JPH11228942A - Water-repellent fluid and production of water-repellent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-repellent fluid which can form a water-repellent film having high strengths, high adhesive properties, durability, and abrasion resistance by controlling the degree of polycondensation of a fluoroalkylated silane compd. as a water-repellent agent and by causing the fluoroalkylated silane compd. in the water-repellent fluid to at least contain a dimer and a trimer. SOLUTION: Pref., at least a dimer and a trimer are formed in the water- repellent fluid by controlling the dehydration time in the polycondensation after the hydrolysis of starting materials comprising a fluoroalkylated silane compd., a diluting solvent, and an acidic water soln. Pref., the ratio (η) of the trimer to the dimer in the polymer is 0.06-0.5. The polymer in the fluid may comprise a monomer, a dimer, a trimer, and a tetramer and higher and pref. comprises at least 60 wt.% monomer, 1-25 wt.% dimer, 0.06-12.5 wt.% trimer, and up to 5 wt.% tetramer and higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent liquid for forming a water-repellent film on a surface of a glass substrate or the like, and a method for producing the water-repellent film. An object of the present invention is to provide a method for producing a water-repellent liquid and a water-repellent film which can be used for window materials, mirrors for bathrooms or automobiles, and various other transparent articles in various fields such as industrial use.

[0002]

2. Description of the Related Art In recent years, a transparent water-repellent coating which has both excellent durability and water repellency and maintains excellent water repellency for a long time has been desired. To meet these needs, for example, it is necessary to provide a water-repellent substrate provided with a water-repellent thin film having high abrasion resistance (traverse resistance).

[0003] In view of this, Japanese Patent Application No. Hei.
-294106 (Japanese Unexamined Patent Publication No. 9-132433) discloses a unique and fine uneven shape controlled on a glass surface with a high hardness, a high mechanical strength, and a high specific surface area excellent in durability. Forming a base film having a surface layer surface,
By forming a water-repellent film covering the base film, the adhesion efficiency and adhesion of the water-repellent film are improved, and the light resistance is further improved.

[0004] Further, Japanese Patent Application No. Hei.
No. 131595 (Japanese Unexamined Patent Publication No. 9-309746) discloses a method of forming a water-repellent film on the surface of a glass substrate while keeping the temperature of the glass substrate at about 90 to 200 ° C. A water-repellent film layer is to be formed on the surface (in some cases, the surface of a finely uneven glass substrate with streak-like scratches having directionality), and it is remarkably excellent in weather resistance, abrasion resistance, scratch resistance and durability. It is designed to exhibit excellent water repellency.

Japanese Patent Application Laid-Open No. 3-24737 discloses a pretreatment step in which the surface of a glass substrate is polished and cleaned by using a polishing powder, and a method for producing water-repellent glass. Coating a silicon-based water repellent, which has been replaced with fluorine atoms by 5% or more, on a pre-treated glass substrate to form a coating film;
The coated film is cured and adhered to a glass substrate to have a thickness of 0.1
And a curing step of forming a water-repellent cured film of about 2 μm. In the pretreatment step, polishing and washing are performed by using fine abrasive powder such as alumina or cerium oxide (1 μm or less). It is described that a water-repellent coating film first reacts with a silanol group present on the glass surface to form an adhesion film, and then proceeds to cure the surface in the thickness direction.

Japanese Patent Application Laid-Open Nos. 58-122797 and 58-129082 describe water- and oil-repellents for glass surfaces, which are washed and washed with acetone, and then washed with a 1% hydrochloric acid solution. Prepare a glass plate (soda-lime glass) dried after immersion, apply the prepared water / oil repellent solvent solution to the surface with an applicator, and apply it at 120 ° C or 160 ° C in 100% relative humidity. It is described that curing was performed for 20 minutes.

[0007]

For example, the water-repellent glass described in Japanese Patent Application No. 7-294106 filed by the present applicant can sufficiently respond to the above-mentioned needs. However, there is a demand for a water-repellent glass which has a complicated and simple two-layer structure of a unique base film and a water-repellent film, is a simple and simple single-layer film, and has higher performance. is there.

[0008] Japanese Patent Application No. Hei 8-
The water-repellent glass described in, for example, No. 131595 is a water-repellent glass whose performance is improved by a single-layer film and has a performance closer to the water-repellent glass, but the workability at the time of production, particularly the handling is sufficient. It is difficult to say that the method is simple and efficient.

In the pretreatment for polishing the glass substrate surface in the method for producing water-repellent glass described in Japanese Patent Application Laid-Open No. Hei 3-247375, although the abrasion resistance is improved, the long-term stability is sufficiently satisfied. It is hard to say what you can do.

The washing and pretreatment with hydrochloric acid disclosed in Japanese Patent Application Laid-Open Nos. 58-122979 and 58-129082, which are disclosed in Japanese Patent Application Laid-Open Nos. 58-129082, are the same as described above. It is hard to say that the long-term stability of wear properties is sufficiently satisfactory.

That is, the conventional method of forming a base film to improve the durability performance requires complicated management conditions and steps and is costly. On the other hand, the structure without the base film is generally water-repellent. The reactivity between the agent component and the glass surface is insufficient, and satisfactory durability has not been obtained as long as a water-repellent liquid obtained by simply diluting or hydrolyzing a fluoroalkyl group-containing silane compound is used.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and is intended to control the degree of polycondensation of a fluoroalkyl group-containing silane compound so that the fluoroalkyl group-containing silane compound has at least Dimer and 3
The water-repellent coating obtained by the water-repellent liquid containing the polymerization degree composed of the monomer has remarkably excellent abrasion resistance (traverse resistance).
Having. This water-repellent coating has high hardness and high adhesion, has both durability and abrasion resistance, and can maintain excellent water-repellent performance over a longer period of time.

That is, the present invention provides a method for applying a water-repellent liquid containing a fluoroalkyl group-containing silane compound as an active ingredient to a substrate surface and fixing the fluoroalkyl group on the substrate surface to form a water-repellent film. In the water-repellent liquid used, the fluoroalkyl group-containing silane compound in the water-repellent liquid relates to a water-repellent liquid containing a polymer composed of at least a dimer and a trimer, wherein the water-repellent liquid contains a fluoroalkyl group-containing liquid. Preferably, the silane compound is hydrolyzed and polycondensed.

The ratio of the trimer to the dimer (η = trimer / dimer) in the polymer is preferably 0.06 to 0.5, and the ratio of the formation of the polymer is more preferable. Is 2
It is preferable that the content of the monomer is 1 to 25% by weight and the content of the trimer is 0.06 to 12.5% by weight.

Further, the polymer in the water-repellent liquid may be composed of a monomer, a dimer, a trimer and a tetramer or more. 1 to 25 dimers
It is preferable that the content by weight of trimers is 0.06 to 12.5% by weight, and that of tetramers or more is 5% by weight or less.

The content of the fluoroalkyl group-containing silane compound in the water-repellent liquid is preferably from 2% by weight to 20% by weight. Further, the present invention includes a step of applying a water-repellent liquid prepared by hydrolyzing and condensation-polymerizing a solution containing a fluoroalkyl group-containing silane compound as an active ingredient to a substrate surface, and then included in the water-repellent liquid. And a curing step of forming a water-repellent film by fixing a fluoroalkyl group on the surface of the base material.

By controlling the dehydration time during the condensation polymerization after hydrolyzing the starting material comprising the fluoroalkyl group-containing silane compound, the diluting solvent and the acidic aqueous solution, at least the dimer and trimer are contained in the water-repellent liquid. It is preferable to form a monomer.

As the diluting solvent, it is preferable to use a solvent other than the alcohol corresponding to the type of the alkoxy group in the alkoxy group-containing silane compound of the water repellent. Further, when the substrate is glass, it is preferable to apply a water-repellent liquid to the surface whose surface has been modified by polishing and acid-treating the surface of the glass substrate.

Further, the surface on which the water-repellent film layer is formed is preferably a top surface of glass produced by a float method or a fire-making surface produced by a roll-out method. A water-repellent liquid can be applied to the glass surface whose surface has been modified.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The water repellent for forming the highly durable water repellent film of the present invention comprises a water repellent comprising a fluoroalkyl group-containing silane compound, a solvent for dilution, and an acidic aqueous solution as a catalyst. After mixing quantitatively, the mixture is stirred for a predetermined time to terminate the hydrolysis reaction, and then a dehydrating agent is added to the solution, followed by a dehydration treatment for a predetermined time to perform condensation polymerization.

As the above-mentioned starting materials, water repellents
Fluoroalkylalkoxysilane-based compound or fluoro
Polyalkylhalogenated silane compounds
For example, CF_ThreeCH_TwoCH_TwoSi (OR)_Three ,
CF_Three(CF_Two)_FiveCH_TwoCH_TwoSi (OR)_Three , CF
_Three(CF_Two)_FiveCH_TwoCH_TwoSiR (OR)_Two , CF_Three(C
F _Two)₇CH_TwoCH_TwoSi (OR)_Three , CF_Three(CF_Two)₇C
H_TwoCH_TwoSiR (OR)_Two, CF_ThreeCH_TwoCH_TwoSiCl_Three 
 , CF_Three(CF_Two)_FiveCH_TwoCH_TwoSiCl_Three , CF _Three(C
F_Two)_FiveCH_TwoCH_TwoSiRCl_Two , CF_Three(CF_Two)₇CH
_TwoCH_TwoSiCl_Three, CF_Three(CF_Two)₇CH_TwoCH_TwoSiRC
l_TwoEtc. can be used. In the above chemical formula,
R is CH_Three, C_TwoH_Five, C_ThreeH₇Is shown.

Examples of the diluting solvent include isopropyl alcohol (hereinafter abbreviated as "i-PA") and lower alcohol solvents having 5 or less carbon atoms such as methanol and ethanol. Ethers and ketones can be used in addition to alcohols. In particular, alcohol containing isopropyl alcohol as a main component is preferable as a diluting solvent in preparing a coating solution.

The acidic aqueous solution as a catalyst is 0.0
An inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid or the like, or an organic acid such as acetic acid or citric acid having a concentration of 1N or more, preferably about 0.1N to 13N can be used.

The water repellent: diluting solvent: acidic aqueous solution
The weight ratio is preferably in the range of 1: 5 to 40: 0.09 to 1.0, but is not limited to these ranges. Next, the hydrolysis and polycondensation reaction of the fluoroalkyl group-containing silane compound will be described.

(1) Hydrolysis Reaction A fluoroalkyl (Rf) group-containing silane compound (the following formula is an example of an alkoxysilane compound) is relatively easily hydrolyzed by reacting with water under an acid catalyst as shown in the following formula. Decomposed. The hydrolysis reaction requires about 90 minutes, preferably about 120 minutes, to complete the hydrolysis reaction (stirring), but is not limited thereto.

[0026]

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The polycondensation reaction of the hydrolyzate in the above reaction has a water repellent concentration of about 20% or less, compared with many other alkoxysilane compounds (eg, tetraethoxysilane, methyltriethoxysilane, etc.). Very slow, mostly monomeric and difficult to gel.

The hydrolyzate (monomer) of the fluoroalkyl group-containing silane compound (FAS) obtained by the above formula is
A silanol group (-SiOH) on the glass surface undergoes a dehydration-condensation polymerization reaction as shown in the following formula, and is immobilized on a glass substrate or becomes a high polymer (multi-molecule).

However, due to the bulkiness and rigidity of the fluoroalkyl (Rf) group, the polycondensation reaction between FASs does not easily proceed, and basically the monomer selectively reacts with the glass substrate. This tendency is stronger as the Rf group becomes longer.

Reaction with glass

[0031]

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(2) Polycondensation reaction Reaction between FASs Reaction between FASs increases the degree of polymerization.

・ Dimerization

[0034]

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・ Trimerization

[0036]

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The water content of the water-repellent liquid is usually about 4
The water content is preferably measured by, for example, a Karl Fisher coulometric titration method.

As the dehydrating agent, silica gel, synthetic zeolite, activated alumina and the like can be used.
It is not limited to this. Further, the present invention is not particularly limited to a case where condensation polymerization is carried out after termination of hydrolysis or a case where condensation polymerization is started during hydrolysis.

As the base material, any material such as glass, plastic, ceramics, etc., whose surface contains active hydrogen such as hydroxyl group (-OH) can be used, and the surface does not contain active hydrogen. In this case, a material in which a hydroxyl group has been introduced to the surface of a substrate by a plasma treatment or a corona treatment can be applied.

As a glass substrate, which is one of the representative substrates, inorganic glass such as float glass or glass produced by a roll-out method, which is generally used for architectural window glass and automotive window glass, is used. Transparent plate glass is preferred, colorless or colored, and its type or color,
The combination with other functional films, the shape, etc. are not particularly limited. Further, as a bent sheet glass, various tempered glasses and strength-up glasses can be used. Can also be used as glass. The coating may be formed on both surfaces of the glass substrate.

Further, the conditions for applying the water-repellent liquid on the surface of the glass substrate are usually such that the atmospheric humidity is about 75% RH or less.
% RH or more is preferable, but not limited thereto.

Further, regarding the surface state of the glass substrate,
For example, in the case of float glass, there is a clear difference between the top surface and the bottom surface of the glass, and it is preferable to coat the top surface of the float glass as a fire-making surface. It is also preferable to cover the flaming surface that is not in contact with the transport rolls, etc., but it is also possible to cover the bottom surface or the non-firing surface in some cases.

If the surface of the glass substrate to which the water-repellent liquid is applied is polished in advance and the surface is modified by an acid treatment, the strength of the coating film and the like are preferably increased, but the method is carried out as follows.

In the polishing treatment for modifying the surface of the glass substrate, the top surface of the float glass, the roll-out glass surface, or the bent or / and tempered glass surface containing little tin is removed by cerium oxide (ceria). And / or a surface abrasive that is a fine powder (average particle size of about 5 μm or less, preferably about 1 μm or less) containing an inorganic metal oxide such as aluminum oxide (alumina) or / and silicon oxide as a main component, On a polishing surface such as a brush, sponge or cloth in a wet or dry system, by appropriately changing the type and size of powder used, the material of the polishing surface and the contact pressure with the glass substrate, etc. It is preferable to perform polishing while controlling the surface flaw state and the polishing state.

Next, the polished glass surface is treated with an aqueous solution prepared by adding an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid or an organic acid such as acetic acid, formic acid or oxalic acid so as to have a pH of 4 or less, for example. For example, the temperature of the acid treatment liquid is 5 ° C. to 70 ° C., and the treatment time is 10 seconds to 10 seconds.
The acid treatment is carried out under the condition of not more than 1 minute so as to efficiently generate silanol groups by extracting sodium ions from the polished glass surface and breaking siloxane bonds. In the water-repellent treatment, it can contribute to fixation of the water-repellent fluoroalkyl group.

The acid treatment is carried out by immersion in an acid solution, but is not particularly limited as long as an acid treatment effect equivalent or similar to the immersion method can be obtained, such as a spray method or a flow method. Can be adopted instead.

Further, as a method of applying a film to a glass substrate, a hand coating (rubbing method), a nozzle flow coating method,
Known coating methods such as dipping method, spray method, reverse coating method, flexo method, printing method, flow coating method or spin coating method, and a combination thereof, as well as various coating methods proposed by the present applicant. It can be appropriately adopted. As for the film forming conditions, for example, it is preferable to form a film by drying and curing at 80 ° C. or more and 350 ° C. or less for 1 minute to 60 minutes.

[0048]

According to the present invention, the hydrolysis reaction of the water-repellent liquid is more completely terminated, and thereafter the water content is adjusted by using a dehydrating agent or the like to increase the degree of polycondensation, and at least dimer and trimer are formed. By controlling the water-repellent liquid to form and coating the substrate surface under a controlled coating environment to form a thin film, the reactivity between the water-repellent component and the substrate surface is made more efficient, It is possible to optimize the existing density of the fluoroalkyl group per unit area. The obtained water repellent film has remarkably excellent abrasion resistance, has high hardness and high adhesion and has durability, and has a long-term excellent water repellency, for example, a contact angle of about 95 °. Or more can be maintained.

[0049]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A water-repellent liquid was prepared as follows. As a raw material of a water-repellent liquid composition for forming a water-repellent film, a fluoroalkylalkoxysilane [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ S
i (OCH ₃ ) ₃ (hereinafter abbreviated as “FAS”), manufactured by Toshiba Silicone; TSL8233], and isopropyl alcohol as a diluting solvent (hereinafter abbreviated as “i-PA”); manufactured by Kishida Chemical And 0.1N-nitric acid (manufactured by Kishida Chemical Co., Ltd.), which is an acid catalyst, and the mixing ratio thereof is FAS: i-PA:
0.1N-HNO3 = 1: 25: 0.3 (unit: g), and the mixture was stirred at room temperature for about 2 hours to terminate the hydrolysis reaction.

Next, a synthetic zeolite [Molecular Sieve 4] as a dehydrating agent was added to the solution after the completion of the hydrolysis reaction.
A, manufactured by Kishida Chemical Co., Ltd.], and immersion and standing for 18 hours (dehydration time) to complete the dehydration while allowing the polycondensation reaction to take place, followed by filtration using a filter paper (manufactured by Advantech, No. 7) to remove the molecular weight. -But 4A was separated and removed to obtain a coating water-repellent liquid.

Subsequently, the production of the water-repellent substrate was carried out as follows. The surface of a float glass substrate having a size of 200 mm × 300 mm × 3.5 mm is polished using a polishing liquid and a brush polisher to sufficiently remove the abrasive, and then at 35 ° C.
In a 0.1N aqueous sulfuric acid solution for 1 minute. After that, the glass substrate 1 is washed with water and dried with a commercially available glass washing machine, and the temperature and the humidity are kept at 23 ° C. and 45% RH.
2 ml / sheet of a water-repellent liquid was dropped per sheet, and the entire surface of the glass was sufficiently stretched with a cotton cloth (trade name: Bencott), and then air-dried for about 5 minutes. Subsequently, the glass substrate is put into a muffle furnace, and a heat treatment (hereinafter, referred to as “curing”) is performed so that the temperature of the glass substrate reaches 140 ° C. in 5 minutes. Excessive water repellent remaining clouded was wiped with a cotton cloth impregnated with i-PA to obtain a transparent water repellent glass substrate. In addition, the above polishing liquid is
MIRAKE (A + B) (Mitsui Metals): Water = 1: 100
(% By weight) of the suspension was used.

Next, the measurement of the degree of polymerization of the water-repellent liquid, the water-repellency test of the water-repellent substrate and the abrasion resistance (traverse resistance) test were carried out by the following methods. [Measurement of degree of polymerization] Measurement method: Gel permeation chromatography (hereinafter abbreviated as “GPC”) Measurement equipment: High-speed GPC device HLC-8020 (manufactured by Tosoh) Column: TSKgelG4000H-HR, G3000H-HR, G2000H -HR and G2000H-HR (both manufactured by Tosoh Corporation) connected in series with four columns (each 30 cm) (column temperature is maintained at 40 ° C) Detector: Differential refractometer (Detector temperature is (Hold at 38 ° C) Eluent: tetrahydrofuran (flow rate: 1 l / min) Injection amount of water-repellent liquid: 50 μl The water-repellent liquid sample for GPC measurement contains water-repellent liquid in order to inactivate silanol groups. The hydrolysis and condensation polymerization of FAS is one of the TMS (trimethylsilyl) agents,
Trimethylchlorosilane ((CH ₃ ) ₃ SiCl: TMC
The hydrolyzate and polycondensate of FAS in the water-repellent liquid were converted to TMS using S), and then the sample (water-repellent liquid) was filtered through a filter having a pore size of 0.5 μm. The reaction conditions for TMS conversion were as follows: 0.57 g of T
MCS was added and the mixture was stirred at room temperature for 1 h. GPC obtained
From each peak in the chart, FA
S monomer (Monomer), dimer (Dime)
r) The presence of trimers and trimers was confirmed, and the respective retention times were 32.5,
30.8, 29.9 and 29.3 to 28.5 minutes could be identified.

The abundance ratio of each polymer was determined from the ratio of the peak areas. For example, the abundance ratio (η) of the trimer to the dimer is η = (peak area by trimer)
/ (Peak area by dimer). (However, it was assumed that the refractive index of a monomer, a dimer, a trimer, a tetramer or more does not change).

[Water repellency test] Measuring equipment: CA-X200 type manufactured by Kyowa Interface Science Measurement environment: in the air (about 25 ° C.) Water: water drop of pure water (2 μl) Evaluation: drop the above water drop on a glass surface, Measure the angle (°) between the glass and the water droplet (namely, the contact angle). The contact angle before the test is indicated by θ ₀ (°), and the contact angle after each test is indicated by θ (°).

[Abrasion resistance test] Test machine: Traverse type sliding test machine (manufactured by our company) Sample size: about 200 mm × 300 mm Load on friction cloth: 0.1 kg / cm ^{2 on} canvas cloth (JIS L 3102-1206) Stroke: 100 mm reciprocal sliding (the number of reciprocations is the number of reciprocations) Sliding speed: 30 reciprocations / min Evaluation: Measurement of contact angle θ (°) after 3,500 times of sliding.

The results are shown in Table 1 (moisture content in water-repellent liquid at each dehydration time and η value obtained by GPC (existence ratio of trimer to dimer of FAS in water-repellent liquid, η = 3 (The peak area of the body / the peak area of the dimer) and the abrasion resistance of the obtained water-repellent glass), the η value is 0.25, and the abrasion resistance (traverse resistance) is as follows: The contact angle after the test was 95 ° or more, which was extremely good. In Table 1, (◎) in the column of traverse resistance indicates an extremely good value of the contact angle after the test of 95 ° or more.
(Mark) indicates a good value of the contact angle after test of 90 ° to 95 °, and (x mark) indicates a rejected value where the contact angle after the test is less than 90 °. The water content in the water-repellent liquid is 66
It was 0 ppm.

Example 2 Compared with Example 1, the dehydration time was set to 6 hours. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0.17, and the abrasion resistance (traverse resistance) was extremely good because the contact angle after the test was 95 ° or more. The water content of the water repellent liquid was 1420 ppm.

Example 3 In comparison with Example 1, the dehydration time was set to 4 hours. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0.11, and the abrasion resistance (traverse resistance) was extremely good, with the contact angle after the test being 95 ° or more. The water content of the water repellent liquid was 22,10 ppm.

Example 4 In comparison with Example 1, the dehydration time was set to 2.5 hours. The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.08,
Abrasion resistance (traverse resistance) is 90 ° after test.
９５95 °, which was a pass. The water content of the water-repellent liquid was 2,780 ppm.

Comparative Example 1 Compared with Example 1, the dewatering time was set to 0 hour. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0, and the abrasion resistance (traverse resistance) was unacceptable because the contact angle after the test was less than 90 °. The water content of the water-repellent liquid was 9770.
ppm.

Comparative Example 2 Compared with Example 1, the dewatering time was 0.75 hours. The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.02, and the abrasion resistance (traverse resistance) was 9 degrees after the test.
It was less than 0 ° and was rejected. The water content in the water-repellent liquid was 5,240 ppm.

Comparative Example 3 The dehydration time was changed to 1.5 hours as compared with Example 1. The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.05,
Abrasion resistance (traverse resistance) is 90 ° after test.
And was rejected. The water content in the water-repellent liquid was 3,600 ppm.

FIG. 1 shows the water-repellent liquid sampled at each of the dehydration times in Examples 1 to 4 and Comparative Examples 1 to 3 as TMS.
2 shows a GPC chart measured after the formation. As described above, it was found that the following tendency was exhibited in the relationship between the dehydration time and the wear resistance (traverse resistance). As a result, when no dehydration treatment is performed, or when the dehydration time is as short as 1.5 hours, RT =
Almost no peak was observed due to the trimer of FAS at 29.9 minutes (RT = retention time) or the polymer at least equal to the tetramer of FAS at 28.5 to 29.3 minutes. On the other hand, when the contact angle becomes 90 ° or more after the abrasion resistance (traverse resistance) test and the dehydration time is 2.5 hours or more, a peak due to trimers starts to appear, and as the dehydration time elapses, the trimers become The peak increased, and a peak due to a higher order polymer of the fourth or higher order appeared. From this, wear resistance (traverse resistance)
(The contact angle is 90 or more), it is necessary to form a higher-order polymer of FAS. In particular, for the formation of a trimer, at least η (with respect to the dimer of FAS in the water-repellent liquid) It can be seen that the condition of trimer abundance, η = peak area of trimer / peak area of dimer) ≧ 0.06 is required.

Example 5 In comparison with Example 1, the water-repellent liquid was stored for 3 days. Using the stored water-repellent liquid, a water-repellent glass was produced. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0.29, and the abrasion resistance (traverse resistance) was extremely good, showing a contact angle of 95 ° or more after the test. The water content in the water-repellent liquid was 1250 ppm.

Example 6 In comparison with Example 1, the water-repellent liquid was stored for 6 days. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0.41, and the contact angle of the wear resistance (traverse resistance) after the test was 90 ° to 9 °.
5 °, which was a pass. The water content in the water-repellent liquid is 1
It was 570 ppm.

Comparative Example 4 In comparison with Example 1, the water-repellent liquid was stored for 9 days. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0.52, and the abrasion resistance (traverse resistance) after the test was not acceptable because the contact angle was less than 90 °. The water content of the water-repellent liquid is 23
It was 60 ppm. FIG. 2 shows the fifth and sixth embodiments.
7 shows a GPC chart of a water-repellent liquid sampled in Comparative Example 4 and stored for each number of storage days after TMS conversion. Note that FIG.
In Example 1, the number of storage days is 0, and Example 1 is also described.

As described above, it was found that the following tendency was exhibited in the relationship between the storage days and the abrasion resistance (traverse resistance). As a result, as the number of storage days increased, the peak of the FAS caused by the higher polymer gradually increased. This indicates that the water content in the water-repellent liquid is also increasing, and the condensation polymerization reaction is gradually progressing with storage, and the acceleration of the condensation polymerization reaction by the addition of the dehydrating agent continues even after the removal of the dehydrating agent. It indicates that. On the other hand, the abrasion resistance (traverse resistance) is significantly degraded when the storage days are 9 days or more, and the degree of polycondensation of FAS is in an appropriate range for the abrasion resistance (traverse resistance), that is, 0.1%. It can be seen that the control needs to be performed so that 06 ≦ η ≦ 0.5.

Example 7 Compared to Example 1, the type of solvent was ethanol (EtO
H). The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.18, and the abrasion resistance (traverse resistance) was extremely good, with a contact angle of 95 ° or more after the test.

Example 8 Compared to Example 1, the solvent was butanol (n-B
uOH). The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.26, and abrasion resistance (traverse resistance) was obtained.
Was very good, showing a contact angle of 95 ° or more after the test.

Example 9 In comparison with Example 1, the solvent was changed to acetone. The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.30, and the abrasion resistance (traverse resistance) was extremely good, with a contact angle of 95 ° or more after the test.

Comparative Example 5 Compared with Example 1, the solvent was changed to methanol (MeO
H). The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.02, and the wear resistance (traverse resistance) was unacceptable. FIG. 3 is a chart showing the results of GPC measurement of each of the water-repellent liquids after TMS conversion for Examples 7 to 9 and Comparative Example 5. FIG. 3 also shows Example 1 using isopropyl alcohol (i-PA) as a solvent.

As described above, it was found that the following tendency was exhibited in the relationship between the type of the solvent and the abrasion resistance (traverse resistance). As a result, when the solvent was other than methanol, the GPC chart showed that the trimer around RT = 29.9 minutes or RT = 28.5.
A peak due to a polymer of ４29.3 / tetramer or more was clearly seen, and the η value was in the range of 0.06 to 0.5. On the other hand, when methanol was used as the solvent, almost no trimer or higher peak was observed, and η was 0.02. When the solvent was other than methanol, the abrasion resistance (traverse resistance) was as good as 101 to 106, but was significantly reduced to 78 to 104 in the case of methanol. From these, it is necessary to form a higher-order polymer of FAS in order to secure high abrasion resistance (abrasion resistance). In particular, for the formation of a trimer, 0.06 ≦ η ≦ 0. It turns out that it is necessary to control to 5.

Example 10 In comparison with Example 1, the type of water repellent was changed to heptadecafluorodecyltriisopropoxysilane (CF ₃ (CF ₂ ) ₇ C
H ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ : Toshiba Silicone XC95-
A9715) and the solvent type was ethanol (EtO
In (H), the dehydration time was changed to 16 hours. The other conditions were the same as in Example 1. As a result, as shown in Table 1, the value of η was 0.21,
The abrasion resistance (traverse resistance) was such that the contact angle after the test was 95%.
° or higher, which was extremely good.

Example 11 Compared to Example 1, the type of water repellent was heptadecafluorodecyltriisopropoxysilane, the type of solvent was butanol (n-BuOH) and the dehydration time was the same as in Example 10. Was changed to 16 hours, respectively. The other conditions were the same as in Example 1. result,
As shown in Table 1, the value of η was 0.38, and the abrasion resistance (traverse resistance) showed a contact angle of 95 ° or more after the test, which was extremely good.

Comparative Example 6 In comparison with Example 1, the type of water repellent was heptadecafluorodecyltriisopropoxysilane and the type of solvent was isopropyl alcohol (i-PA) in the same manner as in Example 8.
In addition, the dehydration time was changed to 16 hours. The other conditions were the same as in Example 1.
As a result, as shown in Table 1, the value of η was 0, and the wear resistance (traverse resistance) was unacceptable. FIG. 4 is a chart showing the results of GPC measurement of each of the water-repellent liquids of Examples 10 to 11 and Comparative Example 6 after TMS conversion.

As described above, it was found that the following tendency was exhibited in the relationship between the type of the water repellent / the type of the solvent and the abrasion resistance (traverse resistance). As a result, when isopropyl alcohol was used as the solvent (that is, alcohol as a solvent having the same group as the alkoxy group in the fluoroalkoxy group-containing silane compound used as the water repellent), RT = Only a peak due to the monomer at 32.5 min was observed, and a trimer of RT = 29.9 / RT = 28.5-
No peak due to a polymer of 29.3 times tetramer or more was observed. On the other hand, when the solvent is ethanol or n-butanol, a peak of trimer or more is observed, and the abundance ratio (η) of trimer to dimer is η = 0.
21 and 0.38. When the solvent is isopropyl alcohol, abrasion resistance (traverse resistance)
However, when ethanol or n-butanol was used, the abrasion resistance (traverse resistance) was as good as 103 to 106 or 95 to 105. From these, in order to ensure high abrasion resistance (traverse resistance), it is necessary to form a higher-order polymer of FAS. In particular, for formation of a trimer, 0.06 ≦
It is understood that it is necessary to control η ≦ 0.5.

Further, i-PA was used as a solvent (Example 1).
The abundance ratio of each polymer of FAS monomer, dimer, trimer and tetramer or more in the dewatered water-repellent liquid prepared by using water and acetone (Example 9) was determined by GPC measurement. Table 2 shows the results estimated from the above. Thus, the FAS in the dewatered water-repellent liquid for ensuring high abrasion resistance (traverse resistance)
The monomer, dimer, trimer, tetramer or higher proportion of
60% by weight or more, 25% by weight or less, 12.5%
Wt% or less, and 5 wt% or less.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

As described above, according to the present invention,
Highly durable water-repellent substrates such as glass exhibiting extremely excellent abrasion resistance (traverse resistance) and maintaining high water-repellent performance stably and reliably in mass production. It improves the homogeneity of the glass and does not impair the optical characteristics, so it can be used not only for architectural purposes but also for automotive window materials, ship and aircraft window materials, bathroom and automotive mirrors, industrial glass, and various other products. It is possible to provide a useful water-repellent liquid that can be widely used and has high utility value.

[Brief description of the drawings]

FIG. 1 is a GPC chart of a water-repellent liquid at each dehydration time.

FIG. 2 is a GPC chart of a water-repellent liquid for each storage period.

FIG. 3 is a GPC chart of a water-repellent liquid prepared with various solvents (1).

FIG. 4 is a GPC chart of a water-repellent liquid prepared with various solvents (2).

Claims (12)

[Claims] 1. A water-repellent liquid comprising a water-repellent liquid containing a fluoroalkyl group-containing silane compound as an active ingredient, which is applied to the surface of a substrate to fix the fluoroalkyl group on the surface of the substrate and form a water-repellent film. The water-repellent liquid, wherein the fluoroalkyl group-containing silane compound in the liquid-repellent liquid contains at least a polymer composed of a dimer and a trimer. 2. The water-repellent material according to claim 1, wherein the ratio of trimer to dimer (η = trimer / dimer) in the polymer is 0.06 to 0.5. liquid. 3. The method according to claim 1, wherein the formation ratio of the polymer in the water-repellent liquid is 1 to 25% by weight for the dimer and 0.06 to 12.5% by weight for the trimer. 3. The water repellent liquid according to any one of claims 1 to 2. 4. The polymer in the water-repellent liquid is a monomer, dimer,
The water-repellent liquid according to any one of claims 1 to 3, wherein the water-repellent liquid comprises a monomer and a tetramer or more. 5. A method for forming a polymer in a water-repellent liquid, wherein a proportion of a monomer is 60% by weight or more, a dimer is 1 to 25% by weight, a trimer is 0.06 to 12.5% by weight, The water-repellent liquid according to any one of claims 1 to 4, wherein the content of the tetramer or more is 5% by weight or less. 6. The water-repellent liquid according to claim 1, wherein the water-repellent liquid is obtained by hydrolyzing and polycondensing a silane compound containing a fluoroalkyl group. 7. The water-repellent liquid according to claim 1, wherein the content of the fluoroalkyl group-containing silane compound in the water-repellent liquid is 2 to 20% by weight. 8. A step of applying a water-repellent liquid prepared by hydrolyzing and polycondensing a solution containing a fluoroalkyl group-containing silane compound as an active ingredient to the surface of a substrate, and then contained in the water-repellent liquid. A method for producing a water-repellent coating, comprising: a curing step of fixing a fluoroalkyl group to the surface of the substrate to form a water-repellent coating. 9. A water-repellent liquid comprising at least a dimer and a trimer in a water-repellent liquid by controlling the dehydration time in hydrolyzing a starting material comprising a fluoroalkyl group-containing silane compound, a diluting solvent and an acidic aqueous solution and then conducting condensation polymerization. The method for producing a water-repellent coating according to claim 8, wherein a monomer is formed. 10. A solvent other than alcohol corresponding to the type of alkoxy group in the alkoxy group-containing silane compound of the water repellent is used as the diluting solvent.
10. A method for producing a water-repellent coating according to any one of claims 9 to 9. 11. The water-repellent coating according to claim 8, wherein the base material is glass, and a water-repellent liquid is applied to the surface of the glass whose surface has been modified by polishing and acid treatment. Production method. 12. The water-repellent material according to claim 8, wherein the surface of the substrate is a top surface of a glass substrate manufactured by a float method or a fired surface of a glass substrate manufactured by a roll-out method. Manufacturing method of coating.