JP2743707B2 - Glass with mixed coating and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent film formed on a glass substrate and can be used, for example, as a water-repellent glass.

[0002]

2. Description of the Related Art Conventionally, carbon and fluorine have been coated on the surface of glass in order to impart water repellency to glass and reaction tubes. For example, in JP-A-2-18847,
It discloses a method of forming a carbon coating by supplying a carrier gas containing a carbon film forming raw material to the glass surface after reducing the glass surface with hydrogen gas.

[0003]

However, in the above method, there is a disadvantage that the adhesion between the glass substrate and the carbon coating is not sufficient, and the carbon coating is easily peeled off. It is considered that the reason why the adhesion is not excellent is that the glass substrate and carbon are bonded by an intermolecular force. Therefore, an object of the present invention is to improve the adhesion between the glass substrate and the mixed coating by bonding the glass substrate and the mixed coating with a covalent bond having a bonding force larger than the intermolecular force.

[0004]

According to the present invention, there is provided a gas coated with a mixed film according to the present invention.
The glass has at least a metal oxide and charcoal on the glass substrate surface.
Element or at least metal oxide, carbon and fluorine
Forming a mixed coating having water repellency by mixing,
At the interface between the glass substrate and the mixed coating, the mixed coating
The mole fraction of the metal oxide in the film is 5% or more
Wherein the production method according to the present invention further comprises a vapor deposition method.
It is characterized by being. Here, the glass substrate
Shall have a metal oxide in the component.
Use a glass made of silicate glass, soda lime glass, etc.
Can be used. In addition, with the metal oxide in the mixed coating
For example, SiO_Two, TiO_Two, ZrO_Two, Y _TwoO_Three, A
l_TwoO_Three, PbO, CaO, MgO, B_TwoO_Three, Fe_Two
O_Three, Na_TwoO, K_TwoO, Li_TwoOne or two such as O
More than species can be employed. The mole fraction is the substance
Amount representing the composition of the system, the number of moles of one component and the number of moles of all components
Is referred to as the mole fraction of one component. Molar amount of each component
The sum of the rates is equal to 1 (100%). In addition,
Are chemical vapor deposition (CVD), ion plating,
It is a physical vapor deposition method (PVD) such as vacuum vapor deposition.

[0005]

In the present invention, the glass serving as the base material and the mixed film formed on the surface of the glass base material contain a metal oxide. It is considered that the metal in the base material and the metal in the base material have a covalent bond via oxygen. Therefore, the glass substrate and the mixed film show a strong bonding force.

[0006]

Embodiments of the present invention will be described below with reference to the drawings. (Example 1) In a vacuum chamber of a binary RF magnetron sputtering apparatus, two targets of SiO ₂ and C were provided, and soda lime glass was also provided as a coating substrate. Then, the vacuum chamber was evacuated to 2 × 10 ⁻³ Pa or less, and the soda lime glass was heated to 300 ° C.
Next, Ar gas was introduced so that the pressure in the vacuum chamber became 0.1 Pa, and a voltage was applied to each target as shown in FIG. 2 to perform sputtering film formation. In this way, as shown in FIG. 1, Si, O,
C, mixed film 2 was obtained.

[0007] Si, O, C in the depth direction from the surface of the glass with the mixed film is analyzed by AES (Auger electron spectroscopy).
FIG. 3 shows the results of the quantitative analysis according to the above. FIG. 3 shows the distance (nm) from the outermost surface of the mixed film and the atomic concentration (a) of each atom.
t%), which indicates that a Si, O, and C mixed film of about 60 nm is formed on soda lime glass. The mole fraction of carbon was 55% at the interface between the glass substrate and the mixed coating, and the mole fraction of SiO ₂ was 4%.
5%. Drop water drops on this mixed coated glass,
When the contact angle between the glass with the mixed coating and the water droplet was examined, it was 8
0 °, indicating good water repellency. Also, to investigate the adhesion between this mixed film and soda lime glass,
A fastness test was performed on the surface of the glass with the mixed coating under a condition of rubbing 3,000 reciprocations with a dry flannel cloth while applying a load of 300 g / cm ² . As a result, the film rubbed with the dried flannel cloth under the friction condition of 3000 reciprocations did not show any change as compared with that before the test, indicating that the adhesion was good. Incidentally, the visible light transmittance of this film is 85%.
And very high values. (Test 1) In Example 1, although the atomic concentration of carbon was constant at 20 at%, various RF powers were set in order to form various mixed coatings in which the atomic concentration of carbon was kept constant.
In each case, sputtering was performed in the same manner as in Example 1 except that the film thickness was set to 100 nm. Then, the visible light transmittance of each mixed film was examined, and the result is shown in FIG. FIG. 4 shows that under the conditions such as the present test, the visible light transmittance becomes 70% or more when the constant carbon atom concentration is 70% or less, and the visibility is ensured from the viewpoint of vehicle safety. Conforms to the standard values required for In other words, it can be seen that the lower the carbon concentration, the more excellent the light transmittance. (Example 2) Sputter deposition was performed in the same manner as in Example 1 except that RF power was applied for 60 minutes to obtain a Si, O, and C mixed film of about 190 nm on soda lime glass. The visible light transmittance of this thick film is 70%. As in the present embodiment, the metal oxide contained in the mixed film has a light-transmitting property, and when a mixed film having a low carbon concentration that is not excellent in the light-transmitting property is formed, the light-transmitting property is maintained. ,
Since the film thickness can be made extremely large, it becomes possible to produce water-repellent glass having excellent wear resistance. (Comparative Example) For comparison, a sputtering film was formed in the same manner as in Example 1 except that only the target was C.
This was performed for 0 minutes to obtain a glass with a carbon coating. From the surface of the glass with the carbon coating thus obtained, C, S in the depth direction were obtained.
When i and O were quantitatively analyzed by AES, a carbon film of about 20 nm was formed almost directly on the soda-lime glass shown in FIG. When the contact angle between the glass with the carbon coating and the water droplets was examined in the same manner as in Example 1, the contact angle was 90 degrees, indicating good water repellency. The surface of the glass with the carbon coating was subjected to a fastness test in the same manner as in Example 1. As a result, at the 50th reciprocation, all the carbon coatings peeled off, and the contact angle became 50 degrees. (Test 2) In order to obtain various samples having different molar concentrations of the metal oxides in the mixed film at the interface between the soda lime glass and the mixed film, the RF power (W) was varied to obtain various samples. Change the abundance ratio of C, Si, O
Other than that, the sputtering film formation was performed in the same manner as in Example 1. FIG. 6 shows the results of measuring the contact angles before and after performing the same robustness test as in Example 1 using the various samples thus obtained. Until the mole fraction of SiO _{2 in} the mixed coating of FIG. 6 reaches 20%, the contact angle becomes small before and after the fastness test. This is probably because the adhesion between the substrate and the mixed film was not sufficient, and the mixed film was peeled off in the fastness test. Although the contact angle was small even when the molar fraction of SiO ₂ in the mixed coating exceeded 70%, this was because the molar fraction of carbon, which is a water-repellent element, in the mixed coating was low. It is.
Therefore, good adhesion is obtained when the mole fraction of SiO _2, that is, the metal oxide is 5% or more, more preferably 20% or more, and the carbon carbon mole fraction is 10% or more, more preferably 30% or more. The above shows the best water repellency. (Embodiment 3) This mixed-coated glass was obtained by changing the RF power from that of Embodiment 1. Other configurations are the same as in the first embodiment. That is, in the glass with the mixed film, the RF power (W) was changed with time as shown in FIG. 7, and the film was formed by sputtering. C in the depth direction from the surface of the glass with the mixed film thus obtained,
When Si and O were quantitatively analyzed by AES, as shown in FIG. 8, a mixed film of C, Si, and O having a thickness of about 60 nm was formed on the glass substrate. From this figure, it can be seen that the carbon concentration increases toward the mixed coating surface.
At the interface between the glass substrate and the mixed film, the molar fraction of carbon was 36.3%, and the molar fraction of SiO ₂ was 63.6.
%. When the contact angle between the glass with the mixed coating film and the water droplets was examined in the same manner as in Example 1, the contact angle was 85 °, indicating better water repellency than Example 1. This is because the concentration of carbon, which is an element having water repellency, increases toward the surface of the mixed coating. Further, as for the adhesion, a fastness test was conducted in the same manner as in Example 1, and as a result, no change was observed in the mixed film before and after the test, indicating that the adhesion was good. The visible light transmittance of the glass with the mixed coating film is as high as 75%. As in the present embodiment, the concentration of the metal oxide is increased at the interface between the glass substrate and the mixed coating, and the carbon concentration is increased on the mixed coating surface. A mixed coating having excellent water repellency and excellent water repellency can be obtained on a glass substrate. (Example 4) Two targets of SiO ₂ and C were provided in a vacuum layer of a binary RF magnetron sputtering apparatus, and soda lime glass was also provided. Then, the vacuum layer was evacuated to 2 × 10 ⁻³ Pa or less, and the soda lime glass was heated to 300 ° C. Next, a mixed gas obtained by mixing 20 vol% of CF ₄ gas in Ar gas is introduced so that the pressure in the vacuum layer becomes 0.1 Pa, and a voltage is applied to each target as shown in FIG. Was done. In this way, S
A mixed coating of i, O, C, and F was obtained.

[0008] From the surface of the glass with the mixed coating to the depth
Si, O, C, and F in AES (Auger electron spectroscopy
Analysis), as shown in FIG.
Approximately 60 nm of Si, O, C, F on soda lime glass
Was formed. In addition, mixed with glass substrate
At the interface of the film, the mole fraction of carbon is 28%
Is 50% and SiO_TwoHas a molar fraction of 20%
is there. Implement the contact angle between the glass with the mixed coating and the water droplet
When examined in the same manner as in Example 1, it was 100 °
Water repellency was shown. Generally good water repellency with fluorine alone
Performance is not obtained, but fluorine and carbon coexist in the mixed coating.
The water repellency is enhanced by the synergistic effect
is there. Also, the adhesion was firmly fixed in the same manner as in Example 1.
As a result of conducting a fastness test, mixing before and after the test
No change was seen in the coating, indicating good adhesion
Was. By the way, the visible light transmittance of this film is very high at 85%.
Shows a high value. (Example 5) Except for applying the RF power for 65 minutes,
Sputtering film was formed in the same manner as in Example 4
Approximately 200 nm of Si, O, C, F
A membrane was obtained. And the visible light transmittance of this thick film is 70%.
Is shown. In Test 1, the higher the carbon concentration, the higher the light transmission
The same is true for fluorine.
Can be considered. Included in mixed coatings as in this example
Charcoal whose metal oxide has translucency and is not excellent in translucency
When a mixed film with a low concentration of silicon and fluorine is formed,
Extremely thick film thickness while maintaining translucency
Therefore, the production of water-repellent glass with excellent wear resistance
Can be manufactured. (Test 3) At the interface between soda lime glass and mixed film
With different mole fractions of metal oxides in the mixed coating
RF power (W) must be varied to obtain various samples.
By changing the abundance ratio of C, Si, and O in the mixed coating,
Otherwise, the sputtering film formation was performed in the same manner as in Example 3.
Was. Using various samples obtained in this way,
The contact angle was measured before and after performing the same robustness test as in Example 1.
The results are shown in FIG. SiO in the mixed coating of FIG._Two
Before and after the robustness test, until the mole fraction of
At a small contact angle. It is mixed with the substrate
The adhesion with the composite film is not enough,
It is considered that the mixed coating was peeled off. Also, mixed coating
SiO inside_TwoContact angle is small even if the mole fraction of
This is to reduce the water repellency in the mixed coating.
The mole fractions of carbon and fluorine are low
That's why. Therefore, SiO_TwoThat is, the mole of metal oxide
Good adhesion is obtained when the fraction is 5% or more, and more preferable.
Or the sum of the mole fractions of carbon and fluorine
Is 5% or more, more preferably 25% or more.
Shows good water repellency. (Embodiment 6) The glass with the mixed coating is the same as that of Embodiment 4.
And obtained by changing the RF power. Other configurations are
This is the same as the fourth embodiment. That is, the gas with the mixed coating
In the Lass, as shown in FIG. 12, the RF power (W) is
Both were changed, and sputtering film formation was performed. Like this
From the surface of the glass with mixed coating obtained
When C, Si, O and F were quantitatively analyzed by AES,
As shown in FIG. 13, about 60 nm of C on a glass substrate,
A mixed film of Si, O, and F was formed. Also this figure
From that the carbon concentration increases toward the mixed coating surface.
I understand. In addition, at the interface between the glass substrate and the mixed coating
The molar fraction of carbon is 10.6% and the molar fraction of fluorine is 3
1.9% SiO_TwoIs 57.4%.
The contact angle between the glass with the mixed thin film and the water droplet was determined as in Example 1.
It is 110 degrees when examined in the same manner, and has good water repellency.
Noh showed. This is due to the water repellency towards the mixed coating surface
Due to the high concentration of carbon
is there. Also, the adhesion was firmly fixed in the same manner as in Example 1.
As a result of performing a fastness test, the mixed coating was observed before and after the test.
No change was observed, indicating good adhesion.
Was. The visible light transmittance of the glass with the mixed coating is
It shows a very high value of 80%. As in this embodiment
In addition, the metal oxide concentration at the interface between the glass substrate and the mixed coating
To increase the carbon concentration on the mixed coating surface.
By making the element have a concentration gradient,
A glass-based mixed coating with excellent adhesion and excellent water repellency
Can be obtained on wood. (Example 7) A binary RF ion pump equipped with two evaporation crucibles
SiO in the vacuum layer of the rating device _TwoAnd the evaporation material of C
And soda lime glass as a coating substrate
Equipped. And the vacuum chamber is 2 × 10^-3Up to Pa
And heat soda lime glass to 300 ° C
did. Next, 2 × 10^-1Lead to Pa
And then CF_Four3 × 10 gas^-1To be Pa
Introduce 300W power to RF coil and plasma
Generated. Next, apply a voltage of 10 KV to the electron gun
And the beam current for each evaporating material as shown in FIG.
Was changed to form a film. In this way, soda rai
A mixed film of Si, O, C, and F was obtained on the glass. This mix
Si, O, C, in the depth direction from the surface of the glass
F was quantitatively analyzed by AES. As shown in FIG.
Approximately 50 nm of Si, O,
A mixed film of the C and F mixed films was formed. In addition, Gala
At the interface between the substrate and the mixed coating, the mole fraction of carbon is 2
8%, the mole fraction of fluorine is 50%, SiO_TwoMole of
The fraction is 22%. The glass with this mixed film and the water drop
Was measured in the same manner as in Example 1.
And exhibited good water repellency. In addition,
A fastness test was conducted in the same manner as in Example 1
As a result, no change was observed in the mixed film before and after the test.
Mixed film formed by on-plating
However, it was shown that the adhesion was good. By the way
The visible light transmittance of the film is as high as 85%.
You. (Embodiment 8) Binary RF magnetron sputtering apparatus
TiO in the vacuum chamber_TwoAnd two targets C
Both were also equipped with transparent quartz glass as the coating substrate. So
Then, the vacuum chamber is 2 × 10^-3Vacuum to below Pa
Then, the transparent quartz was heated to 300 ° C. Next, Arga
CF_Four20% by volume mixed gas
Introduce the pressure inside the vacuum chamber to 0.1 Pa, and
A voltage was applied to the target as shown in FIG.
A ring film was formed. In this way, T
A mixed coating of i, O, C, and F was obtained. Gala with this mixed film
Ti, O, C, F in the depth direction from the surface of
As a result of quantitative analysis, as shown in FIG.
About 50 nm of Ti, O, C, F mixed coating on glass
Had been formed. The interface between the transparent quartz glass and the mixed coating
, The mole fraction of carbon is 25% and the mole fraction of fluorine is
The rate is 67%, TiO_TwoIs 8%. this
The contact angle between the glass with the mixed coating and the water droplet was the same as in Example 1.
It was 105 degrees when examined, and good water repellency
Indicated. In addition, the adhesion was the same as in Example 1.
As a result of conducting a robustness test and examining
No change was observed in the composite film,_TwoUsing the target
It was also shown that the adhesion was good. by the way
The visible light transmittance of this film is as high as 80%.
ing.

The element concentration in the mixed film is not limited to the embodiment, and by setting variously, a glass with a mixed film according to the intended use can be obtained. In this embodiment, all of the mixed coatings are substantially composed of metal oxide and carbon, or metal oxide, carbon and fluorine, but other elements may be added as long as adhesion or water repellency is not impaired.

[0010]

As described in detail above, the mixed coating containing metal oxide and carbon, or the mixed coating containing metal oxide, carbon and fluorine has water repellency and excellent adhesion to the glass substrate, so that glass By coating the substrate with such a mixed film, a water-repellent film that is difficult to peel off can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a glass with a mixed coating of Example 1.

FIG. 2 is a graph showing a relationship between a film forming time and RF power according to Example 1.

FIG. 3 is a graph showing the relationship between the distance from the outermost surface of the mixed coating film and the atomic concentration according to Example 1.

FIG. 4 is a graph showing the relationship between carbon concentration and visible light transmittance according to Test 1.

FIG. 5 is a graph showing a relationship between a distance from an outermost surface of a carbon coating and an atomic concentration according to a comparative example.

FIG. 6 relates to SiO ₂ in the mixed film in connection with Test 1.
3 is a graph showing the relationship between the mole fraction of the sample and the contact angle before and after the fastness test.

FIG. 7 is a graph showing a relationship between a film forming time and RF power according to Example 3.

FIG. 8 is a graph showing the relationship between the distance from the outermost surface of the mixed coating and the atomic concentration according to Example 3.

FIG. 9 is a graph showing the relationship between the film formation time and RF power according to Example 4.

FIG. 10 is a graph showing the relationship between the distance from the outermost surface of the mixed coating and the atomic concentration according to Example 4.

FIG. 11 shows SiO ₂ in the mixed film according to Test 2.
3 is a graph showing the relationship between the mole fraction of the sample and the contact angle before and after the fastness test.

FIG. 12 is a graph showing a relationship between a deposition time and RF power according to Example 6.

FIG. 13 is a graph showing the relationship between the distance from the outermost surface of the mixed coating and the atomic concentration according to Example 6.

FIG. 14 is a graph showing the relationship between the film formation time and the beam current according to Example 7.

FIG. 15 is a graph showing the relationship between the distance from the outermost surface of the mixed coating and the atomic concentration according to Example 7.

FIG. 16 is a graph showing the relationship between the deposition time and RF power according to Example 8.

FIG. 17 is a graph showing the relationship between the distance from the outermost surface of the mixed coating and the atomic concentration according to Example 8.

[Explanation of symbols]

 1: Glass substrate 2: Mixed coating

Claims (4)

(57) [Claims] 1. A water-repellent mixed coating formed by mixing at least a metal oxide and carbon on a surface of a glass substrate, and at an interface between the glass substrate and the mixed film,
The mole fraction of the metal oxide in the mixed coating is 5%
A glass with a mixed coating characterized by the above. 2. A water-repellent mixed coating formed by mixing at least a metal oxide, carbon, and fluorine on a surface of a glass substrate, and the mixed coating at the interface between the glass substrate and the mixed coating is formed. A glass with a mixed coating, wherein the metal oxide has a molar fraction of 5% or more. 3. The method for producing glass with a mixed film according to claim 1, wherein a water-repellent mixed film formed by mixing at least a metal oxide and carbon is obtained on the surface of the glass substrate by vapor deposition. . 4. The mixed-coated glass according to claim 2, wherein a water-repellent mixed coating obtained by mixing at least a metal oxide, carbon and fluorine is obtained on the surface of the glass substrate by vapor deposition. Production method.