coated was washed with celico was prepared.
Tetrachlorosilane 0.5g was added to ethanol 99.5g, and it stirred for 30 minutes, and produced the base layer coating liquid.
Tetrachlorosilane 0.5g was added to 99.5 g of decamethylcyclopentasiloxane (KF-995: manufactured by Shin-Etsu Silicone), which is a silicone solvent, and stirred for 30 minutes to prepare an upper layer coating solution.
Apply the flow coating method to the surface of a glass plate that has been washed with a ground layer coating solution under the conditions of a temperature of 20 ° C. and a relative humidity of 30% RH (absolute humidity 4.3 × 10 ⁻³ kg / kg (DA)). And dried for about 30 minutes under the same conditions to obtain an underlayer-coated glass plate.
The upper layer coating solution is applied on the underlayer of the underlayer-coated glass plate by a flow coat method under the conditions of a temperature of 20 ° C. and a relative humidity of 30% RH (absolute humidity 4,3 × 10 ⁻³ kg / kg (DA)). Immediately after application, the excess upper layer coating solution on the surface of the glass plate was washed away using the solvent used in the production of the upper layer coating solution, and the glass plate surface was left wet with this solvent for 1 minute under the same conditions. . Thereafter, the silicone solvent on the surface of the glass plate was washed away with ethanol and dried under the same conditions for about 30 minutes to obtain the low friction coating-coated glass plate of Example 7.
The contact angle and the dynamic friction coefficient were measured for the coating film of the low friction coating-coated glass plate of Example 7, and the results are shown in Table 1.
The low-friction coating-coated glass plate of Example 2 was obtained by subjecting the coating of the low-friction coating-coated glass plate of Example 7 to plasma jet treatment described below under the same conditions as in Example 1. The surface roughness, contact angle, and dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Example 2 and the results are shown in Table 1.

[Example 3 and Example 8]
As a base material, a glass plate whose surface to be coated was washed with celico was prepared.
0.5 g of tetrachlorosilane (made by Shin-Etsu Silicone), which is a chlorosilyl group-containing compound, was added to 99.5 g of an isoparaffin-based hydrocarbon solvent (Isosol 300: manufactured by Shin Nippon Petrochemical Co., Ltd.) and stirred for 30 minutes to prepare a coating solution. . This coating solution was applied to the surface of a glass plate that had been cleaned with celico under the conditions of a temperature of 20 ° C. and a relative humidity of 30% RH (absolute humidity 4.3 × 10 ⁻³ kg / kg (DA)) by a flow coating method. . Then, the excess coating solution on the surface of the glass plate was immediately washed away using the solvent used for the production of the coating solution, and the glass plate surface was left wet with this solvent for 1 minute under the same conditions. Thereafter, the isoparaffinic hydrocarbon solvent on the surface of the glass plate was washed away with ethanol and dried under the same conditions for about 30 minutes to obtain a low friction coating-coated glass plate of Example 8. The contact angle and the coefficient of dynamic friction were measured for the coating of this low-friction coating-coated glass plate, and the results are shown in Table 1.
The low-friction coating-coated glass plate of Example 3 was obtained by subjecting the coating of the low-friction coating-coated glass plate of Example 8 to plasma jet treatment described below under the same conditions as in Example 1. The surface roughness, the contact angle, and the dynamic friction coefficient were measured for the coating of the low-friction coating-coated glass plate of Example 3, and the results are shown in Table 1.

[Example 4 and Reference Example 1]
97.38 g of ethanol (water content 0.35 mass%), 0.6 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) as silicon alkoxide and heptadecafluorodecyltrimethoxysilane (CF as organosilane containing a fluoroalkyl group) ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , manufactured by Shin-Etsu Silicone Co., Ltd. (0.02 g) was added, stirred for 30 minutes, and then stirred with concentrated hydrochloric acid (concentration 35% by mass, By adding 2.0 g of Kanto Chemical Co., Ltd., a water repellent coating solution (coating solution) was obtained. Water was mainly contained in ethanol and concentrated hydrochloric acid, and the total amount was 1.64 g. Therefore, the content of water contained in this water-repellent coating solution was 1.64% by mass. And hydrochloric acid corresponded to 0.15 normality. Further, tetraethoxysilane contained in this water-repellent coating solution was 0.173% by mass in terms of silica, and heptadecafluorodecyltrimethoxysilane was 0.0021% by mass in terms of silica.
This water-repellent coating solution is applied to the surface of a cleaned glass substrate by a flow coating method under conditions of room temperature (20 ° C.) and relative humidity of 40% RH (5.9 × 10 ⁻³ kg / kg (DA)). And applied. The glass plate was coated with the low friction coating film of Reference Example 1 by drying for about 30 minutes under the same conditions. This low-friction coating-coated glass plate corresponds to the water-repellent coating-coated glass plate of Example 2 of Patent Document 4.
The surface roughness, the contact angle, and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Reference Example 1, and the results are shown in Table 1.
The low-friction coating-coated glass plate of Reference Example 1 was subjected to plasma jet treatment under the same conditions as in Example 1 to obtain the low-friction coating-coated glass plate of Example 4. The surface roughness, the contact angle, and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Example 4, and the results are shown in Table 1.

[Example 5 and Reference Example 2]
The same conditions as in Reference Example 1 except that the relative humidity was changed to 55% RH (absolute humidity: 8.1 × 10 ⁻³ kg / kg (DA)) as a condition for applying and drying the water repellent coating solution. Thus, a low friction coating-coated glass plate of Reference Example 2 was obtained. This low-friction coating-coated glass plate corresponds to the water-repellent coating-coated glass plate of Example 3 of Patent Document 4.
The surface roughness, the contact angle, and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Reference Example 2, and the results are shown in Table 1.
The low-friction coating-coated glass plate of Example 5 was obtained by subjecting the coating of the low-friction coating-coated glass plate of Reference Example 2 to plasma jet treatment under the same conditions as in Example 1. The contact angle and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Example 5, and the results are shown in Table 1.

[Comparative Example 1 and Comparative Example 3]
As a base material, a glass plate whose surface to be coated was washed with celico was prepared.
Using the base coating liquid of Example 2, the surface of the glass plate was coated in the same manner as the base layer of Example 2, and the coating-coated glass plate of Comparative Example 3 was obtained.
The contact angle and the dynamic friction coefficient were measured for the coating of the low friction coating coated glass plate of Comparative Example 3, and the results are shown in Table 1.
The film-coated glass plate of Comparative Example 3 was subjected to plasma jet treatment under the same conditions as in Example 1 to obtain a film-coated glass plate of Comparative Example 1. The surface roughness, the contact angle, and the dynamic friction coefficient were measured for the coating of the coating-coated glass plate of Comparative Example 1, and the results are shown in Table 1.

[Comparative Example 2 and Comparative Example 4]
As a base material, a glass plate was prepared and used as an uncoated glass plate of Comparative Example 4 (hereinafter referred to as a normal glass plate).
The contact angle and dynamic friction coefficient were measured on the surface of the normal glass plate of Comparative Example 4, and the results are shown in Table 1.
Plasma jet treatment was performed on the surface of the normal glass plate of Comparative Example 4 under the same conditions as in Example 1 to obtain a normal glass plate after the plasma jet treatment of Comparative Example 2. Surface roughness, contact angle, and dynamic friction coefficient were measured on the treated surface of the normal glass plate of Comparative Example 2, and the results are shown in Table 1.

Hereinafter, consideration will be given with reference to the measurement values listed in Table 1.
[Dynamic friction coefficient]
The dynamic friction coefficients of the normal glass plate of Comparative Example 4 in the dry state and the wet state were 0.59 and 0.28, respectively, and the absolute value of the difference (hereinafter simply referred to as the difference) was 0.31. . The dynamic friction coefficients of the dry state and the wet state of the normal glass plate treated with the plasma jet of Comparative Example 2 were 0.65 and 0.31, respectively, and the difference between them was 0.36. When considering the dynamic friction coefficient of the low-friction coating-coated article of the present invention, the dynamic friction coefficient of this normal glass sheet is the standard. That is, if the dynamic friction coefficient in the wet state of the coated glass plate having hydrophilicity or intermediate wettability between hydrophilicity and water repellency is 0.30 or less, judder improvement can be expected.
The wet friction coefficients of the coated glass plates in Examples 6 to 8 before the plasma jet treatment were 0.26, 0.19, and 0.19, respectively, which were smaller than 0.28 in Comparative Example 4. I understand that. The dynamic friction coefficients in the wet state of the coated glass plates in Examples 1 to 5 after the plasma jet treatment were 0.27, 0.26, 0.25, 0.15, and 0.15, respectively. It can be seen that the coefficient of dynamic friction in the wet state is smaller than 0.31. In particular, the dynamic friction coefficient in the wet state in Examples 4 and 5 is 0.20 or less, which is about half the value of the dynamic friction coefficient 0.31 in the wet state in Comparative Example 2, and is low in the wet state. It can be seen that the friction is improved.
The difference in the dynamic friction coefficient of the film-coated glass plate in Example 4 is 0.43, which is larger than that of the normal glass plate in Comparative Example 4, but this film-coated glass plate has high hydrophilicity, Since water easily spreads in the form of a film, a large difference in the dynamic friction coefficient during sufficient rain does not hinder good wiper operation.
The difference in the dynamic friction coefficient in the examples other than Example 4 is 0.30 or less, the difference in the dynamic friction coefficient in Examples 1 to 3 and 6 to 8 is 0.20 or less. It can be seen that the difference in the dynamic friction coefficient between 2, 6, and 7 is 0.10 or less. Thus, when the difference in the coefficient of dynamic friction becomes small, even when the hydrophilicity is low as in Example 7 or when the wiper is operated with a small amount of rain even if the hydrophilicity is high, judder of the wiper rubber hardly occurs. Good wiper operation can be obtained.
The coating-coated glass plate of Comparative Example 3 has improved hydrophilicity than that of the normal glass plate of Comparative Example 4, but the wet dynamic friction coefficient is higher than that of the normal glass plate of Comparative Example 4. As a result, the improvement effect of judder was low.
It can be seen that the coefficient of kinetic friction between the dry state and the wet state of the coated glass plate of Comparative Example 1 is approximately the same as those of the normal glass plate of Comparative Example 2. This is presumably because the surface roughness Ra of Comparative Example 1 was 0.2 nm, which was the same as that of Comparative Example 2, so that the effect of the coating was not exhibited.
It can be seen that the wet friction coefficient of the coated glass plates having water repellency of Reference Examples 1 and 2 is equal to or higher than that of the normal glass plate of Comparative Example 4. However, in the case of a water-repellent coating, the difference in the dynamic friction coefficient is effective in improving judder, and the difference in the dynamic friction coefficient between Reference Examples 1 and 2 is 0.00 and 0.03, which are 0.10 or less, respectively. Therefore, the judder improvement effect was high.

[Contact angle]
The contact angle of each glass plate before the plasma jet treatment was as follows. It can be seen that the surfaces of the film-coated glass plates of Examples 6 and 8 have hydrophilicity with contact angle values of 7.0 ° and 17.4 ° (20 ° or less), respectively. It can be seen that the surface of the film-coated glass plate of Comparative Example 3 also has hydrophilicity with a contact angle value of 23.6 °.
It can be seen that the surface of the film-coated glass plate of Example 7 has a contact angle value of 70.6 °, indicating intermediate wettability between hydrophilicity and water repellency.
It can be seen that the surface of the film-coated glass plate of Reference Examples 1 and 2 has a high water repellency because the value of the contact angle exceeds 100 °.
The surface of the normal glass plate of Comparative Example 4 had a contact angle value of 53.3 ° and was slightly higher in hydrophilicity, but this was completely removed by wiping in step 2 of the measurement method described above. This is thought to be due to the influence of residues such as organic matter.
The contact angle of each glass plate after the plasma jet treatment was as follows. The contact angles of the surfaces of the film-coated glass plates of Examples 1 to 5 are 0.7 °, 2.7 °, 2.9 °, 6.7 °, and 7.2 ° (10 ° or less), respectively. It can be seen that it has hydrophilicity. In particular, it can be seen that the contact angles of Examples 1 to 3 are 5 ° or less, indicating excellent hydrophilicity. It can be seen that the surface of the film-coated glass plate of Comparative Example 1 also has excellent hydrophilicity with a contact angle of 4.7 °. It can be seen that the surface of the normal glass plate of Comparative Example 2 also has excellent hydrophilicity with a contact angle of 3.8 °.
This is hydrophilic because the organic residue and water repellent components (Reference Examples 1 and 2) contained in the coating liquid remaining on the coating surface and in the coating were removed by the plasma jet treatment. It is considered that the properties of the film mainly composed of silicon oxide appear. And it turns out that the surface of a normal glass plate originally has the outstanding hydrophilicity.

[Surface roughness Ra]
Among the measurement results shown in Table 1, for the measurement results of Examples 1 to 4 and Comparative Example 1 in which the surface roughness Ra after the plasma jet treatment was measured, the surface roughness Ra and the dynamic friction coefficient (dry state (Dry)) And a graph showing the relationship with the wet state (Wet)) is shown in FIG. Since Comparative Example 2 is usually a measurement result on the surface of the glass plate, it was excluded from the graph. In the graph of the dry state, an approximate curve is also shown as a quadratic curve for reference. In the wet state graph, an approximate curve is also shown as a linear curve (straight line) for reference.
The graphs of Examples 6 to 8, Reference Example 1, and Comparative Example 1 before the plasma jet treatment corresponding to the graph of FIG. 1 are shown in FIG. As the surface roughness Ra, the value of the surface roughness Ra after the plasma jet treatment was used. When the surface roughness Ra of Reference Example 1 and Example 4 is compared, the surface roughness Ra of Example 4 is smaller, so the surface roughness of the other examples and comparative examples is also reduced after the plasma jet treatment. Although there is a possibility that it has changed, we decided to use it to find out the tendency of the dynamic friction coefficient before plasma jet treatment. In the graphs of the dry state and the wet state, approximate curves are also shown as secondary curves for reference.
It can be seen that the graph before the plasma jet treatment tends to have a downward quadratic curve in both the dry state and the wet state.
The graph of the wet state after the plasma jet treatment has a tendency of a straight line, unlike the graph before the plasma jet treatment, and the slope thereof is small. Therefore, the surface roughness Ra where no measurement value exists is wide even in the range exceeding 15.2 nm. The wet dynamic friction coefficient is expected to be 0.30 or less in the range. When the surface roughness Ra after the plasma jet treatment is 0.2 nm (Comparative Example 1), the dynamic friction coefficient in the wet state is approximately the same as that of the normal glass plate (Comparative Example 2), but the surface roughness Ra is 0.9 nm. In the case of (Example 4), the dynamic friction coefficient in the wet state is usually about half that of the glass plate (Comparative Example 2). Therefore, if the surface roughness Ra is 0.5 or more, the dynamic friction coefficient in the wet state is 0.00. Expected to be 30 or less.

If the dynamic friction coefficient in the wet state is 0.30 or less, the upper limit value of the surface roughness Ra after the plasma jet treatment is not particularly limited. From the graph of the approximate curve in the wet state shown in FIG. 1 (linear (Wet)), it is expected that the dynamic friction coefficient in the wet state will be 0.30 or less even if the surface roughness Ra is about 20 nm. From the graphs of the two approximate curves shown in FIG. 1 (secondary curve (Dry) and linear (Wet)), if the surface roughness Ra after the plasma jet treatment is about 2 nm to about 18 nm, the dynamic friction coefficient The difference is expected to be 0.30 or less.
Therefore, the lower limit of the surface roughness Ra after the surface treatment such as plasma jet treatment is preferably 0.5 nm, and the upper limit is not particularly limited, but 20 nm is preferable. Considering the difference in the dynamic friction coefficient, the range of the surface roughness Ra after the surface treatment is more preferably 2 to 18 nm.
From the measured value (Dry) of the wet state and the graph of the approximate curve (secondary curve (Wet)) shown in FIG. 2, if the surface roughness Ra before the plasma jet treatment is about 2 nm to 16 nm, the wet state It can be seen that the dynamic friction coefficient is about 0.30. From the graphs of the two approximate curves shown in FIG. 2 (Dry and quadratic curve (Wet)), it can be seen that the difference in the dynamic friction coefficient in this range is 0.20 or less, particularly 0.10 or less. .
Therefore, the lower limit of the surface roughness Ra before the surface treatment is preferably 2 nm, and the upper limit is preferably 16 nm.

It is a graph which shows the relationship between the surface roughness (Ra) after a plasma processing, and a dynamic friction coefficient. It is a graph which shows the relationship between the surface roughness (Ra) before a plasma processing, and a dynamic friction coefficient. It is the schematic which shows the measuring method of a dynamic friction coefficient (flat glass plate). It is the schematic which shows the measuring method of a dynamic friction coefficient (curved glass plate).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Coated article 2 Wiper rubber specimen 3 Towing tool 4 Measuring device 11 Glass plate (flat plate)
12 Coating 13 Glass plate (curved)
21 Wiper rubber 22 Plate-like body 23 Weight 24a Center mark 24b Center mark

Claims (12)

A substrate and a low friction coating formed on the substrate;
The low friction coating is formed on the side in contact with the wiping member,
The low-friction film is mainly composed of silicon oxide,
As a measurement condition for the dynamic friction coefficient between the surface of the low friction coating and the wiping member, when the moving speed of the wiping member on the surface of the low friction coating is 50 cm / min, the dynamic friction coefficient in a wet state Is a low-friction coating-coated article having a value of 0.30 or less.   The low-friction coating-coated article according to claim 1, wherein a contact angle of water on the surface of the low-friction coating is 80 ° or less.   The low-friction coated article according to claim 1 or 2, wherein an absolute value of a difference in dynamic friction coefficient between a dry state and the wet state is 0.30 or less.   The low-friction coating-coated article according to claim 2 or 3, wherein the water contact angle is 20 ° or less.   The low-friction coated article according to any one of claims 1 to 4, wherein organic substances are removed from the surface of the low-friction coating by a surface treatment.   The low-friction coating-coated article according to claim 5, wherein the contact angle of water is 10 ° or less.   The low-friction coating-coated article according to claim 5 or 6, wherein the surface treatment is a plasma jet treatment. (A) Coating in which (B) chlorosilyl group-containing compound and (C) colloidal silica are dissolved in a solvent containing alcohol and / or water, and (B) the chloro group of the chlorosilyl group-containing compound is substituted with an alkoxyl group or a hydroxyl group A liquid is prepared, and the coating liquid is applied to the substrate under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). A method for producing a low-friction coating-coated article that is dried under conditions of an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). (A) Dissolving the (B) chlorosilyl group-containing compound in a solvent containing alcohol and / or water, and (B) preparing an undercoat coating solution in which the chloro group of the chlorosilyl group-containing compound is substituted with an alkoxyl group or a hydroxyl group,
(D) Dissolving the (B) chlorosilyl group-containing compound in a silicone-based solvent to prepare an upper layer coating solution,
Under the conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), the base layer coating solution is applied to the substrate, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 A base layer is formed on the surface of the base material by drying under conditions of × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA),
The upper layer coating solution is applied on the base layer of the base material under conditions of a temperature of 10 to 40 ° C. and an absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). The excess upper layer coating solution on the surface of the substrate is washed away using the solvent used for the preparation of the coating solution, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA ), And then the silicone solvent on the surface of the base material is washed away with alcohol, and the temperature is 10 to 40 ° C. and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA A method for producing a low-friction coating-coated article that dries under the conditions of (E) A coating liquid is prepared by dissolving (B) a chlorosilyl group-containing compound in a hydrocarbon solvent, and the temperature is 10 to 40 ° C., and the absolute humidity is 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). The coating liquid is applied to the substrate under the conditions of the above, and the excess coating liquid on the surface of the base material is washed away using the (E) hydrocarbon solvent used in the preparation of the coating liquid. Let stand for 1 second or more under the condition of absolute humidity 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA), wash away the (E) hydrocarbon solvent on the substrate surface with alcohol, A method for producing a low-friction coating-coated article which is dried under conditions of 40 ° C. and absolute humidity of 1 × 10 ⁻³ to 18 × 10 ⁻³ kg / kg (DA). (F) Silicon alkoxide and / or its hydrolyzate 0.01-2 mass% (silica conversion), (G) Fluoroalkyl group-containing silane compound 0.00001-0.15 mass% (silica conversion), (H) An acid and (I) a coating liquid containing 0 to 20% by mass of water and having an acid concentration of 0.001 to 3 N, or (B) a chlorosilyl group-containing compound and (G) a fluoroalkyl group-containing silane compound Is dissolved in a solvent containing (A) alcohol and / or water and the chloro group of the (B) chlorosilyl group-containing compound is replaced with an alkoxyl group or a hydroxyl group, a coating solution having a temperature of 10 to 40 ° C. and an absolute humidity of 4 .5 × 10 ^-3 in the conditions of ^{~18 × 10 -3 kg / kg (} DA) was applied to the substrate, temperature of 10 to 40 ° C., absolute humidity of ^{4.5 × 10 -3 ~18 × 10 -3} kg / After drying under the conditions of g (DA), a manufacturing method of a low friction coating coated article subjected to a surface treatment to remove the water repellent component surface to form a hydrophilic film.   The method for producing a low-friction coating-coated article according to claim 11, wherein the surface treatment is a plasma jet treatment.

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