JP2003521360A - Transparent substrate having antifouling hydrophobic coating and method for producing the same - Google Patents

Abstract

(57) Abstract A method for applying a hydrophobic, oil-repellent, antifouling optical thin film coating to a transparent substrate is described. The coating is performed using a processing solution containing a preferred concentration of organosilane in the range of 0.05 to 50 mmol / l in a solvent consisting of water; alcohol; ethylene glycol or glycerol; and an acid catalyst. Apply. This processing solution is preferably prepared in a two-step procedure. In a two-step procedure, first the organosilane is reacted in concentrated form and then diluted. After the treatment solution has been applied to the transparent substrate, for example by dip coating, the applied substrate is dried, preferably by flash drying at room temperature, and then heated to a predetermined elevated temperature at a predetermined humidity.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION The present invention relates to optical thin film coatings and methods of applying such coatings, and more particularly to applying hydrophobic, stain-resistant optical thin film coatings. About and

Many optical transparencies (transparencies such as transparencies) include coatings made by laminating multiple thin film layers of precise thickness and refractive index. Usually, when such coatings are obtained from inorganic materials, their exposed surfaces are inherently (inherently) hydrophobic and have a high surface energy. As a result, foreign contaminants in the form of dust, oil and fingerprints adhere strongly to such exposed surfaces.

Such extraneous contaminants can significantly degrade the optical performance of such coatings by partially altering the optical path of incident light (impinging light). Also, the adherence of such extraneous contaminants can be very strong, so that they can only be removed by applying various chemical cleaning agents or by physical removal. However, such cleaning methods can permanently damage the coating and / or the underlying substrate.

One prior art technique for reducing the surface energy of such inorganic coatings is to heat treat the coated substrate at a temperature in the range of 400-800 ° C. to dehydroxylate the —OH groups on its surface. It is to be. This technique is usually insufficient to treat surfaces already exposed to the environment and cannot be used to treat coatings applied to substrates made of plastic. Because, plastic substrates typically have a deformation temperature (deformation t) below the processing temperature.
This is because it has an emperature).

Another conventional technique for reducing the surface energy of such inorganic coatings involves modifying the surface using chemical vapor deposition. Unfortunately, this technique requires the use of relatively expensive vacuum equipment, and
Relatively long reaction times and time to allow chemicals to drain from the chamber are required.

Yet another prior art technique for reducing the surface energy of such inorganic coatings is to deposit a hydrophobic protective coating containing saturated hydrocarbons, fluorocarbons or organosilanes onto the optical coating. That is (deposit). The organic silane base solution usually contains a non-polar solvent such as octane, heptane, toluene, tetrahydrofuran, trichloroethane or a weakly polar solvent,
These solvents are highly flammable or toxic. Therefore, it is not desirable to use these solvents. Known techniques for grafting an organosilane coating to the underlying coated substrate are also soaking in a dry atmosphere (dry nitrogen or dry air) for a relatively long time and with a solvent. It needs to be washed or wiped and then dried by heating at high temperature. If the coating is applied in a higher humidity environment, the coating solution deteriorates and / or the coating becomes non-uniform or translucent.

Furthermore, organosilane coatings typically have optical coefficients that are very similar to that of glass, so that when such coatings are applied to glass substrates, they are not readily available. It may not be visible. However, even small variations in coating thickness can adversely affect the optical performance of many optical substrates with multilayer thin film coatings, and can cause surface contaminants and defects to become noticeable.

[0008] Thus, a low cost, effective optical thin film coating that is hydrophobic, oil-repellant, and does not adversely affect any underlying coatings and / or desirable optical properties of the transparent substrate. It should be recognized that there is a need for a method for applying the above stain-resistant coatings to transparent substrates thereof. The hydrophobic coating is also chemically stable (ie, does not react with various solvents and detergents) and mechanically and environmentally stable (ie, changes in temperature, humidity and UV light). Endure). In addition, the hydrophobic coating is uniform, has no pinholes or spot defects, and its application should not be limited to any particular substrate size. Furthermore, the hydrophobic coating should be applied by a simple dip-coating procedure that does not use toxic or highly flammable solvents, yet the hydrophobic coating is environmentally friendly. (No harm to the environment), it should not require the need for wiping or cleaning during the application process.
The present invention meets these needs and provides additional related advantages.

SUMMARY OF THE INVENTION The present invention is an optical thin film coating that is hydrophobic, oil repellent and stain resistant that does not adversely affect the desired optical properties of any underlying coating and / or transparent substrate. And a method for applying the coating. This hydrophobic coating is chemically stable (i.e., does not react with various solvents and cleaning agents), and mechanically and environmentally stable (i.e., changes in temperature, humidity and UV light). Endure). In addition, the hydrophobic coating is uniform, has no pinholes or spot defects, and its application is not limited to any particular substrate size.
Moreover, the hydrophobic coating is applied without the use of toxic or highly flammable solvents, yet the hydrophobic coating is environmentally friendly and requires the need for wiping and cleaning during the application process. do not do.

More specifically, this hydrophobic, oil-repellent, antifouling thin film coating comprises water;
It is prepared by dipping the substrate in a treatment solution containing an organosilane in a solvent containing an alcohol such as ethanol, propanol, butanol; ethylene glycol or glycerol; and an acid catalyst. The organosilane is preferably at a concentration in the range of 0.05 to 50 mmol per 1000 ml of solution, the solvent being 0.1 to 90% by weight of water, and ethylene glycol and / or glycerol 0.5.
-20% by weight, the balance being alcohol (preferably ethanol or propanol alone or mixed with butanol). The treatment solution is preferably prepared in a two-step procedure. In a two-step procedure, the organosilane is reacted first in concentrated form, then diluted and reacted.

The organosilane contained in the treatment solution has saturated or fluorinated hydrocarbon chains. The hydrocarbon chains are directly bonded to silicon atoms in the underlying substrate by C-Si bonds. The organosilane further has 1 to 3 hydrolyzable groups. These groups are directly bonded to the silicon atom by the bond of C-O-Si. This organosilane has the following formula: (RO) _3-n -Si-{[C _{p + q} H _2p F _2q ]-(CH ₃ or -CF ₃ )} _{1 + n} [where n is 0 to 3 , P + q ≧ 2 (preferably> 8), and R is an alkyl group (preferably CH ₃ — or CH ₃ CH ₂ —)].

The acid catalyst contained in the treatment solution is an inorganic acid or an organic acid, preferably CH ₃ C
O ₂ H, HCl or HNO ₃ . The dip coating treatment procedure requires that the substrate be immersed in the treatment solution for only 1 to 60 seconds and then pulled up at a rate of about 0.001 cm / sec or higher. Applicable to substrates of any size, and multiple substrates at least 1c
The substrates can be immersed simultaneously with the constraint that they are spaced apart by m. Relative humidity during the dip coating process procedure is in the range of 15-95%,
It should preferably be in the range of 40-80%. The temperature should be in the range of 10-40 ° C. Dip-coated substrates should be left at room temperature for at least 1 minute (
Flash dry for preferably 20 minutes) and then heat dry at a temperature in the range of 50-250 ° C for at least 1 minute.

[0013]   The surface of the substrate coated according to the invention may be, for example, SiO 2.₂, Al₂O ₃ , ZnO₂, TiO₂, ITO, In₂O₃, Sb₂O₃, MgF₂, SnO₂As
It should contain various metallic or inorganic components. These surfaces are on the underlying substrate
By coating with such components or containing such inorganic components.
Machine / inorganic composite material, can be formed by bulk material.   Other features and advantages of the invention will be apparent from the following description of preferred embodiments and methods.
Get rid of These are described in connection with the attached figures and by way of example illustrate the principles of the invention.
Explaining.

DESCRIPTION OF THE PREFERRED METHODS A preferred embodiment of the present invention is an inorganic, non-reflective multi-layer coating that substantially reduces the susceptibility to staining of substrates coated thereon. It is in the form of a transparent plastic substrate having the multilayer coating described above with a particular hydrophobic protective coating (overcoat) deposited. in addition,
The protective film is applied in an effective manner without the need for highly flammable or toxic solutions and for long processing times. In particular, the hydrophobic protective film may be obtained by dip-coating the substrate in an aqueous-alcoholic solution containing a fluorinated organosilane, and then drying the coated substrate at a given temperature for a given time and heat drying. Apply by.

The solvent used for the fluorine-treated organic silane solution contains water and an alcohol such as ethanol, propanol or butanol. The solvent optionally further comprises an organic solvent having a boiling point higher than that of the alcohol, such as ethylene glycol, glycerol and the like. All of these solvent components are less flammable and less toxic than the solvents used in prior art methods for applying similar hydrophobic coatings.

The organosilane used in the preferred embodiment of the present invention contains a saturated hydrocarbon chain bonded directly to the metal atom by a C—O— metal bond. The carbon chain may be branched, but contains at least 2, preferably 8 or more carbon atoms. A hydrogen atom bonded to a carbon atom may be replaced by a fluorine atom such as a pre-fluorinated carbon chain or a fluorine-treated carbon chain. The organosilane preferably has 1 to 3 hydrolyzable groups which are directly bonded to the metal atom by a C—O— metal bond. This organosilane has the following formula: (RO) _3-n -Si-{[C _{p + q} H _2p F _2q ]-(CH ₃ or -CF ₃ )} _{1 + n} [where n is 0 to 3 And p + q ≧ 2 (preferably> 8), and R is an alkyl group (preferably CH ₃ — or CH ₃ CH ₂ —)].

The treatment solution may also contain a suitable acid catalyst such as CH ₃ CO ₂ H, HCl, HNO ₃ . The concentration of the organic silane in the treatment solution is in the range of 0.05 to 50 mmol per 1000 ml of the solution, preferably in the range of 0.1 to 10 mmol per 1000 ml of the solution. This solvent contains 0.1 to 90% by weight of water and 0.5 to 20% by weight of ethylene glycol and / or glycerol. The balance of this solvent is alcohol (preferably ethanol or propanol alone or mixed with butanol).
).

The composition of the treatment solution and the method of preparation of the treatment solution have a great influence on the properties of the resulting coating. For example, depending on the details of the preparation method of the treatment solution, and
Depending on the method of application of the treatment solution, treatment solutions containing the same organosilane (or even the same treatment solution) have been improved; or unchanged; or have been significantly or permanently contaminated. (Contains, for example, translucent or irremovable stains); can be used to make non-contaminating (anti-contaminant), hydrophobic, dipped substrates.

The non-staining, hydrophobic coating of the present invention may be, for example, SiO ₂ , Al ₂ O ₃ ,
It is suitable to be applied to a substrate containing a metal component or an inorganic component such as ZnO ₂ , TiO ₂ , ITO, In ₂ O ₃ , Sb ₂ O ₃ , MgF ₂ and SnO ₂ . The substrate can be made of bulk material such as glass sheet, aluminum foil and the like. Alternatively, the substrate itself can be a coating of inorganic components formed on any suitable substrate. The substrates are preferably, but not necessarily, cleaned and surface-contaminated prior to applying the non-staining, hydrophobic coating. Other features of the invention will be apparent from the description of the following non-limiting examples.

Example 1 Treatment solutions were prepared in a two-step procedure. First, 1300 isopropanol, water, HCl and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane were added.
Solution A was prepared by mixing at a relative molar ratio of 11: 290: 1 and magnetic stirring for 2 hours. Next, solution A is solution B containing 56000 parts of water (molar ratio), 1500 parts of ethylene glycol, and 15000 parts of isopropanol.
And magnetically stirred for 1 hour to produce a treatment solution.

A polymethylmethacrylate (PMMA) substrate (40 cm x 15 cm) with a multilayer anti-reflective (AR) inorganic coating was then contacted with the treatment solution for 10 seconds and then at 50% relative humidity. At 0.15 cm / sec. From the processing solution. The substrate is then allowed to evaporate in open air for 20 minutes,
It was then heat dried at 84 ° C for an additional 20 minutes. The contact angle of water to the coated substrate was measured to be 55 ° before treatment and 118 ° after treatment.
Met. The larger the contact angle, the greater the degree of hydrophobicity proves. No visible defects were observed in the treated substrate, nor was a shift in the optical performance of the treated substrate in the spectral region 400-700 nm. The improved stain resistance of the treated substrate made in Example 1 is shown in FIG. Also, no degradation of the optical performance of the treated substrate is observed, as shown by the reflectivity in the spectral region 400-700 nm of FIG.

Example 2 A treatment solution was prepared in exactly the same way as in Example 1, except that the reaction time for preparing Solution A was reduced to 30 minutes. AR-Coated P
The MMA substrate was contacted with the treatment solution for 10 seconds and then pulled up at a rate of 0.15 cm / sec at 50% relative humidity. The substrate was then heat dried at 84 ° C for 20 minutes. As a result of measuring the contact angle of water, it increased from 55 ° before the treatment to only 70 ° after the treatment. No visible defects were observed on the treated substrate. This example shows that the reaction time for preparing solution A was insufficient.

Example 3 First, isopropanol, water, HCl and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane are mixed in a relative molar ratio of 1000: 3: 1: 1 and magnetically stirred for 30 minutes. A processing solution was prepared by preparing Solution A by. Solution A was then treated with additional 5500 parts of isopropanol (molar ratio).
) And magnetically stirred for 15 hours. The AR-coated PMMA substrate was contacted with the treatment solution for 20 minutes and then pulled at a rate of 0.3 cm / sec at 50% relative humidity. The substrates are then placed at 8 for 20 minutes.
It was dried by heating at 4 ° C. As a result of measuring the contact angle of water, it increased from 55 ° before the treatment to 116 ° after the treatment.

Many visible defects on the treated substrate were not observed. This is
It is believed to be caused by the presence of a non-uniform, agglomerated layer of organosilane on the substrate. The particular solvent used, rather than the particular organosilane, appears to be an important parameter. Defects and stains on the treated substrate can be partially removed by washing with isopropanol and then wiping with a cotton cloth. However, if this washing is done before heat drying, the organosilane molecules are prevented from binding to the substrate and the water contact angle remains constant at 55 ° after treatment.

Example 4 First, isopropanol, water, HCl and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane were mixed in a molar ratio of 1800: 74: 2.3: 1 and stirred magnetically for 6 hours. A treatment solution was prepared by preparing solution A by Solution A is then mixed with additional 23,000 parts of water (molar ratio),
Magnetically stirred for 30 minutes.

The AR-coated PMMA substrate was contacted with the treatment solution for 10 seconds and then pulled at a rate of 0.2 cm / sec at 50% relative humidity.
The substrates are then subjected to 20% open air without preliminary flash drying.
Heat dried at 84 ° C for a period of time. As a result of measuring the contact angle of water, 55 ° before treatment
To 112 ° after treatment. No visible defects were observed on the treated substrate. However, the useful life of the treatment solution was measured and was only about 30 hours. Substrates treated with the treatment solution three days after preparation of the treatment solution did not show any significant increase in water contact angle. This indicates that the particular solvent used is important in determining the useful life of the processing solution.

Example 5 A treatment solution was prepared in exactly the same way as in Example 1. The AR-coated PMMA substrate was dip coated in the treatment solution in exactly the same way as done in Example 1. The first set of dip coated substrates was flashed in open air for 20 minutes and then heat dried at 40 ° C for 10 minutes. As a result of measuring the water contact angle of the first set of substrates, 55 ° before treatment to 8 ° after treatment.
Increased to 6 °. The second set of dip coated substrates was immediately heat dried at 84 ° C for 20 minutes without pre-evaporation in open air. As a result of measuring the water contact angle of the second set of substrates, it increased from 55 ° before the treatment to 95 ° to 120 ° after the treatment. Many visible spot defects and organosilane stains were strongly attached to both sets of treated substrates. This example shows that the curing conditions are insufficient, that is,
It indicates that the temperature of heat drying was not high enough or evaporation in open air was omitted.

Example 6 Except that the relative humidity during pulling the substrate out of the treatment solution was reduced to 10%
The treatment solution and AR-coated P were prepared in exactly the same way as in Example 1.
An MMA substrate was prepared. As a result of measuring the water contact angle of these treated substrates, it increased from 55 ° before the treatment to 95 to 120 ° after the treatment. Many visible spot defects and organosilane stains were strongly attached to these substrates. This example shows that the relative humidity during withdrawal of the substrate from the treatment solution affects the resulting coating properties.

Example 7 Instead of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane,
Three treatment solutions were prepared in exactly the same way as in Example 1, except that 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane, octadecyltrichlorosilane and octadecyltriethoxysilane were used. Then AR
The coated PMMA substrate was dip coated in exactly the same way as done in Example 1. As a result of measuring the water contact angle of these treated substrates, it increased from 55 ° before the treatment to 100 to 120 ° after the treatment. This example shows that the present invention has utility in using various organosilane compositions.

Example 8 A treatment solution and an AR-coated PMMA substrate were prepared in exactly the same manner as in Example 1, except that the treatment solution was aged at room temperature for 60 days. It was determined that the substrates treated with the cured solution had substantially the same properties as the substrates treated with the freshly obtained solution. This example shows that the curing of the preferred treatment solution does not adversely affect the usefulness of the treatment solution.

Example 9 (1) Thermal shock test (-30 to 80 ° C, 1000 cycles), (2) Dry cotton abrasion test on AR-coated PMMA substrate treated in the manner disclosed in Example 1.
(500g weight, 1000 times), (3) UV test (carbon arc, 450 hours), (4) Humidity test (60 ° C, 95% relative humidity, 192 hours), and (5) Chemical resistance test ( Gasoline, detergent, 60 ° C., 24 hours). It was confirmed that there was no significant change in the antifouling property and hydrophobicity of the tested substrates.

Example 10 A pair of AR-coated glasses were dip coated in a treatment solution similar to that prepared in Example 1 and then dried overnight (15 hours) at room temperature. It has been determined that the treated glasses have greater resistance to fingerprints and dust contamination. The frequency of need to clean the treated glasses was reduced by 400-1000%. In addition, it has been determined that treated spectacles are much easier to clean than untreated spectacles.

Example 11 An AR-coated PMMA substrate (40 cm x 35 cm) was dip coated in a treating solution prepared in the same manner as described in Example 1. It was confirmed that about 95% of the surface of the substrate had an initial water contact angle of 65 ° and the rest of the substrate surface of about 5% had an initial water contact angle of 77 °. This latter contamination of the surface is believed to be due to such variations in water contact angle. The water contact angle after dip coating and heat drying of this coated substrate in the same manner as described in Example 1 increases to 115-120 ° for the region where the initial water contact angle was 65 °. However, it was confirmed that there was substantially no change in the region where the initial water contact angle was 77 °.

A new treatment solution was prepared in the same manner as in Example 1, except that the amount of solution A was increased compared to the amount of solution B. In short, the same amount of solution A as in Example 1 was added to water 44800 parts (molar ratio), ethylene glycol 1200
Parts and fresh solution B containing 12000 parts isopropanol.
After treating the substrate according to the same procedure as described in Example 1, a uniform, antifouling hydrophobic coating was applied to the entire surface of the substrate, and then the water contact angle was measured.
It was 115 to 120 ° on the entire surface. This example shows that by increasing the concentration of organosilane in the treatment solution, the detrimental effect of the underlying AR coating on fouling can be overcome.

Example 12 After extensive use of the treatment solution prepared as described in Example 1 and / or after aging for a long time, the treatment solution produces a coating with a noticeably increased water contact angle. Generated. Solution A: 30% or more of the old processing solution was added to the old processing solution, preliminarily reacted for 2 hours, and then the replenished solution was stirred for 10 minutes or more, so that the old processing solution was initially effective. You can regain your sex. Such a replenished solution produced a uniform, stain resistant hydrophobic coating over the surface of the AR coated PMMA substrate. This example shows that the processing solution can be replenished without discarding the old solvent and without producing any waste solution. Although the present invention has been described in detail only with respect to the presently preferred embodiments and methods, those skilled in the art will recognize that various modifications can be made without departing from the invention.

[Brief description of drawings]

FIG. 1 shows the effect of applying permanent markers to a transparent substrate having an inorganic, non-reflective, multilayer coating. Here, the left side of the figure is unprocessed,
The right side is treated with a hydrophobic protective film according to the present invention.

FIG. 2 is a graph showing the reflectance of both a transparent substrate having an inorganic non-reflective multilayer coating and a substrate having and without the hydrophobic protective film according to the present invention.

─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D075 CA34 CA36 EB42                 4F100 AA00B AK25B AR00B BA02                       EH46A EH46B EH461 EH462                       EJ86B EJ861 EJ862 JB06A                       JL06A JN01B JN06B JN30A                 4J038 JC32 KA06 NA05 PB08

Claims (29)

[Claims] 1. A method for applying an antifouling and hydrophobic optical coating to a transparent substrate, which essentially comprises a first solution containing an organosilane, an alcohol, water and an acid catalyst in a predetermined relative blending ratio. Is prepared, the first solution is reacted for a predetermined time, the second solution containing water and the first solution are mixed to form a treatment solution, and the treatment solution is applied to the surface of the transparent substrate. And then drying the coated substrate. 2. The organic silane mixed in the first solution has the following formula (RO) _3-n -Si-{[C _{p + q} H _2p F _2q ]-(CH ₃ or —CF ₃ )} _{1 + n} [wherein, n is 0 to 3, p + q ≧ 2, and R is an alkyl group]. 3. The method according to claim 2, wherein p + q> 8 and R is CH ₃ — or CH ₃ CH ₂ —. 4. The organic silane mixed in the first solution is 1H, 1H, 2H,
The method of claim 1, which is 2H-perfluorodecyltriethoxysilane. 5. The organic silane mixed in the first solution is 1H, 1H, 2H,
2. A selected from the group consisting of 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane, octadecyltriethoxysilane, octadecyltrichlorosilane, and mixtures thereof.
The method described. 6. The treatment solution comprises an organosilane at a concentration in the range of about 0.05 to 50 mmol / liter, a first solvent of water at a concentration in the range of about 0.1 to 90% by weight, and A second solvent selected from the group consisting of ethylene, glycol, glycerol, and mixtures thereof in a concentration ranging from 0.5 to 20% by weight, and selected from the group consisting of ethanol, propanol, butanol, and mixtures thereof. The method of claim 1, further comprising: 7. The method of claim 6, wherein the treatment solution contains organosilane at a concentration in the range of about 0.1-10 mmol / liter. 8. The first solution comprises 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, isopropanol, water and an acid catalyst at about 1: 1300: 1.
It contains a relative molar ratio of 1: 290, and the second solution contains water, ethylene glycol, and isopropanol at about 56000.
The method according to claim 1, which comprises a relative molar ratio of 1500: 15000. 9. The method of claim 1, wherein the first solution is reacted for at least about 2 hours. 10. The method of claim 1, wherein the applying step comprises the steps of immersing the substrate in the treatment solution and then withdrawing the substrate from the treatment solution at a predetermined rate. 11. The step of pulling the substrate out of the processing solution is about 0.001 cm.
The method according to claim 1, wherein the method is performed at a speed of at least 1 second. 12. The step of drying the coated substrate comprises:   Initially, the coated substrate is dried in air for a first predetermined time, then   Subsequently, the coated substrate is dried at an elevated temperature for a second predetermined time, The method of claim 1 including steps. 13. The method of claim 12, wherein the step of initially drying the coated substrate occurs for at least about 20 minutes; and the subsequent step of drying the coated substrate occurs for at least about 20 minutes. . 14. The step of initially drying the coated substrate comprises about 10-4.
13. The method of claim 12, wherein the step is carried out at a temperature in the range of 0 [deg.] C; yet the subsequent drying of the coated substrate is carried out at a temperature in the range of about 50-250 [deg.] C. 15. Subsequent drying of the coated substrate comprises 15-95.
13. The method of claim 12, performed in an environment having a humidity in the range of%. 16. Subsequent drying of the coated substrate comprises 40-80.
16. The method of claim 15 performed in an environment having a humidity in the range of%. 17. The method of claim 1, further comprising aging the treatment solution for a plurality of days before using the treatment solution in the coating step. 18. The method of claim 17, further comprising the step of adding an additional amount of the first solution to the treatment solution after the aging step. 19. The method according to claim 1, wherein the substrate used in the coating step contains a material having a metal component or an inorganic component. 20. The method of claim 19, wherein the substrate used in the applying step comprises a polymethylmethacrylate substrate having an inorganic, non-reflective coating. 21. A method of applying an antifouling, hydrophobic optical coating to a transparent substrate, which essentially comprises the following formula (RO) _3-n -Si-{[C _{p + q} H _2p F _2q ]. -(CH ₃ or -CF ₃ )} _{1 + n} [wherein, n is 0 to 3, p + q ≧ 2, and R is an alkyl group], an organic silane, an alcohol, water, and an acid. A group consisting of water, ethylene glycol, glycerol, ethanol, propanol, butanol, and mixtures thereof, in which a first solution containing a catalyst in a predetermined relative blending ratio is mixed, the first solution is reacted for at least 2 hours A second solution containing a solvent selected from, mixing the first solution with the second solution to form a treatment solution, and immersing the treatment solution on the surface of a transparent substrate having an inorganic non-reflective coating Coated, then coated Base and in an environment having a humidity range of 15-95%, drying for a predetermined period of time at elevated temperature, comprising the various steps, the coating process. 22. A method of applying an antifouling, hydrophobic optical coating to a transparent substrate, wherein the organosilane has a concentration in the range of about 0.1 to 10 mmol / liter and about 0.1 to 90% by weight. A first solvent of water at a concentration in the range of, and a second solvent selected from the group consisting of ethylene glycol, glycerol, and mixtures thereof at a concentration in the range of about 0.5 to 20% by weight, ethanol A third solvent selected from the group consisting of :, propanol, butanol, and mixtures thereof; and preparing a treatment solution consisting essentially of: coating the surface of a transparent substrate with the treatment solution; The above coating method, which comprises the steps of: 23. The organosilane has the following formula (RO) _3-n -Si-{[C _{p + q} H _2p F _2q ]-(CH ₃ or -CF ₃ )} _{1 + n} [wherein n is 0 to 3, p + q> 8, and R is CH ₃ — or CH ₃ CH ₂ —.
23. The method of claim 22, wherein 24. The organosilane is selected from 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane, octadecyltriethoxysilane, octadecyltrichlorosilane, and mixtures thereof. 24. The method of claim 23, selected from the group consisting of: 25. The step of drying the coated substrate comprises the steps of:   Initially, the coated substrate is dried in air for a first predetermined time, then   Subsequently, the coated substrate is dried at an elevated temperature for a second predetermined time, 23. The method of claim 22, comprising steps. 26. The method of claim 25, wherein the step of initially drying the coated substrate occurs for at least about 20 minutes; and the subsequent step of drying the coated substrate occurs for at least about 20 minutes. . 27. The initial drying of the coated substrate comprises about 10-4.
26. The method of claim 25, wherein the method is performed at a temperature in the range of 0 [deg.] C; yet the subsequent drying of the coated substrate is performed at a temperature in the range of about 50-250 [deg.] C. 28. The subsequent drying of the coated substrate comprises 40-80.
26. The method of claim 25, performed in an environment having a humidity in the range of%. 29. A transparent substrate having an antifouling, hydrophobic optical thin film coating applied using the method of claim 1.