WO2019181421A1

WO2019181421A1 - Glass substrate with layered films and window glass

Info

Publication number: WO2019181421A1
Application number: PCT/JP2019/007935
Authority: WO
Inventors: 章代松本; 一色　眞誠; 正文秋田
Original assignee: Ａｇｃ株式会社; エージーシーグラスユーロップ; エージーシーフラットグラスノースアメリカ，インコーポレイテッド; エージーシーヴィドロドブラジルリミターダ
Priority date: 2018-03-20
Filing date: 2019-02-28
Publication date: 2019-09-26
Also published as: JPWO2019181421A1

Abstract

Provided is a glass substrate with layered films that has outstanding heat shielding properties and adhesiveness. The glass substrate with layered films comprises a glass substrate, an adhesive layer disposed on at least one surface of the glass substrate, and at least two layered films; the layered films comprise, in order from the glass substrate side, a first dielectric layer, a crystallinity improvement layer, a functional layer, and a second dielectric layer; the first dielectric layer and the second dielectric layer include silicon nitride; the functional layer includes zirconium nitride with an extinction coefficient of over 6.0 at a wavelength of 1500 nm; the layered films have a stress index, defined by formula (1), of at least 70; the adhesive layer includes silicon oxide and has a thickness of 3–20 nm; and the value found by dividing the thickness of the adhesive layer by the stress index is 0.04–0.29.

Description

Glass substrate with laminated film and window glass

The present invention relates to a glass substrate with laminated film and a window glass.

High heat shielding performance is required for building glass panes in hot regions, for example, low-latitude to mid-latitude regions such as Southeast Asia. In order to have high heat shielding performance, it is necessary for the window glass to have a low thermal emissivity. As a window glass having a low thermal emissivity, a film laminate having a glass substrate and a laminated film including a first dielectric layer, a crystallinity improving region, a zirconium nitride layer, and a second dielectric layer is proposed. (Patent Document 1).

International Publication No. 2016/199676

In order to further improve the heat-shielding performance of the glass substrate with a laminated film in Patent Document 1, if the total thickness of the zirconium nitride layer is increased, the glass substrate and the laminated film are easily peeled off, and the adhesion between the two is improved. The present inventors have found that there is a problem.
Then, this invention makes it a subject to provide the glass substrate with a laminated film which is excellent in heat-shielding property and adhesiveness.

The inventors of the present invention have described that the cause of the peeling of the laminated film at the interface between the glass substrate and the laminated film in the glass substrate with the laminated film is that the compressive stress of the zirconium nitride layer in the laminated film is high and the adhesion of the first dielectric layer The present invention was completed by finding out that it is based on low nature.
That is, it discovered that the said subject could be solved by the glass substrate with a laminated film which has the following aspects.

A glass substrate, a glass substrate with a laminated film having an adhesion layer and two or more laminated films provided on at least one surface of the glass substrate;
The laminated film has a configuration including a first dielectric layer, a crystallinity improving layer, a functional layer, and a second dielectric layer in this order from the glass substrate side,
The first dielectric layer and the second dielectric layer comprise silicon nitride;
The functional layer includes zirconium nitride having an extinction coefficient of greater than 6.0 at a wavelength of 1500 nm,
The crystallinity improving layer includes zirconium nitride having an extinction coefficient of less than 2.0 at a wavelength of 1500 nm,
The laminated film has a stress index defined by the following formula (1) of 70 or more,
The adhesion layer includes silicon oxide and has a thickness of 3 to 20 nm;
A glass substrate with a laminated film is provided in which a value obtained by dividing the thickness of the adhesion layer by the stress index is in the range of 0.04 to 0.29.
Stress index = total thickness of functional layer (nm) + 0.2 × total thickness of dielectric layer (nm) + 0.4 × total thickness of crystallinity improving layer (nm) (1)

ADVANTAGE OF THE INVENTION According to this invention, the glass substrate with a laminated film which is excellent in heat-shielding property and adhesiveness can be provided.

It is typical sectional drawing which shows an example of the glass substrate with a laminated film of this invention. It is typical sectional drawing which shows the other example of the glass substrate with a laminated film of this invention.

The following definitions of terms apply throughout this specification and the claims.
The “boundary between the crystallinity improving layer and the functional layer” is defined as follows. When a functional layer is formed on the surface of the crystallinity-improving layer, the atoms constituting the crystallinity-improving layer and the atoms constituting the functional layer are mixed, so the boundary between the crystallinity-improving layer and the functional layer is in the thickness direction. It exists with a certain width. Therefore, by alternately repeating etching by ion sputtering and X-ray photoelectron spectroscopy (XPS) measurement, the atomic concentration is analyzed in the thickness direction from the surface of the laminated film to the interface between the laminated film and the glass substrate. Sputter time range in which the metal atoms contained in the crystallinity-improving layer and the metal atoms contained in the functional layer are detected in the graph of sputtering time and atomic concentration (however, one or both metal atoms were detected as noise) Is the boundary between the crystallinity improving layer and the functional layer.

“Oxygen atom concentration at the boundary between the crystallinity-enhancing layer and the functional layer” refers to sputtering in which atoms contained in the crystallinity-improving layer and atoms contained in the functional layer are detected in the above-described graph of sputtering time and atomic concentration. It is the maximum value of oxygen atom concentration in the time range.
The “thickness of each layer constituting the laminated film” is calculated from “the boundary between the target layer and the upper layer” to “the boundary between the target layer and the lower layer” in the above-described graph of the sputtering time and the atomic concentration. The sputtering time was a value converted from the sputtering rate of the standard sample to the thickness. “Boundary between the target layer and the layer immediately above” and “Boundary between the target layer and the layer immediately below” are respectively “the median values of the sputtering times during which atoms included in the target layer and atoms included in the layer directly above are detected. And “the median value of the sputtering time during which atoms contained in the target layer and atoms contained in the immediate lower layer are detected”.

“Thickness of adhesion layer” is calculated by converting the sputtering time from “boundary between glass substrate and adhesion layer” to “boundary between adhesion layer and first dielectric layer” from the sputtering rate of the standard sample. Value. The “boundary between the glass substrate and the adhesion layer” is the median value of the sputtering time during which atoms contained in the glass substrate and atoms contained in the adhesion layer are detected in the above-described graph of sputtering time and atomic concentration. Similarly, the “boundary between the adhesion layer and the first dielectric layer” is the median value of the sputtering time during which both atoms contained in the adhesion layer and atoms contained in the first dielectric layer are detected.
The value of “pressure” indicates “absolute pressure” unless otherwise specified. The thickness of the glass substrate is a geometric thickness.
“˜” indicating a numerical range means that numerical values described before and after that are included as a lower limit value and an upper limit value.
1 and 2 are both schematic drawings, and the dimensional ratios thereof are different from actual ones for convenience of explanation.
Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

(Glass substrate with laminated film)
FIG. 1 is a cross-sectional view showing an example of a glass substrate with a laminated film of the present invention. The glass substrate with a laminated film 10 includes a glass substrate 21, an adhesion layer 61 provided on one surface of the glass substrate 21, a first laminated film 22, and a second laminated film 23. The 1st laminated film 22 has the structure which has the 1st dielectric material layer 31, the 1st crystallinity improvement layer 41, the 1st functional layer 51, and the 2nd dielectric material layer 32 in order from the glass substrate 21 side. Consists of. The second laminated film 23 includes, from the glass substrate 21 side, a third dielectric layer 33 that also serves as the second dielectric layer 32 of the first laminated film 22, a second crystallinity improving layer 42, 2 functional layers 52 and a fourth dielectric layer 34 in this order.

FIG. 2 is a cross-sectional view showing another example of the glass substrate with a laminated film of the present invention. The glass substrate 11 with a laminated film includes a glass substrate 21, an adhesion layer 61 provided on one surface of the glass substrate 21, a first laminated film 22, a second laminated film 23, and a third laminated film 24. The third laminated film 24 includes a fifth dielectric layer 35 that also serves as the fourth dielectric layer 34 of the second laminated film 23, a third crystallinity improving layer 43, a third functional layer 53, and a third functional layer 53. 6 dielectric layers 36 in order.

The laminated film 22 may have a sacrificial layer between the first dielectric layer 31 and the first crystallinity improving layer 41, and the first functional layer 51, the second dielectric layer 32, and the like. A sacrificial layer may be provided between them. Similarly, the laminated

films

23 and 24 may have a sacrificial layer.
The sacrificial layer is for suppressing diffusion of nitrogen from the first dielectric layer to the crystallinity improving layer and diffusion of nitrogen from the second dielectric layer to the functional layer during the heat treatment. It is preferably a metal layer made of any one of aluminum, titanium, chromium, niobium, molybdenum, hafnium, zirconium, or a combination thereof.
The laminated film 23 may have a top layer on the surface of the fourth dielectric layer 34 farthest from the glass substrate 21. Similarly, the laminated film 24 may have a top layer on the surface of the sixth dielectric layer 36.
The laminated films 22 to 24 are provided on at least one surface of the glass substrate 21. The laminated films 22 to 24 may be provided on both surfaces of the glass substrate 21.

Examples of the glass substrate 21 include soda lime glass, aluminosilicate glass, non-alkali glass, and borosilicate glass, and soda lime glass is preferable.
The thickness of the glass substrate 21 is appropriately set according to the use of the laminated film-attached glass substrate. When a glass substrate with a laminated film is used as a window glass, the thickness of the glass substrate 21 is preferably 0.5 to 12 mm.

The adhesion layer 61 contains silicon oxide and has a thickness of 3 to 20 nm. The silicon oxide is preferably doped with boron, aluminum, titanium, nickel, zinc, molybdenum, tin, tungsten, zirconium or niobium, and more preferably with aluminum or zirconium. When silicon oxide is doped with aluminum or zirconium, the sputtering stability can be improved in the sputtering method. The silicon oxide doped with aluminum is expressed as Si _1-α O _z · Al _α , where α is 0.03 to 0.50 and z is 1.0 to 2.0. Zirconium-doped silicon oxide is expressed as Si _1-α O _z · Zr _α , where α is 0.03 to 0.50 and z is 1.0 to 2.0.
When the thickness of the adhesion layer 61 is 3 nm or more, the glass substrate with a laminated film 10 has excellent adhesion. When the thickness is 20 nm or less, the laminated film-attached glass substrate 10 can realize an appearance with few defects. The thickness of the adhesion layer 61 is preferably 5 to 15 nm, and more preferably 7 to 15 nm.

The first dielectric layer 31 and the second dielectric layer 32 include silicon nitride. The silicon nitride is preferably doped with boron, aluminum, titanium, nickel, zinc, molybdenum, tin, tungsten, zirconium or niobium, and more preferably with aluminum or zirconium. Silicon nitride doped with aluminum is expressed as Si _1-α N _y · Al _α , where α is 0.03 to 0.50 and y is 1.0 to 2.0. Zirconium-doped silicon nitride is expressed as Si _1-α N _y · Zr _α , where α is 0.03 to 0.50 and y is 1.0 to 2.0.
The first dielectric layer 31 and the second dielectric layer 32 may contain impurities (carbon atoms, oxygen atoms, etc.) that are inevitably introduced during film formation. The first dielectric layer 31 and the second dielectric layer 32 may be a single layer or a combination of two or more different types of layers.

The thickness of the first dielectric layer 31 and the second dielectric layer 32 is preferably 1.5 to 200 nm. If this thickness is 1.5 nm or more, the first functional layer 51 is protected from deterioration due to oxygen and moisture, and thus the laminated film-attached glass substrate 10 has excellent durability. If this thickness is 200 nm or less, the glass substrate 10 with a laminated film can obtain good productivity.

The first crystallinity improving layer 41 improves the crystallinity of zirconium nitride contained in the first functional layer 51 formed immediately above.
The first crystallinity improving layer 41 includes zirconium nitride having an extinction coefficient of less than 2.0 at a wavelength of 1500 nm. Zirconium nitride is preferably present in the first crystallinity-improving layer 41 at a portion in contact with the first functional layer 51.
The thickness of the first crystallinity improving layer 41 is preferably 3 to 30 nm, more preferably 4.5 to 20 nm. If this thickness is in the range of 3 to 30 nm, the surface roughness of the first crystallinity-improving layer 41 becomes small, and the crystallinity of zirconium nitride contained in the first functional layer 51 becomes sufficiently high. The glass substrate with film 10 has excellent heat shielding properties.

The first functional layer 51 includes zirconium nitride having an extinction coefficient of more than 6.0 at a wavelength of 1500 nm. The first functional layer 51 may contain impurities (carbon atoms, oxygen atoms, other metal atoms, etc.) that are inevitably introduced during film formation. The first functional layer 51 is formed in contact with the first crystallinity improving layer 41 and immediately above it.
The thickness of the first functional layer 51 is preferably 3 to 60 nm, and more preferably 10 to 40 nm. If this thickness is 3 nm or more, the heat-shielding property of the glass substrate 10 with a laminated film is further increased. If this thickness is 60 nm or less, the glass substrate 10 with a laminated film can have moderately visible light transmittance.

The materials and thicknesses of the third to sixth dielectric layers 33 to 36 are the same as those of the first dielectric layer 31 and the second dielectric layer 32, and the preferred embodiments are also the same. The third to sixth dielectric layers 33 to 36 may contain impurities (carbon atoms, oxygen atoms, etc.) inevitably introduced at the time of film formation.

The materials and thicknesses of the second crystallinity enhancement layer 42 and the third crystallinity enhancement layer 43 are the same as those of the first crystallinity enhancement layer 41, and the preferred forms are also the same. The second and third

crystallinity improving layers

42 and 43 may contain impurities (carbon atoms, oxygen atoms, etc.) inevitably introduced during film formation.

The materials and thicknesses of the second functional layer 52 and the third functional layer 53 are the same as those of the first functional layer 51, and the preferred forms are also the same. The second and third functional layers 52 and 53 may contain impurities (carbon atoms, oxygen atoms, etc.) that are inevitably introduced during film formation.

The glass substrate with a laminated film of the present invention is preferably such that the laminated film does not peel after 4 cycles of the salt spray test specified in JIS C60068-2-52. More preferably, the laminated film does not peel off after 5 cycles of the salt spray test. In the glass substrate with a laminated film of the present invention, when the total thickness of all functional layers is 30 nm or more, the adhesion in the salt spray test is greatly improved.
The glass substrate with a laminated film of the present invention preferably has a solar heat acquisition rate specified in ISO 9050: 2003 of 0.36 or less, more preferably 0.30 or less.

(Adhesion layer thickness / stress index ratio)
The laminated film of the present invention has a stress index defined by the following formula (1) of 70 or more.
Stress index = total thickness of functional layer (nm) + 0.2 × total thickness of dielectric layer (nm) + 0.4 × total thickness of crystallinity improving layer (nm) (1)
The present inventors have found that when a laminated film is provided directly on a glass substrate, if the laminated film has a stress index of 70 or more, it is easy to peel in a salt spray test. When the laminated film has a configuration in which a first dielectric layer containing silicon nitride, a crystallinity improving layer containing zirconium nitride, a functional layer containing zirconium nitride, and a second dielectric layer containing silicon nitride are sequentially formed, each layer Therefore, the stress of the laminated film tends to be as high as 5000 to 30000 MPa. Furthermore, a laminated film having a stress index of 70 or more calculated in consideration of the thickness of each layer has a stress of 8000 to 35000 MPa, and thus easily peels off in a salt spray test.

The stress index of the laminated film is preferably 70 to 230, more preferably 70 to 150, and particularly preferably 70 to 100. When the stress index of the laminated film is 70 or more, the glass substrate with the laminated film has excellent heat shielding properties. When the stress index of the laminated film is 230 or less, the glass substrate with the laminated film becomes difficult to peel off in the salt spray test when an adhesion layer is provided. Furthermore, since the visible light absorptance of the functional layer can be reduced to a certain value or less, the glass substrate with a laminated film can have a visible light transmittance of 3% or more measured in accordance with ISO 9050: 2003.

As a result of intensive studies, the present inventors have introduced an adhesion layer 61 containing silicon oxide and having a thickness of 3 to 20 nm between the glass substrate and the laminated film, and the thickness of the adhesion layer 61 is set to the laminated film. It was found that when the value divided by the stress index of 0.04 to 0.29 is within the range, the glass substrate with a laminated film has excellent heat shielding properties and adhesion. The reason is not necessarily clear, but by selecting the thickness of the adhesion layer 61 and the laminated films 22 to 24 in which this value is in the range of 0.04 to 0.29, the laminated films 22 to 24 including the zirconium nitride layer are selected. We believe that we were able to achieve adhesion that can withstand the stress of. This value is preferably in the range of 0.09 to 0.25, and more preferably in the range of 0.09 to 0.20.

(Ratio of adhesion layer thickness / total thickness of laminated film)
The ratio of the thickness of the adhesion layer 61 to the total thickness of the laminated film is preferably in the range of 0.009 to 0.102. When this ratio is 0.009 or more, the glass substrate with a laminated film can have excellent adhesion in a salt spray test. When this ratio is 0.102 or less, the laminated film-attached glass substrate can realize an appearance with few defects.

(Ratio of thickness of second functional layer / thickness of first functional layer)
The ratio of the thickness of the second functional layer 52 to the thickness of the first functional layer 51 is preferably in the range of 1.05 to 2.60. When this ratio is 1.05 or more, stress is prevented from concentrating on the interface between the glass and the laminated film, and the glass substrate with the laminated film has excellent adhesion. On the other hand, when this ratio is 2.60 or less, the balance of film formation speed can be maintained, and the glass substrate with a laminated film can maintain good productivity. This ratio is more preferably in the range of 1.10 to 2.50, and still more preferably in the range of 1.20 to 2.40.

(Value of oxygen atom concentration at the boundary between the crystallinity improving layer and the functional layer)
The oxygen atom concentration at the boundary between the first crystallinity improving layer 41 and the first functional layer 51 is preferably 20 atomic% or less, more preferably 15 atomic% or less, and 10 atomic% or less. More preferably it is. When the oxygen atom concentration is 20 atomic% or less, the crystallinity of zirconium nitride contained in the first functional layer 51 is improved, and the glass substrate with a laminated film can have excellent heat shielding properties. The lower the oxygen atom concentration, the better. The lower limit is 0 atomic%.
The oxygen atom concentration at the boundary between the second and third crystallinity enhancement layers 42 and 43 and the second and third functional layers 52 and 53 is the same as the first crystallinity enhancement layer 41 and the first functional layer 51. It is preferable to be in the same numerical range as the oxygen atom concentration at the boundary.

(Manufacturing method of glass substrate with laminated film)
The glass substrate 10 with a laminated film of the present invention has an adhesion layer 61, a first dielectric layer 31, a first crystallinity improving layer 41, a first functional layer 51, a second dielectric on the surface of the glass substrate 21. The body layer 32, the second crystallinity improving layer 42, the second functional layer 52, and the fourth dielectric layer 34 can be manufactured in sequence.
In the glass substrate 11 with a laminated film of the present invention, the third crystallinity improving layer 43, the third functional layer, and the sixth dielectric layer 36 are sequentially formed on the surface of the fourth dielectric layer 34. Can be manufactured.
Examples of the film forming method include a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, and the like, and the sputtering method is preferable from the viewpoint of excellent thickness uniformity and productivity.
(Window glass)
The glass substrate 11 with a laminated film of the present invention can be used as a window glass having a single glass substrate. A window glass having a single glass substrate is lightweight and has excellent productivity. Moreover, it is preferable that the laminated glass is provided in the indoor side in the window glass which has one glass substrate. By providing the laminated film on the indoor side, the heat insulating property of the window glass is improved.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Examples 1 to 7 are examples, examples 11, 13, 14, and 15 are comparative examples, and example 12 is a reference example.

(Thickness of each layer)
The thickness of each layer in the laminated film is measured with a spectroscopic ellipsometer (measured at 50 °, 60 °, and 70 ° incident angles using M-2000 manufactured by JA Woollam), and transmission spectrum (manufactured by Hitachi, Ltd.). U-4100, measured in the wavelength range of 250 to 2500 nm), film surface reflection spectrum (measured in the wavelength range of 250 to 2500 nm at an incident angle of 5 ° using U-4100 manufactured by Hitachi, Ltd.), It was determined from the solution of the complex refractive index and film thickness obtained to satisfy all of the glass surface reflection spectrum (measured in the wavelength range of 250 to 2500 nm at an incident angle of 5 ° using U-4100 manufactured by Hitachi, Ltd.). .
The thickness of the adhesion layer was measured by a method of alternately repeating etching by ion sputtering and X-ray photoelectron spectroscopy (XPS) measurement.

(Extinction coefficient)
The extinction coefficient at a wavelength of 1500 nm of the crystallinity improving layer and the functional layer was determined as follows.
With respect to the glass substrate with the laminated film, a spectral spectrum was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). In addition, polarization information was measured using a spectroscopic ellipsometer (manufactured by JA Woollam Co., Ltd., M-2000). Using the obtained spectral transmission spectrum, spectral reflection spectrum (film surface and glass surface) and polarization information, the optical model was fitted to determine the extinction coefficient.

(Oxygen atom concentration at the boundary between the crystallinity enhancement layer and the functional layer)
Using a scanning X-ray photoelectron spectrometer (PHI 5000 VersaProbe manufactured by ULVAC-PHI), the beam diameter is 100 μm, and the atomic concentration is analyzed in the thickness direction from the surface of the laminated film to the interface between the laminated film and the glass substrate. It was. At this time, argon gas was used as an etching gas, the gas pressure was 1.5 × 10 ⁻² Pa, the acceleration voltage was 1 kV, and the ion beam diameter was 1 × 1 mm. The oxygen atom concentration at the boundary between the crystallinity enhancement layer and the functional layer was determined from the measurement results.
When there were two or more laminated films, the oxygen atom concentration at the boundary between the crystallinity improving layer and the functional layer was determined, and the smallest value was adopted.

(Example 1)
As the glass substrate 21, a soda-lime glass plate having a size of 100 mm in length, 100 mm in width, and 3 mm in thickness was prepared.
As shown in Table 1 and Table 2, the adhesion layer 61 and the

laminated films

22 and 23 were formed on one surface of the glass substrate 21 to obtain the laminated film-attached glass substrate 10. The adhesion layer 61 and the

laminated films

22 and 23 were formed by a sputtering method.
The adhesion layer 61 (Si _1-α O _z · Al _α ) is formed using a Si—Al (10 mass%) target and a mixed gas of argon gas and oxygen gas (argon gas: oxygen gas) as a discharge gas. = 7: 5 (sccm)). The pressure during film formation was 0.5 Pa.
The first dielectric layer 31 and the second dielectric layer 32 (Si _1-α N _y · Al _α ) were formed by using a Si (90 mass%)-Al (10 mass%) target and discharging. A mixed gas of argon gas and nitrogen gas (argon gas: nitrogen gas = 3: 2 (sccm)) was used as the gas. The pressure during film formation was 0.4 Pa.

In forming the first crystallinity improving layer 41 (ZrN _x ), a Zr target was used and nitrogen gas was used as a discharge gas. The pressure during film formation was 0.4 Pa.
For forming the first functional layer 51 (ZrN), a Zr target is used, and a mixed gas of argon gas and nitrogen gas (argon gas: nitrogen gas = 4.9: 1 (sccm)) is used as a discharge gas. It was. The pressure during film formation was 0.3 Pa.
The thicknesses of the second crystallinity improving layer 42, the second functional layer 52, and the fourth dielectric layer 34 were adjusted to the thicknesses shown in Tables 1 and 2 by changing the substrate transport speed.

(Examples 2-7, Examples 11-15)
By carrying out in the same manner as in Example 1 except that each element of the glass substrate, the adhesion layer, and the laminated film in the glass substrate with the laminated film is configured as shown in Table 1 and Table 2, the glass substrate with

laminated film

10 or 11 was obtained.

(Heat insulation)
Spectral spectrum measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) and a total hemispherical emissivity measuring apparatus (manufactured by Koei Co., Ltd., PM-E2) Using the measured emissivity value, the solar heat acquisition rate (g value) and the visible light transmittance were calculated based on ISO 9050: 2003. A g value of 0.36 or less is considered to have practically sufficient heat shielding properties. A visible light transmittance of 3 to 45% is considered to have sufficient transparency for practical use. The results are shown in Table 3.

(Adhesion)
The glass substrates 10 and 11 with laminated films were evaluated according to the severity (6) described in JIS C60068-2-52 salt spray test method. Evaluation was performed by visual observation and observation with an optical microscope. A tolerance of 0 or 1 is considered to have practically sufficient adhesion. The results are shown in Table 3.
Resistance 0: No peeling occurred until 5 cycles.
Resistance 1: Peeling did not occur until 4 cycles, but peeling occurred after 5 cycles.
Resistance 2: No peeling occurred until 3 cycles, but peeling occurred after 4 cycles.
Resistance 3: Peeling did not occur until 2 cycles, but peeling occurred after 3 cycles.
Resistance: No peeling occurred after 4: 1 cycle, but peeling occurred after 2 cycles.
Resistance: Delamination occurred after 5: 1 cycle.

(appearance)
The glass substrates 10 and 11 with laminated films were evaluated visually. The presence or absence of peeling was confirmed using a laser microscope. The results are shown in Table 3.
A: Discoloration such as white spots and peeling were not confirmed.
X: Discoloration or peeling such as white spots was confirmed.

In Table 3, “-” indicates that there is no corresponding layer or data.
The glass substrates with laminated films of Examples 1 to 7 were excellent in heat shielding properties and adhesion. The glass substrates with laminated films of Examples 11 and 13 to 15 had low adhesion, and the glass substrates with laminated films of Example 14 had problems in appearance.

The glass substrate with a laminated film of the present invention is useful for architectural window glass, vehicle window glass, and the like as heat shielding glass.
It should be noted that the entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-053485 filed on March 20, 2018 is cited here as disclosure of the specification of the present invention. Incorporate.

10, 11: Glass substrate with laminated film, 21: Glass substrate, 22: First laminated film, 23: Second laminated film, 31: First dielectric layer, 41: First crystallinity improving layer, 51: first functional layer, 32: second dielectric layer, 42: second crystallinity improving layer, 52: second functional layer, 34: fourth dielectric layer, 43: third crystal Improvement layer, 53: third functional layer, 36: sixth dielectric layer

Claims

A glass substrate, a glass substrate with a laminated film having an adhesion layer and two or more laminated films provided on at least one surface of the glass substrate;
The laminated film has a configuration including a first dielectric layer, a crystallinity improving layer, a functional layer, and a second dielectric layer in this order from the glass substrate side,
The first dielectric layer and the second dielectric layer comprise silicon nitride;
The functional layer includes zirconium nitride having an extinction coefficient of greater than 6.0 at a wavelength of 1500 nm,
The crystallinity improving layer includes zirconium nitride having an extinction coefficient of less than 2.0 at a wavelength of 1500 nm,
The laminated film has a stress index defined by the following formula (1) of 70 or more,
The adhesion layer includes silicon oxide and has a thickness of 3 to 20 nm;
A glass substrate with a laminated film, wherein a value obtained by dividing the thickness of the adhesion layer by the stress index is in the range of 0.04 to 0.29.
Stress index = total thickness of functional layer (nm) + 0.2 × total thickness of dielectric layer (nm) + 0.4 × total thickness of crystallinity improving layer (nm) (1)
The total thickness of the functional layers is the total thickness of all the functional layers, and the total thickness of the dielectric layers is the total thickness of all the dielectric layers. The thickness is a total value of the thicknesses of all the crystallinity improving layers.
The functional layer has, in order, a first functional layer closest to the glass substrate and a second functional layer closest to the glass substrate;
The laminated film according to claim 1, wherein the ratio of the thickness (nm) of the second functional layer to the thickness (nm) of the first functional layer is in the range of 1.05 to 2.60. With glass substrate.
The glass substrate with a laminated film according to claim 1 or 2, wherein an oxygen atom concentration at a boundary between the crystallinity improving layer and the functional layer is 20 atomic% or less.
The glass substrate with a laminated film according to any one of claims 1 to 3, wherein the adhesion layer contains aluminum or zirconium.
The adhesion layer is made of Si 1-α O z · Al α (where α is 0.03 to 0.50 and z is 1.0 to 2.0), or Si 1-α O z. 5. With a laminated film according to any one of claims 1 to 4, comprising Zr α (where α is 0.03 to 0.50 and z is 1.0 to 2.0). Glass substrate.
6. The glass substrate with a laminated film according to claim 1, wherein the first dielectric layer and the second dielectric layer contain silicon nitride doped with aluminum or zirconium.
The first dielectric layer and the second dielectric layer are Si 1−α N y · Al α (where α is 0.03 to 0.50 and y is 1.0 to 2.0). Or Si 1-α N y · Zr α (where α is 0.03 to 0.50 and y is 1.0 to 2.0). Glass substrate with laminated film.
The ratio of the thickness (nm) of the adhesion layer to the total thickness (nm) of the stacked film is in the range of 0.009 to 0.102. Glass substrate with laminated film.
The glass substrate with a laminated film according to any one of claims 1 to 8, wherein the total thickness of the functional layers is 30 nm or more.
The thickness of each functional layer is in the range of 3 to 60 nm, the thickness of each dielectric layer is in the range of 1.5 to 200 nm, and the thickness of each crystallinity improving layer is 3 to The glass substrate with a laminated film according to any one of claims 1 to 9, which is in a range of 30 nm.
The glass substrate with a laminated film according to any one of claims 1 to 10, wherein the solar heat gain (g value) obtained based on ISO 9050 (2003) is 0.36 or less.
The glass substrate with a laminated film according to any one of Claims 1 to 11, wherein the visible light transmittance determined based on ISO 9050 (2003) is 3% to 45%.
The glass substrate with a laminated film according to any one of claims 1 to 12, wherein the laminated film does not peel after 4 cycles of the salt spray test specified in JIS C60068-2-52.
A window glass having the glass substrate with a laminated film according to any one of claims 1 to 13, wherein the glass substrate is a single sheet.
The window glass according to claim 14, wherein the laminated film is provided on the indoor side.