JP3744736B2 - Highly slidable base material and method for producing the same - Google Patents

Description

[0001]
[Field of the Invention]
INDUSTRIAL APPLICABILITY The present invention is a method for producing a highly slidable base material exhibiting extremely excellent water slidability (water droplet slidability) that can be used particularly for architectural window glass, vehicle window glass, mirrors, and other industrial window glass. About.
[0002]
[Prior art]
In order to obtain high water repellency durability (light resistance and abrasion resistance), a great many inventions have been made on water-repellent glass obtained by treating a substrate surface with a fluoroalkyl group-containing silane compound. For example, JP-A-6-16455 discloses that it is very effective to provide a base film such as silica having an uneven shape on the glass surface. Japanese Patent No. 2500188 discloses a method for forming a water- and oil-repellent monomolecular film on a glass surface, and Japanese Patent Application Laid-Open No. 10-59745 discloses that a glass surface to be water-repellent treated is ceria polished and further acid-treated. A method of increasing the activity of the substrate and a method of using a fluoroalkyl group-containing silane compound having an increased or controlled degree of polymerization as a water repellent treatment liquid are disclosed. Further, JP-A-8-325037 discloses that a fluoroalkyl group-containing silane compound is treated after forming an alkali barrier layer containing no alkali metal or having a low alkali metal content in the vicinity of the glass substrate surface. A method for obtaining a highly durable water-repellent treated glass is disclosed. Furthermore, Japanese Patent Laid-Open No. 9-48639 discloses that a fluoroalkyl group-containing silane compound is treated after forming a surface with a reduced amount of alkali components such as sodium by making the glass substrate surface a dealkalized layer. Discloses improving heat resistance, water resistance and weather resistance.
[0003]
On the other hand, studies have been made with an emphasis on further improving the water drop slidability, and high water slidability or high water slidability glass has been proposed. For example, a composition containing a silicone wax, an organopolysiloxane, a surfactant and the like has been invented. Japanese Patent Publication No. 50-15473 discloses a composition comprising an alkylpolysiloxane and an acid, No. 301742 discloses a composition containing an amino-modified silicone oil and a surfactant.
[0004]
Further, a composition having both high water repellency durability (light resistance and abrasion resistance) and excellent water droplet sliding property has been invented. JP-A-11-116943 discloses a perfluoroalkyl group-containing silane compound. A surface treating agent comprising a composition in which at least the terminal F atom of the fluoroalkyl group is substituted with an H atom is disclosed. JP-A-8-12375 discloses a water-repellent article in which a composition obtained by hydrolyzing a perfluoroalkyl group-containing silane compound and polydimethylsiloxane is applied to a glass substrate or the like.
[0005]
[Problems to be solved by the invention]
However, high water repellency (light resistance) described in JP-A-6-16455, JP-A-2500188, JP-A-10-59745, JP-A-8-325037, and JP-A-9-48639. The water-repellent glass in which the substrate surface is treated with a fluoroalkyl group-containing silane compound having high resistance and wear resistance) has poor water drop slidability (water slidability), for example, an inclination angle of 30 ° which is an attachment angle of an automotive windshield In this case, at least when the volume of the water droplet is not more than about 40 to 60 μl at rest, the water droplet does not slide down and remains on the glass surface.
[0006]
Also, those obtained by the methods of Japanese Patent Publication No. 50-15473 and Japanese Patent Application Laid-Open No. 5-301742 have good sliding properties (water droplet sliding properties), in which about 30 μl is inclined at 30 °. Although a thing that slides down with water droplets has been obtained, it has not yet achieved high water repellency durability (light resistance and abrasion resistance).
[0007]
Further, in the method described in JP-A-8-12375, a perfluoroalkyl group-containing silane compound and a polydimethylsiloxane compound are mixed and hydrolyzed, and then mixed with the hydrolyzed alkoxysilane compound to prepare a solution. It is shown that this is applied to the surface of a substrate, and a water-repellent article in which a hydrophobic group comprising a bulky and rigid perfluoroalkyl group and a small-sized methyl group is formed on the outer surface layer of the hybrid film at a high concentration Is disclosed. However, this is not a new composition obtained by positively copolymerizing a perfluoroalkyl group-containing silane compound and polydimethylsiloxane, and exhibits a good water sliding property (water droplet sliding property) of about 15 μl or less at a 30 ° inclination. Nothing has been obtained.
[0008]
[Means for Solving the Problems]
The present invention has been made in view of the above-described conventional problems, and has high water repellency durability (light resistance and wear resistance) and excellent water slidability (hereinafter sometimes referred to as “water droplet slidability”). A highly water-slidable substrate and a method for producing the same are provided.
[0009]
  That is, the highly lubricious base material of the present invention comprises perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] on the substrate surface.With the mixing molar ratio of perfluorotrichlorosilane 1 and dimethyl silicone diol being 0.1 to 2.0,In non-aqueous solventsOver 2 hoursA surface treatment agent is prepared by diluting the reaction product mixed and reacted and copolymerized with a diluent solvent.The film is formed by heat treatment at 60 ° C. to 190 ° C.
[0010]
[Chemical Formula 3]
[0011]
[Formula 4]
[0012]
  In the method for producing a highly lubricious base material of the present invention, a perfluoroalkyltrichlorosilane represented by the general formula [1] and a dimethyl silicone diol represented by the general formula [2] are provided on the substrate surface.With the mixing molar ratio of perfluorotrichlorosilane 1 and dimethyl silicone diol being 0.1 to 2.0,In non-aqueous solventsOver 2 hoursA surface treatment agent is prepared by diluting the reaction product mixed and reacted and copolymerized with a diluent solvent.The film is formed by heat treatment at 60 ° C. to 190 ° C.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The highly water-slidable base material of the present invention is obtained by mixing perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] in a non-aqueous solvent on the substrate surface. It can be manufactured by applying a surface treatment agent obtained by diluting a reaction product obtained by reaction and copolymerization with a diluting solvent, followed by drying.
[0014]
[Chemical formula 5]
[0015]
[Chemical 6]
[0016]
Examples of the perfluoroalkyltrichlorosilane represented by the general formula [1] include CF._Three(CF₂)₁₁CH₂CH₂SiCl_Three, CF_Three(CF₂)₉CH₂CH₂SiCl_Three, CF_Three(CF₂)₇CH₂CH₂SiCl_Three, CF_Three(CF₂)_FiveCH₂CH₂SiCl_ThreeEtc. can be used.
[0017]
Examples of the dimethyl silicone diol represented by the general formula [2] include HO— [Si (CH_Three)₂O-]_TenH, HO- [Si (CH_Three)₂O-]₂₀H or the like can be used.
[0018]
Non-aqueous solvents are those having low water solubility and substantially no water content, such as esters such as ethyl acetate, n-butyl acetate and n-hexyl acetate, and aromatic hydrocarbons such as toluene and xylene. , Aliphatic hydrocarbons such as n-butane and n-hexane can be used.
[0019]
As a diluent 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 alcohol, and alcohols mainly composed of i-PA or ethanol are particularly preferable.
[0020]
The mixing molar ratio of the perfluoroalkyltrichlorosilane and dimethylsilicone diol can be freely selected. However, the copolymerization reaction is performed under the conditions of perfluoroalkyltrichlorosilane: dimethylsilicone diol = 1: 0.1-2. It is preferable to carry out the treatment. When the dimethyl silicone diol is 0.1 or less with respect to the perfluoroalkyltrichlorosilane 1, the intended effect of improving the water slidability cannot be obtained. Although good water slidability is obtained, durability performance such as light resistance is greatly lowered, which is not preferable in practice.
The reaction time for mixing the perfluoroalkyltrichlorosilane and dimethyl silicone diol in a non-aqueous solvent for copolymerization must exceed 2 hours, and if it is shorter than that, high lubricity cannot be obtained. It is not preferable.
[0021]
Drying after applying the surface treatment agent may be carried out by air drying after the application of the surface treatment agent, or heat treatment may be performed at a temperature of 190 ° C. or less exceeding room temperature after drying or simultaneously with drying.
When heat treatment is performed, it is necessary to perform the heat treatment at a temperature of 190 ° C. exceeding room temperature, and the OH group of the unreacted fluoroalkyl group-containing silane is bonded to other OH groups by the treatment. However, when the temperature is 200 ° C. or higher, the silicone oil diol for improving the water slidability is easily decomposed by heat, which is not preferable. Moreover, 60 degreeC or more is more preferable at the point of reaction efficiency.
[0022]
The slipperiness for the present invention is a method as described in the evaluation method of the examples described later, for example, on the surface of the sample in a state where the sample having the coating treated with the surface treatment agent is inclined at 30 °. Slowly add pure water dropwise with a microsyringe. At this time, the amount (volume) of water droplets at the time when the water droplets start to move is defined as the slidability (water droplet tumbling property) and expressed in μl. The high water slidability of the present invention refers to a water slidability obtained by the above method of 30 μl or less, more preferably 20 μl or less.
[0023]
The base material having a highly water-slidable film obtained in the present invention has an excellent water repellency along with the water slidability because the water-repellent film made of a fluoroalkyl group-containing silane is immobilized on the surface of the base material. .
[0024]
The base material is not particularly limited, such as glass and plastic. For example, in the case of a glass substrate, a float glass or a roll-out that is usually used for architectural window glass or automobile window glass is used. Inorganic transparent plate glass such as glass produced by the method is preferred, and it is not particularly limited to colorless or colored, as well as its type or color tone, combination with other functional films, glass shape, etc. Of course, various types of tempered glass and strength-enhancing glass can be used as the bent plate glass, and it can be used as a flat plate or a single plate, and can also be used as a double-layer glass or a laminated glass. The coating may be formed on both sides of the glass substrate.
The base material surface to which the surface treatment agent is applied may be provided with a base layer made of a metal oxide.
For example, in the case of a glass substrate, the underlayer is preferably an oxide thin film mainly composed of a metal oxide such as silicon oxide, and the surface treatment agent is applied thereon to cover the highly water-slidable film. As a result, a highly slippery glass having high durability can be obtained.
[0025]
Furthermore, it is particularly preferable to make the surface of the underlayer uneven, since durability is further improved. As the method, for example, at least two or more kinds selected from metal alkoxide compounds or metal acetylacetonate compounds are selected. Two or more compounds having different average molecular weights are mixed with a solvent to form a coating solution, and after coating the solution, it is heated to form a micropit-like or uneven surface layer. Although a method etc. can be employ | adopted, the method of making an underlayer surface uneven | corrugated is not limited to this.
[0026]
The surface treatment agent can be applied to the substrate surface by hand coating, nozzle flow coating method, dipping method, spray method, river coating method, flexo method, printing method, flow coating method or spin coating method. Various coating methods such as a coating method and known coating means such as a combination thereof can be appropriately employed. It can also be used as a simple type spray-type water repellent agent.
[0027]
The following methods were used for the preparation of the surface treatment agent, the production of the coating substrate, and the method for evaluating the practical durability of the resulting slidable substrate, which are items common to the following Examples and Comparative Examples.
[0028]
[Preparation of surface treatment agent]
In FIG. 1, the preparation procedure of a surface treating agent is shown. For the preparation of the surface treatment agent, heptadecafluorodecyltrichlorosilane (CF_Three(CF₂)₇CH₂CH₂SiCl_Three: TSL 8232 manufactured by Toshiba Silicone, hereinafter referred to as “FASC”) and silicone oil diol having an average polymerization degree of 10 and 20 (hereinafter referred to as “N10SOL” and “N20SOL”) were used.
[0029]
For example, as a procedure for the FASC-N10SOL (1: 1) system, 5.00 g of ethyl acetate and 3.90 g of N10SOL were weighed and mixed. Next, 2.50 g of FASC was slowly added dropwise to the mixture with stirring, and the mixture was further stirred at room temperature for 0 to 24 hours to obtain a mother liquor. Next, 1.0 g of the mother liquor was diluted with 9.0 g of i-PA and stirred for about 10 minutes to obtain a surface treating agent. When weighing and adding FASC, it is preferable to keep the humidity in the laboratory below 55% RH in order to prevent FASC from absorbing and hydrolyzing moisture in the atmosphere as much as possible. It was. Table 1 shows the weighed value (g) of each component in each system (ratio in parentheses indicates mixing molar ratio).
[0030]
[Table 1]
[0031]
[Production of substrate for coating]
As the substrate, the following three types were used.
[0032]
1) Baseless type (hereinafter referred to as “Board A”)
A float glass or a tempered glass having a size of 200 mm × 200 mm × 2 mmt was washed with water and dried with an ordinary glass washer (produced by this company).
[0033]
2) Baseless type (hereinafter referred to as “Substrate B”)
The surface of float glass or tempered glass of 200 mm × 200 mm × 2 mmt size is polished with a polishing liquid and a brush polisher, and after sufficiently removing the abrasive, it is placed in a 0.1N sulfuric acid aqueous solution at 35 ° C. for 1 minute. Soaked. Thereafter, it was washed with water and dried with a normal glass washer (produced by our company). The polishing liquid used here was a suspension obtained by mixing approximately 1% of glass abrasive agent Mille A (Mitsui Metal Industry) with water.
[0034]
3) Silica-based underlayer type having an uneven surface shape (hereinafter referred to as “substrate C”)
After polishing the surface of a float glass substrate having a size of 200 mm × 200 mm × 2 mmt with a suspension obtained by mixing about 1% of glass abrasive Mille A (Mitsui Metal Industries) in water and a plus polisher, A sufficiently washed and dried substrate was used as a coated fabric substrate. The undercoat layer coating solution was prepared as follows.
[0035]
Tetraethoxysilane [Si (OC₂H_Five)_Four: TEOS] polymerized sol (average molecular weight Mw: about 1000 to 3000) and tetrabutoxytitanium [Ti (O-Bu) stabilized with acetylacetone_Four] The mixed sol (the amount of tetrabutoxytitanium stabilized with acetylacetone is SiO in terms of oxide)₂A sol solution A was prepared by adding an isopropyl alcohol (iPA) solvent to a molar ratio of about 4 mol% with respect to the total solid content and diluting to a solid content concentration of 5 wt% in terms of oxide. In addition, methyltrimethoxysilane [CH_ThreeSi (OCH_Three)_Three: MTMS], a sol solution B was prepared by adding isopropyl alcohol (iPA) to a polymerization sol (average molecular weight Mw = about 1,000) and diluting it to a solid content concentration of about 20 wt% in terms of oxide. Next, sol solution A; 20 g, sol solution B; 20 g, and butanol (n-BuOH) as a solvent for adjusting the rate of hydrolysis and dehydration condensation reaction; 25 g were mixed at about 50 ° C. Sealed and stirred for about 3 hours (sol solution C). Furthermore, the previous sol solution C was diluted with about 360 g of a mixed solvent of iPA (90 wt%); 324 g and n-BuOH (10 wt%); 36 g to obtain a coating solution.
[0036]
The coating method was a spin coating method. First, a coating glass substrate is set on a spin coater. First, in the coating film region (high-speed spin rotation), spin rotation is started, and after 3 seconds at a rotation speed of 150 rpm, the coating amount of the coating solution is about 20 ml. The solution was dropped to form a film while maintaining the rotation speed for 18 seconds. Subsequently, in the leveling area (spin rotation stop), before the coated coating solution begins to thirst and loses its fluidity, the spin rotation is temporarily stopped and allowed to stand still for 60 seconds, and the drying acceleration area (slow spin rotation) ), Spin rotation was started again and maintained at a low speed of 50 rpm for 40 seconds to accelerate the drying of the coating film, and a gel film with good film formability was obtained.
[0037]
Next, the glass substrate with the gel film is pre-baked at 250 ° C. for 30 minutes, further subjected to main baking at a glass temperature of 630 ° C. to 660 ° C., and SiO having a fine uneven shape on the surface.₂-TiO₂A thin film was obtained.
[0038]
[Method of evaluating practical durability]
The obtained highly slippery glass was evaluated by the following four methods.
[0039]
1) Initial contact angle
The angle formed between the water droplet and the substrate surface when the water droplet was placed on the sample was measured with a contact angle meter.
[0040]
Contact angle meter: Kyowa Interface Science CA-X type
Measurement environment: In the atmosphere (about 25 ℃)
Water: pure water (2 μl).
[0041]
2) Water drop fallability
While the sample is inclined at 30 °, pure water is slowly dropped onto the sample surface with a microsyringe. At this time, the amount (volume) of water droplets at the time when the water droplets started to move was expressed in μl and expressed as “sliding water”.
[0042]
3) Abrasion resistance
Using the following testing machine, the contact angle θ (°) was measured after the number of sliding times (3500 times).
[0043]
Testing machine: Traverse type sliding testing machine (manufactured in-house)
Sliding area: 100mm x 25mm
Friction cloth: canvas cloth (JISL3102-11961-1206)
Load: 0.1kg / cm²
Stroke: 100mm reciprocating sliding (sliding frequency is the number of reciprocating times)
Sliding speed: 30 reciprocations / minute.
[0044]
4) Light resistance
Using the following tester, the contact angle θ (°) after the sample was irradiated with powerful UV light from a metal halide lamp for 2 hours was evaluated.
[0045]
Testing machine: High-speed light resistance testing machine (manufactured in-house)
Lamp: 1.5kW metal halide lamp (M015-L312 made by Eye Graphics)
Lamp-sample distance: 160mm
Table 2 shows the evaluation results of the samples obtained in the following examples and comparative examples.
[0046]
【Example】
Examples of the present invention will be described below.
[0047]
  Example 1
In this example, the mixing ratio of FASC and N10SOL is 1: 1 by molar ratio.
First, 5.00 g of ethyl acetate and 3.90 g of N10SOL were weighed and mixed. Next, 2.50 g of FASC was slowly added dropwise to the mixture with stirring, and the mixture was further stirred for 6 hours at room temperature (20 to 25 ° C.) to obtain a mother liquor. Next, 1.0 g of the mother liquor was diluted with 9.0 g of i-PA and stirred for about 10 minutes to obtain a surface film forming treatment agent. 2 ml / pc of the surface treatment agent was dropped on the substrate A in an environment where the temperature was kept at 25 ° C. and humidity was kept at 45% RH on the substrate A, and the surface was sufficiently stretched over the entire surface of the glass with a cotton cloth (trade name: Bencott). After that, it was air-dried for about 5 minutes. Thereafter, heat treatment was performed at 150 ° C. for about 5 minutes at a glass temperature in a muffle furnace, and the remaining water repellent remaining cloudy was wiped with iPA to obtain a transparent sample. As shown in Table 2, the evaluation results of the obtained sample showed an extremely good water drop sliding property with an initial contact angle of 100 ° and a sliding property of 13 μl. Further, the wear resistance and light resistance were 98 ° and 98 °, and there was almost no change in the contact angle before and after the test.
In Table 2, the FAS column indicates the type of FAS used, and is -Cl3; trichlorosilane type (FASC), -OCH3; trimethoxysilane type. The amount added was 1 mol.
[0048]
  Example 2
The same procedure as in Example 1 was performed except that the surface treatment agent was applied to the substrate B. The obtained sample had an initial contact angle of 102 ° and a sliding property of 8 μl, which showed very good water droplet sliding properties. In addition, the wear resistance and light resistance were 100 ° and 96 °, indicating high practical durability.
[0049]
Example 3
The same procedure as in Example 1 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 99 ° and 95 °.
[0050]
Example 4
Example 2 was repeated except that the reaction time for preparing the surface treatment agent was 12 hours. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0051]
Example 5
Example 3 was repeated except that the reaction time for preparing the surface treatment agent was 12 hours. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0052]
[Table 2]
[0053]
Example 6
Example 2 was repeated except that the reaction time for preparing the surface treatment agent was 24 hours. The sample obtained had an initial contact angle of 99 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0054]
Example 7
Example 3 was repeated except that the reaction time for preparing the surface treatment agent was 24 hours. The obtained sample had an initial contact angle of 100 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0055]
Example 8
The conditions were the same as in Example 2 except that the mixing ratio of FASC and N10SOL was 1: 2. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. The abrasion resistance and light resistance were 97 ° and 96 °, indicating high practical durability.
[0056]
Example 9
The same procedure as in Example 8 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 13 μl, which showed very good water drop sliding properties. Further, the wear resistance and light resistance were 97 ° and 97 °, and high practical durability was exhibited.
[0057]
Example 10
N20SOL having an average degree of polymerization of 20 was used for the silicone oil diol, and the mixing ratio with FASC was 1: 2. Other conditions were the same as in Example 2. The obtained sample had an initial contact angle of 101 ° and a sliding property of 17 μl, which showed good water drop sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 95 °.
[0058]
Example 11
The same procedure as in Example 10 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 98 ° and a sliding property of 15 μl, which showed very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 97 °.
[0059]
Example 12
The sample was prepared in the same manner as Example 2 except that no heat treatment was performed. The obtained sample had an initial contact angle of 100 ° and a sliding property of 10 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0060]
Comparative Example 1
In the preparation of the surface treatment agent, without mixing silicone oil diol, 25 g of iPA as a diluting solvent and 0.1 N nitric acid (HNO as an acid catalyst) are added to 1 g of FASC._Three) Was added and stirred at room temperature for about 2 hours to complete the hydrolysis reaction. Other conditions were the same as in Example 2. The obtained sample had an initial contact angle of 108 °, a sliding property of 50 μl, and the sliding property of water droplets was poor. Further, the wear resistance and light resistance were 70 ° and 100 °, and the wear resistance was not at a practical level.
[0061]
Comparative Example 2
The same procedure as in Comparative Example 1 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 112 ° and a sliding property of 55 μl, which was a bad level. Further, the wear resistance and light resistance were 110 ° and 106 °, and the practical durability was at a level that could be put to practical use, but the sliding property was not satisfactory.
[0062]
Comparative Example 3
In the preparation of the surface treatment agent, N10SOL; 1 g was diluted only with iPA; 9 g without mixing perfluoroalkyltrichlorosilane (FASC). Others were the same as in Example 2. The obtained sample had an initial contact angle of 91 ° and a sliding property of 15 μl, which was a good level of water drop sliding properties, but was wear resistance of 76 ° and light resistance of 80 °, which was not a practical level.
[0063]
Comparative Example 4
In the preparation of the surface treatment agent, N20SOL; 1 g was diluted with iPA; 9 g without mixing perfluoroalkyltrichlorosilane (FASC). Others were the same as in Example 2. The obtained sample had an initial contact angle of 94 ° and a sliding property of 10 μl, which was a good level of water drop sliding properties, but the wear resistance was 89 ° and the light resistance was 89 °, which was not a practical level.
[0064]
Comparative Example 5
The sample was prepared in the same manner as Example 2 except that the heat treatment temperature was set to 200 ° C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 50 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 100 ° and the light resistance was 98 °, which was high practical durability.
[0065]
Comparative Example 6
The sample was prepared in the same manner as in Example 2 except that the heat treatment temperature was set to 350 ° C. The obtained sample had an initial contact angle of 103 ° and a sliding property of 55 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 101 ° and the light resistance was 99 °, which was high practical durability.
[0066]
Comparative Example 7
The same procedure as in Example 2 was conducted except that the reaction time at the time of preparation of the surface treatment agent was 1 hour. The obtained sample had an initial contact angle of 100 ° and a sliding property of 55 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 95 °, the light resistance was 95 °, and the practical durability was good.
[0067]
Comparative Example 8
The same procedure as in Example 2 was performed except that the reaction time during preparation of the surface treatment agent was 2 hours. The obtained sample had an initial contact angle of 103 ° and a sliding property of 50 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 95 °, the light resistance was 95 °, and the practical durability was good.
[0068]
Comparative Example 9
In the preparation of the surface treatment agent, the water repellent agent is heptadecafluorodecyltrimethoxysilane (CF_Three(CF₂)₇CH₂CH₂Si (OCH_Three)_Three: KBS-7803 manufactured by Shin-Etsu Silicone, referred to as FASM). The obtained sample had an initial contact angle of 107 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 96 °, and the practical durability was good.
[0069]
Comparative Example 10
Comparative Example 9 was carried out except that the reaction time for preparing the surface treating agent was 24 hours. The obtained sample had an initial contact angle of 107 ° and a sliding property of 45 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0070]
Comparative Example 11
When preparing the surface treating agent, it was the same as Comparative Example 9 except that a silicone oil diol having an average degree of polymerization of 20 was used. The obtained sample had an initial contact angle of 110 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0071]
Comparative Example 12
The same procedure as in Comparative Example 11 was conducted except that the reaction time for preparing the surface treatment agent was 24 hours. The obtained sample had an initial contact angle of 110 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0072]
【The invention's effect】
The present invention relates to a novel highly slidable base material exhibiting extremely excellent water drop slidability (slidability) and a method for producing the same, and the slidability (30 ° inclination) is 10 μl or less, and is excellent in practical use. Excellent water repellency and water slidability with durability. As a result, it has become possible to improve the water drop sliding property of the fluorine-based water repellent, which has been a problem in the past, without significantly impairing the durability.
[Brief description of the drawings]
FIG. 1 is a flowchart showing a preparation process of a surface treatment agent of the present invention.

Claims (3)

On the surface of the substrate, the mixing molar ratio of perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] is 0 with respect to the perfluorotrichlorosilane 1. A surface treatment agent obtained by diluting a reaction product obtained by mixing and reacting in a non-aqueous solvent for more than 2 hours under a condition of 1 to 2.0 with a diluting solvent was applied , and A highly water-slidable substrate characterized in that a film is formed by heat treatment at 190 ° C.
The highly lubricious base material according to claim 1, wherein a base layer made of a metal oxide is provided on the surface of the base material . On the surface of the substrate, the mixing molar ratio of perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] is 0 with respect to the perfluorotrichlorosilane 1. A surface treatment agent obtained by diluting a reaction product obtained by mixing and reacting in a non-aqueous solvent for more than 2 hours under a condition of 1 to 2.0 with a diluting solvent was applied , and A method for producing a highly slidable base material, characterized in that a film is formed by heat treatment at 190 ° C.