JP2002012452A - High water slip substrate and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high water slip substrate having both durability in high water repellency, and excellent light resistance and wear resistance, together with excellent water slip property (droplet slidable property). SOLUTION: The water slip coating is formed by applying a copolymer of fluoroalkyltrichlorosilan and silanol-terminated polydimethylsiloxane on a silica coupling layer formed on the surface of the transparent substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to, in particular, architectural glazings,
The present invention relates to a highly water-slidable substrate which can be used for vehicle window glasses, mirrors, other industrial window glasses, etc., and exhibits extremely excellent water-sliding property (water-dropping property) and a method for producing the same.

[0002]

2. Description of the Related Art In order to obtain high water-repellent durability (light resistance and abrasion resistance), a great number of inventions have been made on water-repellent glass obtained by treating a substrate surface with a fluoroalkyl group-containing silane compound. . For example, Japanese Patent Application Laid-Open No. 6-16455 discloses that it is very effective to provide a base film such as silica having an uneven shape on a glass surface. On the other hand, those having no base film are described in US Pat.
Japanese Patent Application Laid-Open No. 00178 discloses a method for forming a water- and oil-repellent monomolecular film on a glass surface. And a method using a fluoroalkyl group-containing silane compound having an increased or controlled degree of polymerization as a water-repellent treatment liquid. Further, JP-A-8-325037 discloses that after forming an alkali barrier layer containing no alkali metal or having a small alkali metal content in the vicinity of a glass substrate surface, a fluoroalkyl group-containing silane compound is treated. A method for obtaining a highly durable water-repellent treated glass is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 9-48639 discloses a method of treating a glass substrate surface with an alkali-free layer to reduce the amount of an alkali component such as sodium and then treating a fluoroalkyl group-containing silane compound. Discloses that the heat resistance, the water resistance and the weather resistance are improved.

On the other hand, studies have been made with an emphasis on further improving the water sliding property (water drop sliding property), and a high water drop falling property or high water sliding glass has been proposed. For example, a composition containing a silicone wax, an organopolysiloxane, a surfactant and the like has been invented.
JP-A No. 15473 discloses a composition comprising an alkylpolysiloxane and an acid, and JP-A-5-301742 discloses a composition containing an amino-modified silicone oil and a surfactant.

Further, Japanese Patent Application Laid-Open No. 11-116943 discloses a surface treating agent comprising a composition in which at least the terminal F atom of the fluoroalkyl group of a perfluoroalkyl group-containing silane compound is substituted with an H atom, Furthermore, JP-A-2000-26758 discloses a coating composition capable of forming a water-slidable film as a hydroxyl-containing vinyl polymer, an epoxy-terminated siloxane polymer, a sulfonic acid compound, a polyisocyanate compound which may be blocked and melamine. With a coating composition capable of forming a water-slidable film containing at least one crosslinking agent component selected from a resin and a surfactant selected from a specific dialkyl sulfosuccinate and an alkylene oxide silane, a falling angle at a water droplet volume of 10 μl. Shows very excellent properties of 5 # or less It has been disclosed.

[0005]

However, the above-mentioned Japanese Patent Application Laid-Open Nos. 6-16455, 2500178, 10-59745, and 8-3250 disclose the above-mentioned JP-A-6-16455, JP-A-2500178, JP-A-10-59745, and JP-A-8-3250.
No. 37, JP-A-9-48639 describes a water-repellent glass obtained by treating a substrate surface with a fluoroalkyl group-containing silane compound having high water-repellent durability (light resistance and abrasion resistance). Poor (slipperiness), for example, at a 30 ° inclination, which is the mounting angle of a windshield for automobiles, the volume of at least water droplets at rest is about 40 to
If it is not more than 60 μl, there is a problem that water drops do not slide down and remain on the glass surface.

Further, those obtained by the methods described in Japanese Patent Publication No. 50-15473 and Japanese Patent Application Laid-Open No. 5-301742 have good water-sliding properties (water-dropping properties).
Although a material that slides down with a water drop of about 15 μl at an angle of inclination has been obtained, it has not yet reached high durability (light resistance and abrasion resistance).

Furthermore, the coating obtained in JP-A-11-116943 is not sufficiently durable, and the water-slidable coating obtained in JP-A-2000-26758 has low transparency. It is limited to use as a coating material.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has high durability (light resistance and abrasion resistance) and excellent water sliding property (hereinafter referred to as "water drop sliding property"). And a method for manufacturing the same with high transparency and high water-slidability.

That is, the highly water-slidable substrate of the present invention has a fluoroalkyltrichlorosilane represented by the general formula [1] and a general formula [2] on a silica coupling layer formed on the surface of a transparent substrate. A water-slidable film formed of a copolymer of silanol-terminated polydimethylsiloxane.

CF ₃ (CF ₂ ) _m (CH ₂ ) ₂ SiCl ₃ [1] (where m is an integer of 0 to 11) HO- [Si (CH ₃ ) ₂ O-] _n H [2] ( Wherein n is an integer of 1 to 50) Further, the highly water-slidable substrate of the present invention is characterized in that the silica coupling layer comprises a hydrolyzate of tetraalkoxysilane or a coating solution obtained by diluting tetraisocyanatesilane. A film thickness of at least 2 formed by coating on a glass substrate surface
It is characterized by being a silica film of 0 nm or less.

Further, in the highly water-slidable substrate of the present invention, the water-slidable film is a mixture of the fluoroalkyltrichlorosilane represented by the general formula [1] and the silanol-terminated polydimethylsiloxane represented by the general formula [2]. The molar ratio is 1: 0.
It is characterized in that the composition is a composition which has been subjected to a copolymerization reaction as Nos. 1-2.

Further, a method of manufacturing a highly water-slidable substrate according to the present invention is characterized in that a highly water-slidable substrate is manufactured by the following steps. (1) a step of applying a hydrolyzate of tetraalkoxysilane or a coating solution for an underlayer containing tetraisocyanatesilane as a main component on the surface of the transparent substrate; (2) drying and / or drying
Or a step of performing a heat treatment at a temperature of 190 ° C. or less to form a silica coupling layer as an underlayer; (3) a fluoroalkyltrichlorosilane represented by the general formula [1] and a silanol represented by the general formula [2] A step of applying a coating liquid for a water-slidable film comprising a copolymer of terminal polydimethylsiloxane, (4) a step of drying and / or heat-treating at a temperature of 190 ° C. or lower to form a water-slidable film, CF ₃ (CF ₂ ) _m (CH ₂ ) ₂ SiCl ₃ [1] (where m is an integer from 0 to 11) HO- [Si (CH ₃ ) ₂ O-] _n H [2] (where n = 1 to 50) Further, in the method for producing a highly water-slidable substrate according to the present invention, the coating liquid for the underlayer may be a hydrolyzate of tetraalkoxysilane having a concentration of 0.1 to 5.0 wt% or 0.1 to 5.0 wt%. 0wt%
It is characterized by comprising tetraisocyanate silane at a concentration.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The highly water-slidable substrate of the present invention can be manufactured by the following steps as a typical method. (1) a step of applying a hydrolyzate of tetraalkoxysilane or a coating solution for an underlayer containing tetraisocyanatesilane as a main component on the surface of the transparent substrate; (2) drying and / or drying
Or a step of performing a heat treatment at a temperature of 190 ° C. or less to form a silica coupling layer as an underlayer; (3) a fluoroalkyltrichlorosilane represented by the general formula [1] and a silanol represented by the general formula [2] A step of applying a coating liquid for a water-slidable film comprising a copolymer of terminal polydimethylsiloxane, (4) a step of drying and / or heat-treating at a temperature of 190 ° C. or lower to form a water-slidable film, CF ₃ (CF ₂ ) _m (CH ₂ ) ₂ SiCl ₃ [1] (where m is an integer from 0 to 11) HO- [Si (CH ₃ ) ₂ O-] _n H [2] (where n = 1 to 50) It is necessary to provide an underlayer comprising a silica coupling layer on the surface of the substrate on which the water-slidable film is formed.

The silica coupling layer is formed by applying a coating solution containing a hydrolyzate of tetraalkoxysilane or tetraisocyanatesilane to the surface of the substrate, followed by drying and / or heat treatment at a temperature of 190 ° C. or less. Can be formed. In addition, the coating liquid is 0.1 to
It is preferable to be composed of a 5.0 wt% concentration of a tetraalkoxysilane hydrolyzate or a 0.1 to 5.0 wt% concentration of tetraisocyanate silane. As the hydrolyzate of the tetraalkoxysilane, those prepared by adding a small amount of water and an acid catalyst such as hydrochloric acid, nitric acid, and acetic acid using tetramethoxysilane, tetraethoxysilane, and the like as a starting material can be used. In addition, when obtaining a dilute solution of the above-mentioned tetraisocyanate silane, a solvent containing substantially no water, that is, ethyl acetate, n-butyl acetate, n-hexyl acetate or the like can be used.

The coating solution for the coupling layer thus obtained is uniformly applied to a clean glass substrate by hand coating or spraying, and then dried at room temperature for about 5 minutes to obtain a film having a thickness of at least 20 nm. The following silica film is formed. A high concentration of silanol groups (Si-OH) are formed on the surface of the coupling layer made of silica, and these become reaction active sites for immobilizing the water-sliding composition on the surface, and the initial water-sliding properties are obtained. And play an important role in improving durability.

After the coating solution for the coupling layer is applied, the coating solution may be dried naturally by air drying, or may be subjected to a heat treatment at a temperature exceeding room temperature and 190 ° C. or less after drying or simultaneously with drying. In the case of performing the heat treatment, it is necessary to perform the heat treatment at a temperature higher than room temperature and equal to or lower than 190 ° C., thereby removing the solvent and moisture from the film and generating more silanol groups. It is. However, heat treatment at a temperature of 200 ° C. or more is not preferable because the generated silanol groups form siloxane bonds due to a dehydration condensation reaction, and as a result, the concentration of the silanol groups decreases. Depending on the type of coating solution used,
It is preferable to sufficiently dry the film at a temperature from room temperature to about 100 ° C. from the viewpoint of increasing the mechanical strength and the reactivity with the water-slidable composition.

The perfluoroalkyltrichlorosilane represented by the general formula [1] includes, for example, CF
₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₉ C
H ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiC
l ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃ , CF ₃ CH
₂ CH ₂ SiCl ₃ or the like can be used. Examples of the silanol-terminated polydimethylsiloxane represented by the general formula [2] include HO- [Si (CH ₃ ) ₂ O-] ₁₀ H and H
O- [Si (CH ₃ ) ₂ O-] ₂₀ H or the like can be used.

The solvent containing substantially no water is a solvent having low solubility in water, for example, esters such as ethyl acetate, n-butyl acetate and n-hexyl acetate, and aromatic hydrocarbons such as toluene and xylene. Hydrogens, n-butane, n
-Aliphatic hydrocarbons such as hexane can be used. As a diluting solvent, in addition to isopropyl alcohol (hereinafter abbreviated as "i-PA"), a lower alcohol solvent having 5 or less carbon atoms such as methanol and ethanol may be used. Ethers and ketones can be used in addition to phenol, and alcohols containing i-PA or ethanol as a main component are preferable.

The mixing molar ratio of the perfluoroalkyltrichlorosilane and the silanol-terminated polydimethylsiloxane can be freely selected, but perfluoroalkyltrichlorosilane: silanol-terminated polydimethylsiloxane = 1: 0.1 to 2 It is preferable to carry out the copolymerization reaction under the following conditions. If the perfluoroalkyltrichlorosilane 1 has a silanol-terminated polydimethylsiloxane of 0.1 or less, the intended effect of improving the slipperiness cannot be obtained. In the case of 2 or more, although good slipperiness is obtained, durability such as light resistance is significantly reduced, which is not preferable in practical use. As for the average polymerization degree of the silanol-terminated polydimethylsiloxane, the reactivity of the terminal silanol groups decreases as the polymerization degree increases. Is desirably 50 or less.

The reaction time for mixing and copolymerizing the perfluoroalkyltrichlorosilane and the silanol-terminated polydimethylsiloxane in a solvent substantially free of water needs to be longer than 2 hours. If it is short, the copolymerization reaction has hardly progressed, and a large amount of perfluoroalkylsilane monomer remains in the coating solution, so that the polydimethylsiloxane component is not effectively fixed on the substrate surface, and high water slip cannot be obtained. It is not preferable.

For drying after applying the surface treatment agent, the surface treatment agent may be air-dried after application, or may be subjected to a heat treatment at a temperature exceeding room temperature and 190 ° C. or less after drying or simultaneously with drying. I can do it. In the case of performing the heat treatment, it is necessary to perform the heat treatment at a temperature higher than room temperature and equal to or lower than 190 ° C., whereby the OH groups of the unreacted fluoroalkyl group-containing silane are combined with other OH groups. However, heat treatment at a temperature of 200 ° C. or higher is not preferable because the polydimethylsiloxane component for improving the lubricity tends to be thermally decomposed. In addition, 60 to 1 in terms of reaction efficiency.
50 ° C. is more preferred.

The water-sliding property in the present invention is defined as a method described in the evaluation method of the following Examples, for example, in a state where a substrate sample having a film treated with the surface treatment agent is inclined at 30 °. Pure water is slowly dropped on the sample surface with a microsyringe. At this time, the amount (volume) of the water droplet at the time when the water droplet moves at least 2 cm in at least 10 seconds.
Is defined as the slipperiness (water-dropping property), and is indicated by “μl”. The high lubricity of the present invention means that the lubricity obtained by the above method is 10 μl or less. The substrate having a highly water-slidable film obtained by the present invention has excellent water repellency as well as the above-mentioned water-slidability because the silica coupling layer is formed on the substrate surface.

The substrate is not particularly limited, such as glass and plastic. For example, in the case of a glass substrate, float glass or glass commonly used for architectural window glass, automotive window glass, or the like is used. -An inorganic transparent plate glass such as a glass produced by a roll-out method is preferable, and colorless or colored, and its type or color tone, a combination with another functional film, and the shape of the glass are not particularly limited. , As well as various types of tempered glass and strength-up glass as well as bent glass,
It can be used as a flat plate or a single plate, and can also be used as a double glazing or a laminated glass. The coating may be formed on both surfaces of the glass substrate.

The method for applying the coating solution for the underlayer or the coating solution for the water-slidable film onto the substrate surface includes hand coating, nozzle flow coating, dipping, spraying, and river coating.
Various coating methods such as a coating method, a flexographic method, a printing method, a flow coating method or a spin coating method, and a known coating method such as a combination thereof can be appropriately employed. It can also be used as a simple type of spray-type water-repellent agent.

[0025]

EXAMPLES The methods for preparing a substrate, preparing a water-repellent liquid, and evaluating the practical durability of the obtained water-repellent substrate, which are items common to the following Examples and Comparative Examples, are as follows. Was.

[Preparation of Substrate] (1) Substrate A: tetraethoxysilane [Si (OC ₂ H ₅ )]
₄ : hereinafter referred to as TEOS] treatment using a hydrolyzate 200 mm x 200 mm x 2 mmt size float glass or tempered glass surface is polished with a polishing solution and a brush polisher, and a glass washer (a product of our company) Was washed with water and dried. The polishing liquid used here was
Approximately 1% glass polishing agent MIRAKE A (manufactured by Mitsui Kinzoku Kogyo)
Was mixed with water. Then, use Echinen for 1
A 0.1N nitric acid aqueous solution was added to TEOS diluted to wt%, and the mixture was stirred at room temperature for about 2 hours to obtain a coating solution. The film was formed by a spray method at a discharge rate of 3.2 g / pc, the film was formed at a humidity of 30% RH or less, and then air-dried at room temperature to obtain a substrate A. The obtained silica coupling layer was a highly transparent and uniform silica film having a thickness of 20 nm or less.

(2) Substrate B: Treatment with tetraisocyanate silane [Si (NCO) ₄ ] Polishing and washing of the glass were performed in the same manner as in 1) above. Then, tetraisocyanate silane (product name: SI-400 / Matsumoto Pharmaceutical Co., Ltd.) diluted to 2 wt% with an ester solvent such as ethyl acetate, n-butyl acetate, or n-hexyl acetate.
Was impregnated into 1 ml cotton cloth (product name: Bencott / Asahi Kasei), hand-coated, and air-dried or heat-treated at room temperature to 300 ° C. for 10 minutes to obtain a substrate B. The obtained silica coupling layer was a highly transparent and uniform silica film having a thickness of 20 nm or less.

(3) Substrate C: No base treatment Polishing and cleaning of the glass were performed in the same manner as in 1) above. Then, it was immersed in a 0.1N sulfuric acid aqueous solution at 35 ° C for 1 minute,
What was washed and dried with a glass washer (manufactured by our company) was used as a substrate C.

(4) Substrate D: Silica-based Underlayer Having Irregular Surface Shape Polishing and cleaning of glass were performed in the same manner as in 1) above. Next, a substrate on which a silica-based base layer having an uneven surface shape was formed was used as a substrate D. In addition, the coating liquid for the underlayer was prepared in the following manner.

Tetraethoxysilane [Si (OC
₂ H ₅ ) ₄ : TEOS] polymerization sol (average molecular weight Mw: about 1
000-3000) and Goyu amount of the mixed sol (tetrabutoxytitanium stabilized with the acetylacetone with tetrabutoxytitanium stabilized with acetylacetone [Ti (O-Bu) _4] for SiO ₂ in terms of the oxide A sol solution A was obtained by adding an isopropyl alcohol (i-PA) solvent and diluting the solution to a solid content concentration of 5% by weight in terms of an oxide. Also, methyltrimethoxysilane [CH ₃ Si (OCH ₃ ) ₃ : MTM
A sol solution B was prepared by adding isopropyl alcohol (i-PA) to the polymerized sol (average molecular weight Mw = about 1,000) of S] and diluting the solid to a concentration of about 20 wt% in terms of oxide as a solid concentration.

Next, 20 g of sol solution A; 20 g of sol solution B;
20 g and butanol (n-BuOH, as a solvent for adjusting the rate of hydrolysis and dehydration condensation reaction)
Water content of 2000 ppm);
For about 3 hours and stirred (Sol C). Furthermore, i-
PA (90 wt%); 324 g and n-BuOH (10 wt%)
%); The sol C was diluted with 36 g of a mixed solvent of about 360 g, and formed into a film by spin coating. Next, the glass substrate with the gel film is pre-baked at 250 ° C. for 30 minutes.
Further, main firing at 610 ° C. to 620 ° C. was performed at a glass temperature to obtain a SiO ₂ —TiO ₂ thin film having fine irregularities on the surface.

(5) Substrate E; Silica Underlayer Having Flat Surface Shape Polishing and cleaning of the glass were performed in the same manner as in 1) above. Subsequently, a substrate on which a silica base layer having a flat surface shape was formed was used as a substrate E. In addition, the coating liquid for the underlayer was prepared in the following manner. CSG- in silica sol
DI-0600 (manufactured by Chisso, solute concentration: 6 wt%) was diluted to 4 wt% with Echinen. Next, a film was formed at 1 mm / s by a dipping method. Next, the glass substrate with the gel film was calcined at 250 ° C. for 30 minutes, and further calcined at a glass temperature of 610 ° C. to 620 ° C. to obtain a silica thin film having a smooth (flat) surface shape. The thickness of the obtained silica thin film is Dektak30 manufactured by Sloan technology.
30 was about 40 nm.

[Preparation of water-sliding liquid] The water-sliding liquid is perfluoroalkyltrichlorosilane (CF ₃ (CF ₂ ) _m CH ₂ CH ₂ S
iCl ₃ : hereinafter referred to as CmFASC) and an average degree of polymerization of 7, 1
Silanol terminated polydimethylsiloxanes such as 0 and 20 (hereinafter N7SOL, N10SOL and N20S
OL, etc.) and proceeded with these copolymerization reactions. FIG. 1 shows the preparation procedure of the synovial fluid and the mixing ratio (weight ratio) of each component. In addition, at the time of mixing of FASC, NnSOL was diluted with a solvent containing substantially no water to a predetermined concentration, and then slowly dropped with stirring.

[Preparation of water-slidable glass] About 1 to 2 ml of the above-mentioned water-slidable liquid was soaked into a cotton cloth (product name: Bencott) on the above-mentioned substrates A to E, and then hand-dried.
Heat treatment was performed at 50 ° C. for 10 minutes. Next, the excess water-slippery component was wiped off with a paper towel to obtain a water-slidable glass.

[Evaluation of Practical Durability] A method of evaluating a water-slidable substrate will be described.

(1) Initial contact angle The angle between a water droplet and the substrate surface when about 2 μl of pure water was placed on the sample was measured with a contact angle meter. In addition, it measured in air | atmosphere (about 25 degreeC) using Kyowa Interface Science CA-X type as a contact angle meter.

(2) Water-sliding property (water-dropping property) With a sample inclined at 30 °, pure water is slowly dropped on the sample surface with a microsyringe, and a point at which the water drop moves 2 cm or more in at least 10 seconds. The amount (volume) of water droplets was defined as the slipperiness (water droplet falling property: μl).

(3) Wear Resistance Using a traverse type sliding tester (manufactured by our company), the contact angle θ after sliding the sample surface with a friction cloth having a load of 0.1 kg / cm ² by 3,500 reciprocations.゜) was measured. The friction cloth is a 25 mm × 25 mm canvas cloth (JIS
L3102-1961-1206) and the sliding speed is 3
0 round trips / minute.

(4) Light Resistance UV irradiation was performed under the following conditions using an I-Super UV tester SUV-W11 manufactured by Iwasaki Electric Co., Ltd., and the irradiation time until the contact angle was reduced to 70 ° was defined as light resistance. (SUV test) Conditions] UV irradiation intensity: 76 mW / cm ² Sample environment: 48 ° C., 20 to 30% RH Measurement method: Contact angle was measured after wiping the sample with i-PA every 200 hours of UV irradiation. Hereinafter, the effects of the present invention will be described using examples and comparative examples.

[0040]

EXAMPLE 1 Heptadecafluorodecyltrichlorosilane (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ : C was used as a starting material.
8FASC) and a silanol-terminated polydimethylsiloxane (N10SOL) having an average degree of polymerization of 10 and a molar ratio of 1: 1 to prepare a slippery liquid according to the procedure described in the above [Preparation of a slippery liquid] (FIG. 1). . This was air-dried according to the above [Preparation of glass substrate-2) and heat-treated at 80 ° C according to the above [Preparation of water repellent glass] to obtain water-slidable glass. The sample performance was evaluated in the manner described in [Evaluation of practical durability]. As a result, the contact angle was 100 °, and the slipperiness was 9 μl. Further, abrasion resistance and light resistance were 98 ° and 900 h, respectively, indicating high practical durability.

[0041]

Example 2 Example 1 was the same as Example 1 except that the mixing molar ratio of the starting materials was changed to C8FASC: N10SOL = 1: 2. As a result, the contact angle was 98 °, and the slipperiness was 9 μl, showing extremely high water repellency and slipperiness. Further, abrasion resistance and light resistance were 97 ° and 900 h, respectively, indicating high practical durability.

[0042]

Example 3 Example 1 was the same as Example 1 except that the glass substrate was Substrate A. As a result, the contact angle was 100 °, and the slipperiness was 9 μl. Furthermore, the abrasion resistance and light resistance are each 98%.
９００ and 900h showed high practical durability.

[0043]

Example 4 In Example 1, the starting material was trifluoride.
Lopropyltrichlorosilane (CF _ThreeCH_TwoCH_TwoSiC
l_Three: C1FASC) and N10SOL
All were the same as Example 1. As a result, the contact angle was 99 °,
The aqueous solution showed extremely high water repellency and water slippage of 7 μl. Further
The abrasion resistance and light resistance are 97 ゜ and 750h, respectively.
It showed high practical durability.

[0044]

Example 5 In Example 1, the starting material was C8FAS
Except that C and N7SOL having an average degree of polymerization of 7 were used, all were the same as Example 1. As a result, the contact angle was 100 °, and the slipperiness was 8 μl, showing extremely high water repellency and slipperiness. further,
The wear resistance and light resistance were 97 ° and 800 h, respectively, indicating high practical durability.

[0045]

Example 6 In Example 1, the starting material was C8FAS
C and N7SOL having an average degree of polymerization of 7 were all the same as in Example 1 except that the glass substrate was Substrate A. result,
Very high water repellency with a contact angle of 100 ° and a water slide of 9 μl.
It showed slipperiness. Further, abrasion resistance and light resistance were 97 ° and 900 h, respectively, indicating high practical durability.

[0046]

Example 7 In Example 1, the starting material was C8FAS
C and N20SOL having an average degree of polymerization of 20 were used, and all were the same as Example 1 except that the mixing molar ratio was 1: 2. As a result, the contact angle was 100 °, and the slipperiness was 10 μl. Further, abrasion resistance and light resistance were 98 ° and 850 h, respectively, indicating high practical durability.

[0047]

Example 8 In Example 1, heincosan fluorododecyltrichlorosilane (CF ₃ (CF ₂ ) ₉ C was used as a starting material.
_{H 2 CH 2 SiCl 3: C10FASC} ) and except for using N20SOL were all the same as in Example 1. As a result, the contact angle was 101 °, and the slipperiness was 10 μl. Furthermore, wear resistance and light resistance are each
It exhibited high practical durability of 100 ° and 900 hours.

[0048]

Example 9 Example 9 was the same as Example 1 except that the heat treatment temperature of the silica coupling layer at the time of producing the glass substrate was 80 ° C. As a result, the contact angle is 9
9 °, the water repellency and water repellency and water repellency were as high as 8 μl. Furthermore, the wear resistance and light resistance are respectively 96 ° and 8 °.
It exhibited high practical durability of 50 hours.

[0049]

Example 10 Example 1 was the same as Example 1 except that the heat treatment temperature of the silica coupling layer at the time of producing the glass substrate was 150 ° C. As a result, the contact angle was 97 °, and the slipperiness was 10 μl, which was very high. Furthermore, abrasion resistance and light resistance are each 95%.
And 850 h, indicating high practical durability.

[0050]

Example 11 The procedure of Example 1 was the same except that the heat treatment after the water-sliding treatment was air-dried. As a result, the contact angle was 96 °, and the slipperiness was 8 μl, showing extremely high water repellency and slipperiness. Further, the abrasion resistance and the light resistance showed high practical durability of 99 ° and 750 h, respectively.

[0051]

Example 12 Example 1 was the same as Example 1 except that the heat treatment after the water-sliding treatment was changed to 150 ° C.
As a result, the contact angle was 100 °, and the slipperiness was 10 μl. Further, abrasion resistance and light resistance were 98 ° and 900 h, respectively, indicating high practical durability.

[0052]

COMPARATIVE EXAMPLE 1 The same procedure as in Example 1 was performed except that the glass substrate was changed to the substrate C. As a result, the contact angle showed high water repellency of 100 °, but the slipperiness was 15 μl.
Although the improvement effect was seen, it still failed at a low level. The wear resistance and light resistance were 98 ° and 6 mm, respectively.
00h, and the light resistance level was slightly lowered.

[0053]

Comparative Example 2 Example 1 was the same as Example 1 except that the glass substrate was D. As a result, the contact angle was 100 °, indicating high water repellency, but the slipperiness was 13 μl.
Although the improvement effect was seen, it still failed at a low level. The abrasion resistance and light resistance were 98% and 9%, respectively.
00h.

[0054]

Comparative Example 3 Example 1 was the same as Example 1 except that the glass substrate was substrate E. As a result, the contact angle was 98 °, indicating high water repellency, but the slipperiness was 20 μl, although the improvement effect was somewhat observed, but the rejection was still at a low level. The wear resistance and light resistance were 96 ° and 700 hours, respectively.

[0055]

Comparative Example 4 In Example 1, trifluoropropyltrimethoxysilane (CF ₃ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ : C1FASM) and N10SOL were all used in the same manner as in Example 1. As a result, the contact angle is 88
゜ and the water repellency were low, but the water slippage was as high as 9 μl.
However, abrasion resistance and light resistance are 65 ° and 350 °, respectively.
h and the durability were greatly reduced, which was not preferable.

[0056]

Comparative Example 5 In Example 1, heptadecafluorodecyltrimethoxysilane (CF ₃ (CF ₂ ) ₇ C
H ₂ CH ₂ Si (OCH ₃ ) ₃ : C8FASM) and N10SO
All were the same as Example 1 except that L was used. result,
Although the contact angle was 107 ° and the water repellency was high, the slipperiness was 25μ.
It was rejected as low as l. The abrasion resistance and light resistance were 103 ° and 600 hours, respectively.

[0057]

Comparative Example 6 In Example 1, heincosan fluorododecyltrimethoxysilane (CF ₃ (CF ₂ ) ₉
CH ₂ CH ₂ Si (OCH ₃ ) ₃ : C10FASM) and N10
All were the same as Example 1 except that SOL was used. As a result, the contact angle was 108 ° and the water repellency was high, but the slipperiness was 2
Rejection was as low as 5 μl. The abrasion resistance and light resistance were 104 ° and 600 hours, respectively.

[0058]

Comparative Example 7 In Example 1, C8FAS was used without using silanol-terminated polydimethylsiloxane as a starting material.
All were the same as Example 1 except that only C was used. As a result, it showed a high water repellency with a contact angle of 111 °, but the slipperiness was extremely low at 50 μl. The abrasion resistance and light resistance were as good as 108 ° and 900 h, respectively.

[0059]

Comparative Example 8 Example 1 was the same as Example 1 except that only N10SOL was used without using a fluoroalkyltrichlorosilane as a starting material. As a result, at a contact angle of 90 °, the slipperiness was 10 μl and the slipperiness was good,
The abrasion resistance and light resistance were 73 ° and 350 h, respectively, and the durability was extremely low, which was not preferable.

[0060]

Comparative Example 9 In Example 1, the starting material was C8FAS
Except that C and N56OL having an average degree of polymerization of 56 were used, all were the same as Example 1. As a result, the contact angle was 110 ° and the water repellency was high, but the water slippage was low at 35 μl. Also,
The abrasion resistance and light resistance were 97 ° and 650 h, respectively.

[0061]

Comparative Example 10 In Example 1, the starting material was C8FA
All were the same as Example 1 except that SC and N243SOL having an average degree of polymerization of 243 were used. As a result, the contact angle 110
The water repellency was high, but the slipperiness was low at 35 μl. The abrasion resistance and light resistance were 97 ° and 65 °, respectively.
0h.

[0062]

[Table 1]

[0063]

As described above, the present invention has both high water repellency and excellent water repellency and excellent light resistance and abrasion resistance. Therefore, when the present invention is used for a window glass for a vehicle, for example, it has excellent repellency. Since it has excellent water-sliding properties as well as water-based properties, it is easy to see the front, side, and rear views in rainy weather, and it is possible to drive safely and maintain high performance for a long period of time.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing a synovial fluid according to the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/06 C09D 183/06 183/08 183/08 (72) Inventor Hiroaki Arai Oguchi-cho, Matsusaka-shi, Mie Prefecture 1510 Central Glass Co., Ltd.Glass Laboratory Co., Ltd. DC01 DC13 DC38 EA07 EB16 EB42 EB43 EB56 EC45 EC54 4G059 AA01 AB01 AC22 FA05 FA11 GA01 GA04 GA11 4J038 DG261 DL021 DL051 GA03 GA15 JC31 JC35 NA04 NA07 NA11 PA14 PB05 PB07 PC03

Claims (5)

[Claims] 1. A copolymer of a fluoroalkyltrichlorosilane represented by the general formula [1] and a silanol-terminated polydimethylsiloxane represented by the general formula [2] on a silica coupling layer formed on the surface of a transparent substrate. A highly water-slidable substrate comprising a water-slidable film formed of a material. CF ₃ (CF ₂ ) _m (CH ₂ ) ₂ SiCl ₃ [1] (where m is an integer from 0 to 11) HO- [Si (CH ₃ ) ₂ O-] _n H [2] (wherein n = 1 to 50 integer) 2. The silica coupling layer is formed by applying a coating solution obtained by diluting a tetraalkoxysilane hydrolyzate or tetraisocyanate silane to the surface of a glass substrate, and has a thickness of at least 20 nm or less. 2. The highly water-slidable substrate according to claim 1, wherein the substrate is a silica film. 3. The high water-sliding film has a mixing molar ratio of the fluoroalkyltrichlorosilane represented by the general formula [1] and the silanol-terminated polydimethylsiloxane represented by the general formula [2] of 1: 0. 2. The highly water-slidable substrate according to claim 1, wherein the composition is a composition which has been subjected to a copolymerization reaction. 4. A method for manufacturing a highly water-slidable substrate, comprising manufacturing a highly water-slidable substrate by the following steps. (1) a step of applying a hydrolyzate of tetraalkoxysilane or a coating solution for an underlayer containing tetraisocyanatesilane as a main component on the surface of the transparent substrate; (2) drying and / or drying
Or a step of performing a heat treatment at a temperature of 190 ° C. or less to form a silica coupling layer as an underlayer; (3) a fluoroalkyltrichlorosilane represented by the general formula [1] and a silanol represented by the general formula [2] A step of applying a coating liquid for a water-slidable film comprising a copolymer of terminal polydimethylsiloxane, (4) a step of drying and / or heat-treating at a temperature of 190 ° C. or lower to form a water-slidable film, CF ₃ (CF ₂ ) _m (CH ₂ ) ₂ SiCl ₃ [1] (where m is an integer from 0 to 11) HO- [Si (CH ₃ ) ₂ O-] _n H [2] (where n = 1 to 50) Integer) 5. The coating solution for the underlayer is 0.1 to 5.0 wt.
5. The method for producing a highly water-slidable substrate according to claim 4, comprising a hydrolyzate of tetraalkoxysilane having a concentration of 0.1% or tetraisocyanate silane having a concentration of 0.1 to 5.0% by weight.