JP2018035005A - Method for producing dielectric multilayer film-attached glass plate, and dielectric multilayer film-attached glass plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a dielectric multilayer film-attached glass plate excellent in scratch resistance.SOLUTION: There is provided a method for producing a dielectric multilayer film-attached glass plate 1 including a glass plate 2 and a dielectric multilayer film 3 laminated on the glass plate 2. The dielectric multilayer film 3 has a first film 4 composed of silicon oxide and a second film 5 composed of a material having a higher refractive index than the silicon oxide. The method comprises the steps of preparing the glass plate 2 and depositing the dielectric multilayer film 3 on the glass plate 2 by sputtering. When the first film 4 is deposited by sputtering, the deposition pressure of the first film 4 is 0.4 Pa or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a glass plate with a dielectric multilayer film, in which a dielectric multilayer film is provided on a glass plate, and to a glass plate with a dielectric multilayer film.

  Conventionally, a glass plate with a dielectric multilayer film in which a dielectric multilayer film is provided on a glass plate has been used. The dielectric multilayer film is used as a functional film such as an antireflection film.

  For example, Patent Document 1 below discloses a glass plate with a dielectric multilayer film as an infrared shielding glass. Patent Document 1 describes a multilayer film in which a tantalum oxide film, a nitride film, and a tantalum oxide film are stacked in this order as a dielectric multilayer film.

  Moreover, the following patent document 2 discloses a glass plate with a dielectric multilayer film as a heat ray shielding glass. In Patent Document 2, a dielectric multilayer film is laminated on a glass substrate provided with a heat ray shielding film. As the dielectric multilayer film, a multilayer film in which a first transparent protective film such as silicon nitride and a second transparent protective film such as zirconium oxide are laminated in this order is used.

  In Patent Document 1 and Patent Document 2, a dielectric multilayer film is formed on a glass plate by sputtering.

Japanese Examined Patent Publication No. 7-64598 JP-A-5-58680

  However, as in Patent Document 1 and Patent Document 2, when a glass plate with a dielectric multilayer film obtained by sputtering is combined with other parts to produce a final product such as an electronic part, the film surface is scratched. There was a thing. That is, the glass plates with dielectric multilayer films of Patent Document 1 and Patent Document 2 were not sufficiently scratch resistant.

  The objective of this invention is providing the manufacturing method of the glass plate with a dielectric multilayer film and the glass plate with a dielectric multilayer film which are excellent in abrasion resistance.

  A manufacturing method of a glass plate with a dielectric multilayer film according to the present invention includes a glass plate and a dielectric multilayer film laminated on the glass plate, and the dielectric multilayer film is made of silicon oxide. A method for producing a glass plate with a dielectric multilayer film, comprising: a first film having a refractive index higher than that of silicon oxide; and the glass sheet is prepared. And a step of forming the dielectric multilayer film on the glass plate by sputtering, and when forming the first film by sputtering, a film forming pressure of the first film is set. It is characterized by being 0.4 Pa or less.

  In the method for manufacturing a glass plate with a dielectric multilayer film according to the present invention, preferably, in the dielectric multilayer film, the first film and the second film are alternately laminated.

  In the method for manufacturing a glass plate with a dielectric multilayer film according to the present invention, preferably, the film formation pressure of the first film is 0.12 Pa or more.

  In the method for manufacturing a glass plate with a dielectric multilayer film according to the present invention, preferably, when the second film is formed by the sputtering, the film formation pressure of the second film is set to 0.4 Pa or less. .

  In the method for manufacturing a glass plate with a dielectric multilayer film according to the present invention, preferably, the second film is made of tantalum oxide.

  In the method for producing a glass plate with a dielectric multilayer film according to the present invention, preferably, the dielectric multilayer film is an antireflection film.

  In the method for manufacturing a glass plate with a dielectric multilayer film according to the present invention, the dielectric multilayer film may be an infrared reflective film.

  A glass plate with a dielectric multilayer film according to the present invention includes a glass plate and a dielectric multilayer film laminated on the glass plate, wherein the dielectric multilayer film is made of silicon oxide. And a second film made of tantalum oxide, the outermost layer of the dielectric multilayer film is the second film, and JIS K 5600-5-4 of the dielectric multilayer film: The pencil hardness measured according to 1999 is 3H or more.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the glass plate with a dielectric multilayer film and the glass plate with a dielectric multilayer film which are excellent in abrasion resistance can be provided.

FIG. 1 is a schematic cross-sectional view showing a glass plate with a dielectric multilayer film obtained by the method for manufacturing a glass plate with a dielectric multilayer film according to an embodiment of the present invention.

  Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. Moreover, in each drawing, the member which has the substantially the same function may be referred with the same code | symbol.

  FIG. 1 is a schematic cross-sectional view showing a glass plate with a dielectric multilayer film obtained by the method for manufacturing a glass plate with a dielectric multilayer film according to an embodiment of the present invention.

  As shown in FIG. 1, a glass plate 1 with a dielectric multilayer film includes a glass plate 2 and a dielectric multilayer film 3. The glass plate 2 has a first main surface 2a and a second main surface 2b facing each other. On the first main surface 2a of the glass plate 2, a dielectric multilayer film 3 is provided. The dielectric multilayer film 3 may also be provided on the second main surface 2b. That is, the dielectric multilayer film 3 may be provided only on one main surface of the first main surface 2a and the second main surface 2b, or provided on both main surfaces. May be.

  The dielectric multilayer film 3 includes a first film 4 and a second film 5. The first film 4 is made of silicon oxide. On the other hand, the second film 5 is composed of a film having a refractive index higher than that of silicon oxide.

  In the present embodiment, the dielectric multilayer film 3 has a configuration in which the first films 4 and the second films 5 are alternately stacked one by one. More specifically, the first film 4 is laminated on the first main surface 2a of the glass plate 2, and the second film 5 and the first film 4 are alternately laminated on the first film 4 one by one. The outermost layer is the second film 5. With such a configuration, the dielectric multilayer film 3 has an antireflection function. In the present invention, the dielectric multilayer film 3 may be another functional film such as an infrared reflecting film. The dielectric multilayer film 3 may have an antireflection function and an infrared reflection function.

  In the present embodiment, the number of layers constituting the dielectric multilayer film 3 is ten. However, in the present invention, the number of layers constituting the dielectric multilayer film 3 is not particularly limited. The number of layers of the dielectric multilayer film 3 is preferably 4 or more, and preferably 50 or less. When the number of layers of the film constituting the dielectric multilayer film 3 is within the above range, it is possible to obtain higher optical characteristics while having higher scratch resistance.

  In the present embodiment, the second film 5 is disposed on the outermost surface 3 a side of the dielectric multilayer film 3. In the present invention, the first film 4 may be disposed on the outermost surface 3a side of the dielectric multilayer film 3, but the first film 4 is disposed on the outermost surface 3a side of the dielectric multilayer film 3 as in the present embodiment. 2 membranes 5 are preferably arranged. In particular, when tantalum oxide is used as the material constituting the second film 5, the chemical resistance of the glass plate 1 with the dielectric multilayer film is further increased by arranging the second film 5 on the outermost surface 3 a side. Can be increased.

  In the present embodiment, the dielectric multilayer film 3 preferably has a pencil hardness of 3H or more measured according to JIS K 5600-5-4: 1999. Thereby, it has much more sufficient abrasion resistance. The pencil hardness is more preferably 4H or more, and further preferably 6H or more.

  Hereinafter, each material which comprises the glass plate with a dielectric multilayer film of this invention is demonstrated in detail.

(Glass plate)
Examples of the glass constituting the glass plate include SiO ₂ —B ₂ O ₃ —RO (R is Mg, Ca, Sr, or Ba) glass, SiO ₂ —B ₂ O ₃ —R ′ ₂ O (R ′ is Li, Na or Ka) glass, SiO ₂ —B ₂ O ₃ —RO—R ′ ₂ O (R ′ is Li, Na or Ka) glass, SnO—P ₂ O ₅ glass, TeO ₂ glass or Bi ₂ O ₃ glass or the like can be used.

  Although it does not specifically limit as thickness of a glass plate, For example, it can be set as 40 micrometers-1200 micrometers.

(Dielectric multilayer film)
The dielectric multilayer film has the following first film and second film.

(First film)
The first film is made of silicon oxide.

  The film thickness per layer of the first film is not particularly limited, but the lower limit value of the film thickness is preferably 1.5 nm or more, more preferably 2 nm or more, and the upper limit value of the film thickness is Preferably it is 200 nm or less, More preferably, it is 150 nm or less.

  When the film thickness per layer of the first film is equal to or more than the above lower limit value, more optimal optical characteristics can be obtained. On the other hand, when the film thickness per layer of the first film is not more than the above upper limit value, it is possible to obtain more optimal optical characteristics while further shortening the film formation time.

(Second film)
The second film is made of a material having a refractive index higher than that of silicon oxide. The material having a refractive index higher than that of silicon oxide is not particularly limited. For example, tantalum oxide, niobium oxide, titanium oxide, hafnium oxide, silicon nitride, zirconium oxide, or the like can be used. These materials may be used alone or in combination. More specifically, the second film 5 of the second, fourth, and sixth layers from the glass plate 2 side in FIG. 1 is made of niobium oxide, and the eighth and tenth layers from the glass plate 2 side. The second film 5 of the eye may be made of tantalum oxide. Tantalum oxide is preferably used as a material for forming a film having a higher refractive index than silicon oxide from the viewpoint of making the film surface less susceptible to scratches and further improving the scratch resistance.

  The film thickness per layer of the second film is not particularly limited, but the lower limit value of the film thickness is preferably 1.5 nm or more, more preferably 2 nm or more, and the upper limit value of the film thickness is Preferably it is 200 nm or less, More preferably, it is 150 nm or less.

  When the film thickness per layer of the second film is equal to or more than the above lower limit value, more optimal optical characteristics can be obtained. On the other hand, when the film thickness per layer of the second film is not more than the above upper limit value, it is possible to obtain more optimal optical characteristics while having more sufficient strength.

  Hereinafter, the manufacturing method as an example of the glass plate 1 with a dielectric multilayer film will be described in detail.

(Production method)
First, the glass plate 2 is prepared. Subsequently, the prepared glass plate 2 is set in a sputtering apparatus. In addition, in the case of sputtering, it is desirable that the temperature of the glass plate 2 shall be 50 degreeC-150 degreeC, for example.

  As a target for the sputtering apparatus, a silicon target and a metal target capable of forming a film having a higher refractive index than silicon oxide are prepared. The silicon target is a target for forming the first film 4. On the other hand, a metal target capable of forming a film having a higher refractive index than silicon oxide is a target for forming the second film 5. Note that as a metal target capable of forming a film having a higher refractive index than silicon oxide, a target such as tantalum, niobium, titanium, hafnium, or zirconium can be used. Among these, it is preferable to use a tantalum target from the viewpoint of further increasing the strength of the obtained film.

  Next, a mixed gas of an inert gas and an oxygen gas is introduced into the sputtering apparatus, a silicon target is sputtered, and the first film 4 is formed on the glass plate 2. At this time, the deposition pressure of the first film 4 is 0.4 Pa or less. As the inert gas, nitrogen gas, argon gas, or a mixed gas of argon gas and nitrogen gas can be used. Preferably, it is a mixed gas of argon gas and nitrogen gas. Note that the mixed gas of the inert gas and the oxygen gas is desirably introduced after the inside of the sputtering apparatus is evacuated by a vacuum pump or the like. Moreover, the mixing ratio of the inert gas and the oxygen gas (inert gas: oxygen gas) is not particularly limited, and can be, for example, in the range of 2: 1 to 8: 1.

  Next, the second film 5 is formed on the first film 4 by sputtering a metal target capable of forming a film having a higher refractive index than silicon oxide. By repeating this operation, a glass with a dielectric multilayer film having a total of 10 layers in which the first film 4 and the second film 5 are alternately laminated on the glass plate 2 one by one. The board 1 can be obtained.

  The feature of the manufacturing method of the present embodiment is that the film forming pressure when forming the first film 4 is 0.4 Pa or less. In this case, since silicon (silicon oxide) can be deposited without lowering the energy of silicon (silicon oxide) knocked out in the state of atoms or molecules, a dense film can be obtained. Therefore, in the manufacturing method of this embodiment, the hardness of the dielectric multilayer film 3 can be increased, and the film surface of the obtained glass plate 1 with a dielectric multilayer film can be made difficult to be damaged. Therefore, the obtained glass plate 1 with a dielectric multilayer film is excellent in scratch resistance.

  From the viewpoint of further improving the scratch resistance of the glass plate 1 with a dielectric multilayer film, the film formation pressure of the first film 4 is preferably 0.3 Pa or less, and preferably 0.25 Pa or less. More preferred.

  The deposition pressure of the first film 4 is preferably 0.12 Pa or more, and more preferably 0.15 Pa or more. In this case, film peeling of the first film 4 can be made more difficult to occur, and the number of pinholes can be further reduced.

  The deposition pressure of the second film 5 is preferably 0.4 Pa or less, more preferably 0.25 Pa or less, and further preferably 0.15 Pa or less. In this case, the film surface of the obtained glass plate 1 with a dielectric multilayer film can be made more difficult to be scratched, and the scratch resistance of the glass plate 1 with a dielectric multilayer film can be further enhanced. The lower limit value of the film formation pressure of the second film 5 is not particularly limited, but is preferably 0.05 Pa or more from the viewpoint of forming the second film 5 more reliably.

  Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.

Example 1
First, a glass plate was prepared. Subsequently, the prepared glass plate was set in a sputtering apparatus. Next, a mixed gas of argon gas and oxygen gas was introduced into the sputtering apparatus, a silicon target was sputtered, and a silicon oxide (SiO ₂ ) film was formed on the glass plate. At this time, the flow rate of argon gas was 300 sccm, and the flow rate of oxygen gas was 120 sccm. The deposition pressure of the SiO ₂ film was 0.3 Pa.

Next, a tantalum oxide (Ta ₂ O ₅ ) film was formed on the SiO ₂ film by sputtering a tantalum target while maintaining a mixed gas of argon gas and oxygen gas at the same flow rate. At this time, the deposition pressure of the Ta ₂ O ₅ film was 0.3 Pa. By repeating this operation, a glass plate with a dielectric multilayer film having a total of 18 layers in which SiO ₂ films and Ta ₂ O ₅ films are alternately laminated one by one on the glass plate 2 is obtained. Obtained. The outermost layer was a Ta ₂ O ₅ film. Further, only when forming the outermost Ta ₂ O ₅ film, the flow rate of argon gas was 100 sccm, the flow rate of oxygen gas was 40 sccm, and the deposition pressure was 0.1 Pa.

(Examples 2 to 7)
Implemented except that the flow rates of argon gas and oxygen gas were changed as shown below, and the film forming pressure when forming the SiO ₂ film and Ta ₂ O ₅ film was changed as shown in Table 1 below. A glass plate with a dielectric multilayer film was obtained in the same manner as in Example 1. In Examples 5 to 7, the flow rate of argon gas (argon flow rate) and the flow rate of oxygen gas (oxygen flow rate) are as follows when forming the SiO ₂ film and when forming the Ta ₂ O ₅ film: Changed as shown.

Example 2 Argon flow rate: 100 sccm, oxygen flow rate: 40 sccm
Example 3 Argon flow rate: 150 sccm, oxygen flow rate: 60 sccm
Example 4 Argon flow rate: 200 sccm, oxygen flow rate: 80 sccm
Example ₂ SiO ₂ film: Argon flow rate: 100 sccm, oxygen flow rate: 40 sccm
Ta ₂ O ₅ film of Example 5: Argon flow rate: 300 sccm, oxygen flow rate: 120 sccm
SiO ₂ film of Example 6 Argon flow rate: 300 sccm, oxygen flow rate: 120 sccm
Ta ₂ O ₅ film of Example 6 Argon flow rate: 100 sccm, oxygen flow rate: 40 sccm
Example 7 SiO ₂ film: Argon flow rate: 200 sccm, oxygen flow rate: 80 sccm
Ta ₂ O ₅ film of Example 7: Argon flow rate: 100 sccm, oxygen flow rate: 40 sccm

(Example 8)
The number of laminated dielectric multilayer films was changed to 17 layers, the outermost layer was changed to a SiO ₂ film (the outermost layer material was SiO ₂ ), and the deposition pressure of the outermost SiO ₂ film was changed to the following Table 1. Dielectric multilayer film in the same manner as in Example 1 except that the flow rate of argon gas and oxygen gas when forming the outermost SiO ₂ film was changed as follows: An attached glass plate was obtained.

Outermost SiO ₂ film: Argon flow rate: 300 sccm, oxygen flow rate: 120 sccm

(Evaluation)
The following evaluation was implemented about the glass plate with a dielectric multilayer film obtained in Examples 1-8. The results are shown in Table 1 below.

Pencil hardness;
The pencil hardness was measured according to JIS K 5600-5-4: 1999. In addition, the presence or absence of the scar at the time of determining pencil hardness was expanded and magnified by 500 times with the optical microscope, and was observed.

Number of pinholes;
The number of pinholes having a diameter of 8 μm or more present per 0.028 m ² of the outermost surface area of the dielectric multilayer film was evaluated.

chemical resistance;
The glass plate with a dielectric multilayer film was immersed in 3% by mass of EC500 (manufactured by Henkel Japan) at 60 ° C. for 800 seconds, and then immersed in a 3% by mass of NaOH solution at 60 ° C. for 60 seconds. The transmittance of the glass plate with a dielectric multilayer film before and after immersion of EC500 and NaOH solution was measured by Hitachi High-Tech, product name “U-4000”, and chemical resistance was evaluated using the following evaluation criteria. did.

[Evaluation criteria]
○: Change in transmittance before and after immersion is 0.15% or less Δ: Change in transmittance before and after immersion is greater than 0.15%

DESCRIPTION OF SYMBOLS 1 ... Glass plate 2 with dielectric multilayer film ... Glass plate 2a, 2b ... 1st, 2nd main surface 3 ... Dielectric multilayer film 3a ... Outermost surface 4,5 ... 1st, 2nd film | membrane

Claims (8)

A glass plate and a dielectric multilayer film laminated on the glass plate, wherein the dielectric multilayer film is a first film made of silicon oxide, and a material having a higher refractive index than the silicon oxide A method for producing a glass plate with a dielectric multilayer film, comprising: a second film constituted by:
Preparing the glass plate;
Forming the dielectric multilayer film by sputtering on the glass plate;
With
A method for producing a glass plate with a dielectric multilayer film, wherein, when the first film is formed by the sputtering, a film forming pressure of the first film is set to 0.4 Pa or less.   The method for producing a glass plate with a dielectric multilayer film according to claim 1, wherein in the dielectric multilayer film, the first film and the second film are alternately laminated.   The manufacturing method of the glass plate with a dielectric multilayer film according to claim 1 or 2, wherein the film formation pressure of the first film is 0.12 Pa or more.   The dielectric multilayer film according to any one of claims 1 to 3, wherein when the second film is formed by the sputtering, a film forming pressure of the second film is set to 0.4 Pa or less. Manufacturing method of glass plate.   The manufacturing method of the glass plate with a dielectric multilayer film of any one of Claims 1-4 with which the said 2nd film | membrane is comprised with the tantalum oxide.   The method for producing a glass plate with a dielectric multilayer film according to any one of claims 1 to 5, wherein the dielectric multilayer film is an antireflection film.   The manufacturing method of the glass plate with a dielectric multilayer film of any one of Claims 1-5 whose said dielectric multilayer film is an infrared reflective film. A glass plate, and a dielectric multilayer film laminated on the glass plate,
The dielectric multilayer film has a first film made of silicon oxide and a second film made of tantalum oxide,
The outermost layer of the dielectric multilayer film is the second film;
The glass plate with a dielectric multilayer film whose pencil hardness measured based on JISK5600-5-4: 1999 of the said dielectric multilayer film is 3H or more.

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