JPH04202027A - Anti-fogging treatment of glass surface - Google Patents

Abstract

PURPOSE:To maintain an anti-fogging effect for a long time by depositing a fluorine-base nonionic surfactant as an anti-fogging agent on a glass by chemical bonding. CONSTITUTION:The surface of glass (e.g. lens) is dipped in a mixture soln. of hydrofluoric acid and antimony trichloride for 10min. or longer and then washed with pure water. Then the glass is dipped in a silane coupling agent soln. for more than 2 hours and washed with pure water. If necessary, the glass surface is treated with low temp. plasma and dipped in a dioxan soln. of cyanuryl chloride. Then the dioxan is neutralized with aq. caustic potash and controlled to pH5 with hydrochloric acid. The glass is taken out, washed successively with aq. hydrochloric acid of pH5 and with pure water, and dipped in a fluorine-base nonionic surfactant aq. soln. for more than 10min. Into this surfactant soln., aq. caustic potash is added, and then after 10min., the glass is taken out, washed with pure water and dried.

Description

[Detailed Description of the Invention] [Industrial Application Field] Transparent glass has become an indispensable material in our daily life. For example, building materials such as window glass,
Because it is transparent glass, which is used in many familiar places such as lenses for glasses and goggles, vehicle viewing windows, showcases, and mirrors, one drawback is that the surface temperature of the glass is lower than the dew point of the atmosphere. When the atmosphere becomes hot and humid, small water droplets adhere to the surface and diffusely reflect light, a phenomenon known as ``fogging''.

This "fog-free" glass is desired for all kinds of applications.

[Conventional technology] Current general anti-fog technologies can be roughly divided into three types.

The first is bulk modification, the second is surface modification,
The other is structural methods such as insulation and dehumidification. The requirements for the anti-fogging performance of a tatami mat are not uniform and vary depending on the purpose and place of use.

In addition, there are various requirements for properties other than anti-fog, such as optical properties, kill resistance, adhesion, and durability, so at present no anti-fog method that satisfies all uses has yet been developed. do not have.

Therefore, in practice, these anti-fog methods must be used depending on the purpose.

Bulk modification is difficult to balance with the original physicochemical properties of the substance, and therefore cannot be expected as an anti-fogging method.

Much research has been conducted on surface modification that imparts antifogging performance only to the surface without impairing the properties of the material.

For example, in a method of kneading a surfactant during film forming, the surfactant is localized near the surface after forming, lowering the surface tension of water and spreading water droplets. This is used in agricultural films, food packaging films, etc.

There is also a method of applying a surfactant to the surface of a similar product, but it has been reported that in both cases, the effect does not last because the surfactant washes off after repeated use.

[Problems to be Solved by the Invention] Although there are various anti-fog technologies, there is a problem in terms of sustainability of the anti-fog effect.

In order to improve this drawback, a surfactant is chemically bonded to the glass surface in an attempt to maintain the antifogging effect.

The technical problem of the present invention is to attach a fluorine-based nonionic surfactant, which is an antifogging agent, to glass through chemical bonding in order to increase the sustainability of the antifogging effect.

[Means for Solving the Problems] As a means for solving the above-mentioned technical problems, the inventors studied methods for surface treatment of glass surfaces and invented three surface treatment methods shown below.

1. Method of etching the surface of glass with a mixed solution of hydrofluoric acid and antimony trichloride and applying a silane coupling agent 2. Method of treating glass with low-temperature plasma 3.1. and 2. This is a method that uses both.

That is, 1° (1) immerse the glass surface in a mixed solution of hydrofluoric acid and antimony trichloride for 10 minutes or more, (2) wash with pure water, (3) immerse in a silane coupling agent aqueous solution for 2 hours or more. After that, (4) washing with pure water, (5) immersing in a dioxane solution of cyanuric chloride, (6) neutralizing the dioxane solution from (5) above with an aqueous potassium hydroxide solution, (7) @Note (6) The solution was adjusted to pH5 with hydrochloric acid (8
) Take out the glass, wash it with hydrochloric acid water of pH 5, and then wash it with pure water. (9) Soak the taken glass in an aqueous fluorine-based nonionic surfactant solution for 10 minutes or more. (10) Add it to the aqueous solution of (9) above. A method for antifogging a glass surface, which comprises adding an aqueous potassium hydroxide solution, taking out the glass after 10 minutes, washing it with pure water, and drying it.

2゜ (1) The glass surface is immersed in a mixed solution of hydrofluoric acid and antimony trichloride for 10 minutes or more, (2) washed with pure water, (3) immersed in a silane coupling agent aqueous solution for 2 hours or more, and then , (4) Cleaning with pure water, (5) Treating the glass surface with low-temperature plasma, (6) Immersing in a dioxane solution of cyanuric chloride, (7) Neutralizing the dioxane solution from (6) above with an aqueous potassium hydroxide solution. (8) Adjust the solution of (7) above to pH5 with hydrochloric acid, (9
) Take out the glass and wash it with hydrochloric acid water of pH 5 and then with pure water. (10) Soak the taken glass in an aqueous fluorine-based nonionic surfactant solution for 10 minutes or more. (11) In the aqueous solution of (10) above. A method for antifogging a glass surface, which comprises adding an aqueous potassium hydroxide solution, taking out the glass after 10 minutes, washing it with pure water, and drying it.

3゜(1) Treat the glass surface with low-temperature plasma, (2) immerse it in a dioxane solution of cyanuric chloride, (3) neutralize the dioxane solution from (2) above with an aqueous potassium hydroxide solution, (4) above ( Adjust the solution of 3) to pH5 with hydrochloric acid,
) Take out the glass and wash it with hydrochloric acid water from P I-(5).
Wash with pure water, (6) immerse the removed glass in a fluorine-based nonionic surfactant aqueous solution for at least 10 minutes, (7) add potassium hydroxide aqueous solution to the aqueous solution in (6), and after 10 minutes, soak the glass. A method for antifogging a glass surface, which comprises taking it out, washing it with pure water, and drying it.

[Effect] 1) Regarding the etching effect of a mixed solution of hydrofluoric acid and antimony trichloride, when looking at the etching effect with an electron microscope, there are small pores of about 0.1 μm on the glass surface, and the glass surface is rough. It was confirmed that the surface was roughened, and it was also found that the longer the processing time, the greater the degree of surface roughening.

Points that must be kept in mind during treatment include the mixing ratio of hydrofluoric acid and antimony trichloride in the mixed solution, reaction temperature, and immersion time. When the concentration of hydrofluoric acid is high, the surface irregularities become large, and when the concentration of antimony chloride is high, the number of microscopic pores decreases and the antifogging effect decreases.

The mixing ratio of hydrofluoric acid/antimony trichloride is by weight.
90/10 to 60/40 is desirable.

The reaction temperature and reaction time are 20~/10℃ and 10~6
It is 0 minutes.

Further, the concentration of hydrofluoric acid is preferably 0.5 to 5%, and the concentration of antimony trichloride solution is preferably 1 to 10%.

2) The reaction of the silane coupling agent on the reaction glass surface before silane coupling is carried out by immersing the glass surface treated with a mixture of hydrofluoric acid and acitimon trichloride in an aqueous solution of the silane coupling agent.

As for the type of silane coupling agent, epoxysilane and aminosilane showed good results. The concentration of the silane coupling agent aqueous solution is preferably 0.5 to 1.0 weight percent.

Good results were obtained when the immersion temperature was 10 to 40°C and the immersion time was 3 to 48 hours.

3) Regarding the plasma power supply, low-temperature plasma was applied for 60 seconds to the glass surface that had been reacted with the silane coupling agent. The plasma power supply includes ], 3.
Using a 56 MHz high frequency power source, nitrogen gas was sent into the reactor containing the sample to generate plasma discharge. A sample was placed in a reactor, and the reactor was vacuumed for 100 minutes, after which a nitrogen gas was pumped in for 1 minute. Then, in order to thin the nitrogen scum, the plasma discharge was continued for another 2 minutes, and the plasma discharge was continued for 60 minutes.
It went up for seconds. The activated surface was then given a soothing lick for 100 minutes.

4) Reaction of cyanuric chloride Prepare a solution by dissolving 0.36 g of cyanuric chloride in 40 mj of dioxane and diluting it 5 times with water. Immerse the previous glass in the solution in a water bath, and after 5 minutes add 6 m of 1N hydrium hydroxide aqueous solution, Q.After another 5 minutes, add hydrochloric acid to adjust the pH.
Adjust it to 5.

Immediately thereafter, the glass was taken out and washed in hydrochloric acid of PH5, and finally washed with pure water.

The reaction formula is as follows.

5) Anti-J+5 of fluorine-based nonionic surfactant 1 g of fluorine-based nonionic surfactant was weighed and dissolved in 200 mJl of pure water. Immerse a piece of glass that has just been reacted with cyanuric chloride in this solution, add 10 m Jl of normal potassium hydroxide aqueous solution after 15 minutes, and wash the grate well with pure water after 10 minutes.

[Example] Example 1 A lens (made of glass) was treated with 3.0% hydrofluoric acid-6 at room temperature.
, 4:1 mixed solution of 0% antimony trichloride solution for 30 minutes and then washed with pure water.

1100 2 g of silane coupling agent A to 198 g of water
A solution was prepared by dissolving ``m''. After the roughened lens was immersed in this solution for 12 hours, it was thoroughly washed with pure water.

40 m of dioxane for each 0.3 m of cyanuric chloride for B
A solution was prepared by dissolving 6 g and diluting it 5 times with water. Immerse the lens in this solution in a water bath, add 6 mj of 1N aqueous potassium hydroxide solution after 5 minutes, and after 5 minutes add hydrochloric acid to adjust the pH to 5. Immediately take out the lens and
PI (5) was washed in hydrochloric acid and finally washed with pure water.

0.1 g of surfactant FSN was weighed and dissolved in 200 m of pure water. The lens reacted with cyanuric chloride was immersed in this solution, and after 15 minutes it was soaked in a normal potassium hydroxide aqueous solution.
After 10 minutes, the lens was thoroughly washed with pure water.

Example 2 Lenses (glasses) were treated with 1.7% hydrofluoric acid-6 at room temperature.
5% each in a 4:1 mixed solution of antimony trichloride solution.
Soak for 0 minutes, then wash with pure water.

2 g of silane coupling agent A~174, 198 m of water,
A solution was prepared in 1 ml. After the roughened lens was immersed in this solution for 24 hours, it was thoroughly washed with pure water.

Next, low-temperature plasma was applied to the lens reacted with the silane coupling agent for 60 seconds. For the plasma power supply, ], 3
．． Using a 56 MHz high frequency power source, nitrogen gas was fed into the reactor containing the lens to reduce the pressure to 0.2+orr or less, and then plasma discharge was generated. First, put a lens in the reactor and create a vacuum for 100 minutes, then remove nitrogen
I sent it in for a minute. Then, in order to thin out the nitrogen scum, the plasma discharge was continued for another 2 minutes, and the plasma discharge was increased for 60 seconds. Thereafter, the vacuum was applied for 100 minutes to soothe the activated surface.

Prepare a solution by dissolving 0.36 g of cyanuric chloride in 40 mj of dioxane and diluting it 5 times with water. Immerse the above lens in this solution in a water bath, add 6 mj of 1N potassium hydroxide aqueous solution with a diameter of 5 minutes, and after another 5 minutes, add hydrochloric acid and P H
Adjusted to 5. Immediately thereafter, the lens was taken out, washed in hydrochloric acid with a pH of 5, and finally washed with pure water.

0.1 g of surfactant FSN was weighed and dissolved in 2001TIJ pure water. A lens reacted with cyanuric chloride was immersed in this solution, and after 15 minutes, 10 mj of a normal aqueous potassium hydroxide solution was added, and after 10 minutes, the lens was thoroughly washed with pure water.

Example 3 Low-temperature plasma was applied to a lens (made of glass) for 120 seconds. A high frequency power source of 13.56 MI (z) was used as the plasma power source, nitrogen gas was fed into the reactor containing the lens, and after the temperature was reduced to 0.2 Torr or less, plasma discharge was generated.

First, a lens was placed in the reactor, the vacuum was applied for 100 minutes, and then nitrogen gas was pumped in for 1 minute.

Then, to thin out the nitrogen scum, leave it for another 2 minutes.
A plasma discharge was generated for 120 seconds. It was then pulled for 100 minutes to soothe the activated surface. Next, a solution was prepared by dissolving 40 m of dioxane and 0°36 g of Q cyanuric chloride and diluting it 5 times with water. Immerse the previous lens in this solution in a water bath, and add 6 ml of 1N potassium hydroxide aqueous solution with a diameter of 5 minutes.
mj was added, and after another 5 minutes, hydrochloric acid was added to adjust the pH to 5. Immediately thereafter, the plate was taken out, washed in hydrochloric acid of pH 5, and finally washed with pure water.

Weigh 0.1g of the surfactant FSN and dissolve it in 200m of pure water. The lens reacted with cyanuric chloride was immersed in this solution, and after 15 minutes it was soaked in a normal potassium hydroxide aqueous solution.
0m'' was added, and after 10 minutes, the lens was thoroughly washed with pure water.

"Effects of the Invention" When we exposed water vapor to lenses that had been anti-fogged by the method described in Examples 1.2 and 3 above and those that had not been treated at all and observed the degree of fogging, we found that the lenses that were not treated were foggy, but the lenses were not treated. The three samples tested did not exhibit any haze.

Furthermore, when comparing lenses treated with a commercially available silicone-based antifogging agent and those treated with the methods of Examples 1, 2, and 3, it was found that the former loses almost no antifogging effect after a few uses. However, samples 1 and 2 according to this example
and 3 had a semi-permanent anti-fog effect.

Claims (1)

[Claims] 1. (1) The glass surface is immersed in a mixed solution of hydrofluoric acid and antimony trichloride for 10 minutes or more, (2) washed with pure water, (3) immersed in a silane coupling agent aqueous solution for 2 hours or more, and then ( 4) Washing with pure water, (5) Immersing in a dioxane solution of cyanuric chloride, (6) Neutralizing the dioxane solution from (5) above with an aqueous potassium hydroxide solution, (7) Adding the solution from (6) above to hydrochloric acid. Adjust to PH5, (8)
Take out the glass, wash it with hydrochloric acid water of pH 5, and then wash it with pure water, (9) immerse the taken glass in a fluorine-based nonionic surfactant aqueous solution for 10 minutes or more, (10) in the aqueous solution of (9) above, A method for antifogging a glass surface, which comprises adding an aqueous potassium hydroxide solution, taking out the glass after 10 minutes, washing it with pure water, and drying it. (1) The glass surface is immersed in a mixed solution of hydrofluoric acid and antimony trichloride for 10 minutes or more, (2) washed with pure water, (3) immersed in a silane coupling agent aqueous solution for 2 hours or more, and then ( 4) cleaning with pure water, (5) treating the glass surface with low-temperature plasma, (6) immersing it in a dioxane solution of cyanuric chloride, (7) neutralizing the dioxane solution from (6) above with an aqueous potassium hydroxide solution, (8) Adjust the solution of (7) above to pH 5 with hydrochloric acid, (9)
Take out the glass, wash it with hydrochloric acid water of pH 5, and then wash it with pure water, (10) immerse the taken glass in an aqueous fluorine-based nonionic surfactant solution for 10 minutes or more, (11) in the aqueous solution of (10) above, A method for antifogging a glass surface, which comprises adding an aqueous potassium hydroxide solution, taking out the glass after 10 minutes, washing it with pure water, and drying it. 3. (1) Treat the glass surface with low-temperature plasma, (2) immerse it in a dioxane solution of cyanuric chloride, (3) neutralize the dioxane solution from (2) above with an aqueous potassium hydroxide solution, (4) perform the steps in (3) above. Adjust the solution to pH 5 with hydrochloric acid, (5)
Take out the glass, wash it with hydrochloric acid water of pH 5, and then wash it with pure water, (6) immerse the taken glass in a fluorine-based nonionic surfactant aqueous solution for 10 minutes or more, (7) in the aqueous solution of (6) above, A method for antifogging a glass surface, which comprises adding an aqueous potassium hydroxide solution, taking out the glass after 10 minutes, washing it with pure water, and drying it.