WO2015060222A1

WO2015060222A1 - Glass plate with thin film, and manufacturing method thereof

Info

Publication number: WO2015060222A1
Application number: PCT/JP2014/077740
Authority: WO
Inventors: 啓明岩岡; 晃一中川; 淳志関; 宏佑長南; 玲大臼井
Original assignee: 旭硝子株式会社
Priority date: 2013-10-24
Filing date: 2014-10-17
Publication date: 2015-04-30
Also published as: JP2016216266A

Abstract

This glass plate with a thin film comprises, in order, a glass substrate, a functional thin film, and a barrier layer. The barrier layer consists essentially of mixed oxides of silicon (Si) and titanium (Ti), the barrier layer comprises a titanium (Ti) rich layer in which the atom content (Atom%) of titanium in the mixed oxides, measured by X-ray photoelectron analysis (ESCA), is higher than the atom content (Atom%) of silicon (Si), and the maximum value of the ratio (Ti/(Si+Ti)(%)) of the atom content of titanium (Ti) to the total atom content of silicon (Si) and titanium (Ti) in the titanium (Ti) rich layer is 80% or greater.

Description

Glass plate with thin film and manufacturing method thereof

The present invention relates to a glass plate with a thin film having functionality used for applications such as architecture and a method for producing the same.

In architectural glass plates such as multi-layer glass and show window glass, an antireflection film is formed on a glass substrate to improve visibility, or a low radiation film (so-called Low-E film) that suppresses heat radiation. ), Or a thin film having various functions such as IR cut and UV cut may be formed.
For example, as an antireflection film, an antireflection film formed by alternately laminating a film made of a low refractive index material (low refractive index film) and a film made of a high refractive index material (high refractive index film), Conventionally known. In particular, an antireflection film formed by alternately laminating a silicon oxide (SiO ₂ ) film as a low refractive index film and a titanium oxide (TiO ₂ ) film as a high refractive index film has a large refractive index difference and is optical. It is widely used because of its superiority in design and low material cost.

Moreover, in the glass plate for construction mentioned above, the weather resistance which can endure long-term use may be calculated | required. For example, Patent Document 1 discloses that a glass-like protective coating is applied to the surface of an antireflection glass on the surface of a transparent glass body for the purpose of improving the weather resistance of the antireflection glass.
Moreover, in order to provide higher weather resistance, it may be required to impart acid resistance and alkali resistance to a thin film having functionality formed on a glass substrate. For example, since the liquid eluted from concrete for construction is mainly alkaline, resistance to this may be required. In addition, since an acidic or alkaline cleaner may be used in cleaning the glass substrate surface, resistance to this may be required.

Japanese Special Table 2012-517396

For these reasons, a functional thin film having both acid resistance and alkali resistance is desired. However, conventional functional thin films of architectural glass have a problem that it is difficult to achieve both acid resistance and alkali resistance.
An object of the present invention is to provide a glass plate with a thin film, which is excellent in acid resistance and alkali resistance and has functionality, in order to solve the above-described problems in the prior art.

In order to achieve the above-described object, the inventors of the present application have earnestly studied to obtain the following knowledge.
(1) Of the antireflection films formed by alternately laminating SiO ₂ films and TiO ₂ films, those having the outermost layer as an SiO ₂ film have good acid resistance but low alkali resistance.
(2) Among the antireflection films formed by alternately laminating SiO ₂ films and TiO ₂ films, those having the outermost layer as a TiO ₂ film have good alkali resistance but low acid resistance.
(3) For this reason, in the case where one of the SiO ₂ film and the TiO ₂ film is the outermost layer, the acid resistance and alkali resistance cannot be achieved at the same time, and a barrier layer imparting acid resistance and alkali resistance is provided. Must be formed on the antireflection film. However, when a barrier layer is formed for this purpose, the barrier layer must be one that does not impair the function of the antireflection film. For example, when the refractive index of the barrier layer is higher than the refractive index of the TiO ₂ film as the high refractive index film, the function of the antireflection film is impaired. For this reason, the refractive index of the barrier layer is required to be not more than the refractive index of the TiO ₂ film as the high refractive index film.
In the antireflection film, the lower the refractive index of the outermost layer, the more dominant. Therefore, the refractive index of the barrier layer may be lower than that of the SiO ₂ film. However, in practice, it is difficult to form a film having a refractive index lower than that of the SiO ₂ film and capable of exhibiting a function as a barrier layer.

The present invention has been made based on the above-described findings, and is a glass plate with a thin film having a glass substrate, a functional thin film, and a barrier layer in this order,
The barrier layer is substantially composed of a mixed oxide of silicon (Si) and titanium (Ti);
The barrier layer is titanium (Atom%) of titanium (Ti) in the mixed oxide measured by X-ray photoelectron analysis (ESCA) higher than the atomic content (Atom%) of silicon (Si) ( Ti) with a rich layer,
The maximum value of the atomic content ratio of titanium (Ti) to the total atomic content ratio of silicon (Si) and titanium (Ti) in the titanium (Ti) rich layer (Ti / (Si + Ti) (%)) is 80%. The glass plate with a thin film which is the above is provided.

In the glass plate with a thin film of the present invention, the ratio of silicon (Si) atomic content (Si / (Ti + Si) (%)) measured by X-ray photoelectron analysis (ESCA) of the surface of the barrier layer is 35% or more. Preferably there is.

Moreover, in the glass plate with a thin film of the present invention, the proportion of silicon (Si) atomic content (Si / (Ti + Si) (%)) measured by X-ray photoelectron analysis (ESCA) of the surface of the barrier layer is 60%. The above is preferable.

In the glass plate with a thin film of the present invention, when the thickness of the barrier layer is L (nm), titanium (Ti) relative to the total atomic content of silicon (Si) and titanium (Ti) in the mixed oxide It is preferable that the portion where the atomic content ratio (Ti / (Si + Ti) (%)) of () has the maximum value is in a position satisfying 0.05 L to 0.95 L in the thickness direction of the barrier layer.

In the glass plate with a thin film of the present invention, when the layer thickness of the barrier layer is L (nm), titanium (Ti) with respect to the total atomic content of silicon (Si) and titanium (Ti) in the mixed oxide The portion where the atomic content ratio (Ti / (Si + Ti) (%)) takes the maximum value is at a position satisfying 0.25 L to 0.75 L in the thickness direction of the barrier layer, and silicon (Si) and The portion where the ratio of the atomic content of titanium (Ti) to the total of the atomic content of titanium (Ti) (Ti / (Si + Ti) (%)) takes the minimum value is at both ends in the layer thickness direction of the barrier layer. It is preferable that it exists in at least one site | part.

In the glass plate with a thin film of the present invention, the layer thickness of the barrier layer is preferably 25 nm or less.

In the glass plate with a thin film of the present invention, it is preferable that the barrier layer is formed using a transfer type atmospheric pressure CVD apparatus.

Further, in the glass plate with a thin film of the present invention, the functional thin film alternately comprises a silicon oxide (SiO ₂ ) film as a low refractive index film and a titanium oxide (TiO ₂ ) film as a high refractive index film. The antireflection film is formed by laminating a total of 2 to 16 layers of an SiO ₂ film having a thickness of 15 nm to 100 nm and a TiO ₂ film having a thickness of 5 nm to 120 nm alternately. It is preferable that

In the glass plate with a thin film of the present invention, the antireflection film may be alternately laminated in the order of the SiO ₂ film and the TiO ₂ film from the glass substrate side.

In the glass plate with a thin film of the present invention, the antireflection film may be alternately laminated in the order of the TiO ₂ film and the SiO ₂ film from the glass substrate side.

In the glass plate with a thin film of the present invention, the functional thin film is preferably a low emission (Low-E) film.

In the glass plate with a thin film of the present invention, the functional thin film is preferably a multilayer film having an IR cut function.

In the glass plate with a thin film of the present invention, the functional thin film is preferably a multilayer film having a UV cut function.

Further, the present invention is a method for producing a glass plate with a thin film having a glass substrate, a functional thin film, and a barrier layer in this order, wherein the barrier layer is formed using a transfer type atmospheric pressure CVD apparatus,
Monosilane (SiH ₄ ) and tetraisopropoxy titanium (TTIP) as main raw materials, oxygen (O ₂ ) as a secondary raw material, a main raw material supply nozzle, an upstream side in the conveyance direction of the glass substrate with respect to the main raw material supply nozzle, and From the auxiliary material supply nozzle provided on the downstream side, comprising a step of supplying onto the glass substrate conveyed in the conveyance type atmospheric pressure CVD apparatus,
The barrier layer is substantially composed of a mixed oxide of silicon (Si) and titanium (Ti);
Titanium in which the barrier layer has an atomic content (Atom%) of titanium (Ti) in the mixed oxide measured by X-ray photoelectron analysis (ESCA) higher than an atomic content (Atom%) of silicon (Si) ( Ti) with a rich layer,
The maximum ratio of the atomic content of titanium (Ti) to the total atomic content of silicon (Si) and titanium (Ti) in the titanium (Ti) rich layer (Ti / (Ti + Si) (%)) is 80% The manufacturing method of the glass plate with a thin film which is the above is provided.

In the glass plate with a thin film of the present invention, by providing a barrier layer having a specific composition on a thin film having functionality, acid resistance and alkali resistance are improved without impairing optical properties such as antireflection properties. Yes.

FIG. 1 is a conceptual diagram for explaining a manufacturing method of a glass plate with a thin film according to one embodiment of the present invention. FIG. 2 is a diagram showing ESCA measurement results in the examples. FIG. 3 is a diagram showing ESCA measurement results in a comparative example.

Hereinafter, the present invention will be described by taking, as an example, a glass plate with an antireflection film on which an antireflection film is formed as an example of a thin film having the functionality of the present invention. However, thin films having various functionalities can be applied to the present invention as long as the effects are not impaired.

A glass plate with a thin film which is one embodiment of the present invention includes a silicon oxide (SiO ₂ ) film as a low refractive index film and a titanium oxide (TiO ₂ ) film as a high refractive index film alternately on a glass substrate. The antireflection film is formed by laminating the film, and the barrier layer having the specific composition described below is formed on the antireflection film.
Hereafter, each component of the glass plate with a thin film of this invention is demonstrated.

<Glass substrate>
The glass substrate in the present invention is not necessarily flat and plate-like, and may be curved or atypical. As the glass substrate, transparent glass plates made of colorless and transparent soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, non-alkali glass, and other various glasses can be used. From the viewpoint of price, soda lime silicate glass is preferable. The plate thickness of the glass substrate is preferably 0.2 to 12 mm.

<Functional thin film>
As a thin film having functionality in the present invention (hereinafter also referred to as a functional thin film), an antireflection (AR) film, a low emission (Low-E) film, an IR cut multilayer film, a UV cut multilayer film, or the like is applicable. . As a method for forming the functional thin film, a CVD method, a PVD method, a sol-gel method, or the like can be used.
For example, the antireflection film is formed by alternately laminating a silicon oxide (SiO ₂ ) film as a low refractive index film and a titanium oxide (TiO ₂ ) film as a high refractive index film. From the glass substrate side, the SiO ₂ film and the TiO ₂ film may be alternately laminated in this order, or the TiO ₂ film and the SiO ₂ film may be alternately laminated in this order. When first formed a TiO ₂ film on a glass substrate (i.e., TiO ₂ film, when alternately stacking the order of SiO ₂ film) is more of a difference in refractive index between the glass substrate increases, SiO ₂ This is preferable in that the number of layers can be reduced as compared with the case where the film is formed first (that is, when the SiO ₂ film and the TiO ₂ film are alternately stacked).
Here, the thickness of the SiO ₂ film is preferably 15 nm or more and 100 nm or less. On the other hand, the thickness of the TiO ₂ film is preferably 5 nm or more and 120 nm or less. The SiO ₂ film and the TiO ₂ film are preferably laminated in a total of 2 to 16 layers.
Note that the SiO ₂ film and the TiO ₂ film constituting the antireflection film may have different film thicknesses. For example, a 10 nm thick TiO ₂ film, a 30 nm thick SiO ₂ film, a 105 nm thick TiO ₂ film, and a 92 nm thick SiO ₂ film may be stacked in this order. The uppermost SiO ₂ film may have a thickness of about ½ of 92 nm.
The film thickness of the antireflection film, that is, the total film thickness of the laminated film of the SiO ₂ film and the TiO ₂ film is preferably 150 to 300 nm, and more preferably 180 to 250 nm.

The film formation method of the SiO ₂ film and the TiO ₂ film is not particularly limited, but the use of the CVD method is easy to apply to a large area, the film formation rate can be easily changed, and the productivity is high and economically advantageous. It is preferable for the reason.
When using the CVD method, the pressure conditions at the time of implementation are not particularly limited, but the implementation at normal pressure is easy to control the atmosphere during film formation, and is highly compatible with existing production equipment, Economically advantageous and preferred.

When the CVD method is used to form the SiO ₂ film, the CVD method may be performed using monosilane (SiH ₄ ) as the main material and oxygen (O ₂ ) as the auxiliary material. At this time, the O ₂ / SiH ₄ molar ratio is preferably 50 or more from the viewpoint of film formation rate. In addition, the temperature of the glass substrate is preferably 530 to 600 ° C. from the viewpoint of film formation speed.
On the other hand, when the CVD method is used to form the TiO ₂ film, the CVD method may be performed using tetraisopropoxy titanium (TTIP) as a raw material. At this time, the temperature of the glass substrate is preferably 530 to 580 ° C. from the viewpoint of film formation speed.

<Barrier layer>
The barrier layer in the present invention consists essentially of a mixed oxide of silicon (Si) and titanium (Ti). In the present invention, “the barrier layer consists essentially of a mixed oxide of silicon (Si) and titanium (Ti)” means that silicon (Si), titanium (Ti) and oxygen (O ) Of the total atomic content is 85 Atom% or more.
As described above, the SiO ₂ film has good acid resistance but low alkali resistance. The TiO ₂ film has good alkali resistance but low acid resistance. By configuring the barrier layer with a mixed oxide of silicon (Si) and titanium (Ti), both acid resistance and alkali resistance can be achieved.
However, in order to achieve both acid resistance and alkali resistance and to obtain a barrier layer having a desired refractive index, it is not sufficient to simply form the barrier layer with a mixed oxide of silicon and titanium. It is necessary to satisfy the points to be stated.

When the barrier layer is substantially composed only of a mixed oxide of silicon (Si) and titanium (Ti), the presence of a certain amount of SiO _{2 on} the surface of the barrier layer improves the acid resistance and alkali resistance. On the other hand, in order to ensure the alkali resistance required for the barrier layer in the present invention, a specific amount of TiO ₂ specified below needs to be present.
However, when a barrier layer having a uniform composition ratio of TiO ₂ and SiO ₂ in the layer thickness direction is formed, the amount of TiO ₂ occupying the entire barrier layer, particularly the lower limit thereof, is determined by the specific amount, and the barrier layer Therefore, it is difficult to obtain a desired refractive index.
The present invention is a layer in which the abundance ratio of TiO ₂ is higher than the abundance ratio of SiO _{2 in} the barrier layer, that is, the atomic content (Atom%) of titanium (Ti) is the atomic content (Atom) of silicon (Si). %)) (Hereinafter referred to as a titanium (Ti) rich layer), by combining silicon (Si) and titanium (Ti) having both good acid resistance and alkali resistance and having a desired refractive index. And a barrier layer made only of mixed oxides.

In one embodiment of the present invention, the barrier layer is formed using a transfer-type atmospheric pressure CVD apparatus.
FIG. 1 is a conceptual diagram for explaining a manufacturing method of a glass plate with a thin film in one embodiment of the present invention, and schematically shows a configuration example of a transport type atmospheric pressure CVD apparatus.
The material supply means 10 of the transport type atmospheric pressure CVD apparatus shown in FIG. 1 is a means for supplying the material to the glass substrate Z transported in the direction of arrow y by the roller 12a of the conveyor belt 12.
A raw material supply means 10 shown in FIG. 1 includes a nozzle (main raw material supply nozzle) 14 for supplying a main raw material, and an upstream side and a downstream side in the transport direction (arrow y direction) of the glass substrate Z with respect to the main raw material supply nozzle 14. The

nozzles

16 and 16 for supplying auxiliary materials (sub-material supply nozzles) 16 and 16 and the

exhaust nozzles

18 and 18 for sucking and removing the gas generated by the reaction and excess materials are configured. The raw material supply means 10 shown in FIG. 1 is a post-mix type raw material supply means for mixing the main raw material from the main raw material supply nozzle 14 and the auxiliary raw material from the auxiliary raw

material supply nozzles

16, 16 on the glass substrate Z. .
The functional thin film, for example, in the case of forming an anti-reflective (AR) film, a total of seven using an injector, six injectors of TiO ₂ and SiO ₂ are seven of the antireflection film as an underlying barrier layer Is formed using. That is, the barrier layer is formed by using one injector.

When forming a barrier layer in one embodiment of the present invention using a transport-type atmospheric pressure CVD apparatus, as shown in FIG. 1, the main raw materials are monosilane (SiH ₄ ) and tetraisopropoxy titanium (TTIP), The raw material is supplied as oxygen (O ₂ ) from the main raw material supply nozzle 14 and the auxiliary raw material supply nozzle 16 onto the glass substrate Z conveyed in the direction of arrow y by the conveyor belt 12. Since TTIP has a higher reactivity than SiH ₄ , the reaction proceeds directly under the raw material supply nozzles (14, 16), and the reaction of SiH ₄ proceeds at the peripheral edge thereof.
Here, since the glass substrate Z which forms a barrier layer is conveyed in a fixed direction (arrow y direction), the formed barrier layer has a composition distribution in the layer thickness direction. Specifically, at the end side in the layer thickness direction, that is, at least on the front side and the back side of the barrier layer, the ratio of silicon (Si) atomic content (of silicon (Si) and titanium (Ti)) The ratio of the atomic content of silicon (Si) to the total atomic content (Si / (Si + Ti) (%))) is high, and the composition of the atomic content of titanium (Ti) is high inside the barrier layer. Distribution. Titanium (Ti) rich layer having a high ratio (Ti / (Si + Ti) (%)) of the atomic content of titanium (Ti) to the total atomic content of silicon (Si) and titanium (Ti) in the barrier layer Incorporating the acid can achieve both acid resistance and alkali resistance. At this time, not only the front surface side of the barrier layer but also the back surface side (for example, the antireflection layer side) is a silicon (Si) atomic content ratio (silicon with respect to the total atomic content of silicon (Si) and titanium (Ti)). (Si) atomic content ratio (Si / (Si + Ti) (%))) may be high.

As described above, the barrier layer in one embodiment of the present invention is a mixture in which the barrier layer is substantially composed of only a mixed oxide of silicon (Si) and titanium (Ti) and is measured by X-ray photoelectron analysis (ESCA). A titanium (Ti) rich layer in which the atomic content (Atom%) of titanium (Ti) in the oxide is higher than the atomic content (Atom%) of silicon (Si) is provided. The maximum value of the titanium (Ti) atom content ratio (Ti / (Ti + Si) (%)) with respect to the total atomic content ratio of silicon (Si) and titanium (Ti) is 80% or more.

On the other hand, in one embodiment of the present invention, the ratio of the atomic content of silicon (Si) on the surface of the barrier layer (the atomic content of silicon (Si) with respect to the total atomic content of silicon (Si) and titanium (Ti) ( Si / (Si + Ti) (%))) is preferably provided with a layer higher than other portions of the barrier layer. If the ratio of silicon (Si) atom content (Si / (Ti + Si) (%)) measured by X-ray photoelectron analysis (ESCA) on the surface of the barrier layer is 35% or more, good acid resistance is obtained. % Or more is preferable, and 50% or more is more preferable. Moreover, if it is 60% or more, since the barrier layer which is excellent also in abrasion resistance is obtained, it is further more preferable. On the other hand, when considering alkali resistance, a single SiO ₂ film has low alkali resistance, but in one embodiment of the present invention, the proportion of silicon (Si) atomic content (Si / (Si + Ti) (%))) is Alkali resistance may be impaired because a certain amount of titanium (Ti) is contained on the surface of the barrier layer that is high (that is, the proportion of SiO ₂ is high) (that is, TiO ₂ is present on the surface of the barrier layer). Absent.

When the composition distribution in the barrier layer is opposite to the above, that is, the ratio of the atomic content of titanium (Ti) (Ti / (Si + Ti) (%)) is high on the surface side of the barrier layer and on the antireflection film side. When the composition ratio of the silicon (Si) atomic content ratio (Si / (Si + Ti) (%)) on the inner side of the barrier layer is high, the atomic content of titanium (Ti) on the surface side of the barrier layer The acid resistance is low because of the high ratio. When the surface side of the barrier layer is eroded by the acid, the ratio of silicon (Si) atomic content is high, and the inner side of the barrier layer is exposed to the surface, so that the alkali resistance of the barrier layer also decreases.

As described above, the barrier layer in one embodiment of the present invention has a composition distribution in the layer thickness direction. Specifically, the atomic ratio of silicon (Si) (Si / (Si + Ti) (%) on both end sides in the layer thickness direction, that is, on the surface side of the barrier layer and on the functional thin film side such as an antireflection film. ))) Is high, and it is more preferable that the ratio of the atomic content of titanium (Ti) (Ti / (Si + Ti) (%)) is high between the two, that is, inside the barrier layer.
Regarding this composition distribution, it is preferable to satisfy the following.
When the layer thickness of the barrier layer is L (nm), the portion where the ratio of titanium (Ti) atom content (Ti / (Si + Ti) (%)) in the mixed oxide takes the maximum value is the layer thickness of the barrier layer. In the direction, it is preferably at a position satisfying 0.05L to 0.95L. Furthermore, it is more preferable that it is 0.25 L to 0.75 L, that is, it is located in the range of 1/4 L from the center of the thickness of the barrier layer because the durability of the barrier layer is improved.
On the other hand, the portion where the ratio of titanium (Ti) atom content (Ti / (Si + Ti) (%)) takes the minimum value is at least one portion of both end portions in the layer thickness direction of the barrier layer, that is, the barrier layer. It is preferable to be in at least one of the surface side portion and the functional thin film side portion such as an antireflection film.

In the barrier layer according to one embodiment of the present invention, the total thickness of the barrier layer is preferably 11 nm or more. If the thickness of the barrier layer is less than 11 nm, the barrier layer may not sufficiently cover the functional thin film. If the functional thin film is, for example, an antireflection film, the alkali resistance of the SiO ₂ layer in the antireflection film is insufficient. become.
The upper limit of the thickness of the barrier layer can be appropriately set depending on the type of the functional thin film to be coated. For example, when the functional thin film is an antireflection film, it is preferably 25 nm or less.

In one embodiment of the present invention, it is desirable to obtain a barrier layer having a desired refractive index so as not to impair the function of the functional thin film protected by the barrier layer.
For example, when the functional thin film is an antireflection film, the refractive index of the barrier layer needs to be 2.25 or less (wavelength 638 nm) in order not to impair the function.
Further, as described above, in order not to impair the function of the antireflection film, the refractive index of the barrier layer is required to be equal to or lower than the refractive index of the TiO ₂ film as the high refractive index film.
In this specification, the refractive index of the barrier layer and the TiO ₂ film is based on the refractive index at a wavelength of 638 nm. The reason is because the wavelength dispersion of the refractive index is relatively small in the visible light wavelength region.
The refractive index of the TiO ₂ film at a wavelength of 638 nm is 2.45.
On the other hand, the barrier layer of one embodiment of the present invention can easily have a refractive index of 2.25 or less by having the composition distribution in the layer thickness direction described above. For this reason, the function of the antireflection film is not impaired by the formation of the barrier layer.

As described above, the barrier layer of one embodiment of the present invention has good acid resistance and alkali resistance. In the examples described later, acid resistance and alkali resistance tests were performed according to JIS R 3221: 2002. Further, a scratch resistance test was conducted by the method described later.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this.

In this example, the barrier layer was formed on the glass substrate with a functional thin film in the slow cooling zone of the float forming line using the transfer type atmospheric pressure CVD apparatus shown in FIG.
Monosilane (SiH ₄ ) and tetraisopropoxytitanium (TTIP) are used as the main raw materials for the barrier layer, and oxygen (O ₂ ) is used as the auxiliary raw materials, which are respectively conveyed from the main raw material supply nozzle 14 and the auxiliary raw material supply nozzle 16 to the conveyor belt. 12 was supplied onto the glass substrate Z on which the functional thin film conveyed in the direction of the arrow y was formed to form a barrier layer. These barrier layers were formed by a single injector.

In this example, for the barrier layer, the amount of tetraisopropoxy titanium (TTIP) supplied per 1 m of film forming width, the ratio of tetraisopropoxy titanium (TTIP) and monosilane (SiH ₄ ) (TTIP / SiH ₄ ), and the barrier layer A plurality of samples having different layer thicknesses were prepared, and acid resistance, alkali resistance, and scratch resistance were evaluated for the obtained barrier layer composed of a mixed oxide of Si and Ti. Moreover, the atomic content rate (Atom%) of the layer thickness direction was measured about Ti atom, Si atom, and O atom contained in a barrier layer using X-ray photoelectron analysis (ESCA). For the measurement, a scanning X-ray photoelectron spectrometer (PHI 5000 VersaProbe, manufactured by ULVAC-PHI) has a beam diameter of 100 μm, and while performing Ar sputtering from the surface of the barrier layer, the barrier layer and the underlying functional thin film The atomic content was analyzed along the layer thickness direction up to the interface with the layer. At this time, argon (Ar) was used as the etching gas, the gas pressure was 1.5 × 10 ⁻² Pa, the acceleration voltage was 1 kV, and the ion beam system was 2 × 2 mm.

From the measurement results, as shown in Table 1, the maximum value of the Ti atom content ratio (Ti / (Ti + Si) (%)) in the barrier layer and the titanium (Ti) atom content ratio take the maximum values. The position (peak position) and the ratio of silicon (Si) atomic content in the surface layer (Si / (Ti + Si) (%)) were determined.
The layer thickness of the barrier layer at this time was defined from the surface of the barrier layer to the position where the titanium (Ti) atomic content was 1/10 of the titanium (Ti) atomic content at the peak position. Further, the position at which the ratio of the titanium (Ti) atom content rate takes the maximum value (the above peak position) is a relative value ((the above peak position) where the total thickness of the barrier layer is 1 L and the surface of the barrier layer is the reference 0 L. / Total barrier layer thickness) × L). At this time, the atomic content on the surface of the barrier layer was defined by the atomic content of the surface layer after removing the outermost surface layer for 1 minute (1 nm) by Ar sputtering. This is to prevent contamination of contaminant components such as carbon on the outermost surface. Further, the layer thickness of the entire barrier layer was defined as the layer thickness including the above-mentioned removed outermost layer.

The acid resistance and alkali resistance tests were carried out according to JIS R 3221: 2002, and pass (OK) or fail (NG) was determined.

The scratch resistance test was performed by dropping 1 ml of the adjustment liquid onto the surface of the barrier layer and applying a load of 1100 g / cm ² to a polishing cloth (wool buff) having a contact surface of 30 × 11 mm. As the adjustment liquid, 1 L of tap water mixed with 1.0 g of JIS Z 8901: 2006 powder and 2 drops of a neutral detergent was used before and after sliding the polishing cloth linearly 420 times. The barrier layer surface was evaluated.

Table 1 shows the formation conditions of the barrier layer and the evaluation results of acid resistance, alkali resistance and scratch resistance. For the evaluation of scratch resistance, Rv (visible light reflectance) was measured and visually confirmed in accordance with JIS Z 8722: 2009 for the test specimen after the test, and the change (ΔRv) in Rv before and after the test was 2.0. % And when the sample was not visually damaged, it was determined to be acceptable (OK). In other cases, it was determined as NG.

Table 1 shows the maximum value of the titanium (Ti) atom content ratio (Ti / (Ti + Si) (%)) in the barrier layer, and the position at which the titanium (Ti) atom content ratio takes the maximum value (peak position). The relative peak position expressed as a ratio to the total thickness (L) of the barrier layer and the ratio of the silicon (Si) atom content on the barrier layer surface (Si / (Ti + Si) (%)) Results are shown.
In Examples 1 to 7, the maximum value of the titanium (Ti) atom content ratio was 80.0% or more, and both the alkali resistance test and the acid resistance test were good results. In Examples 1 to 5, the ratio of the silicon (Si) atom content on the surface of the barrier layer was 60.0% or more, and all exhibited good scratch resistance. On the other hand, Comparative Examples 1 and 2 in which the maximum value of the proportion of titanium (Ti) atom content was less than 80.0% failed in the alkali resistance test. Further, Comparative Example 1 in which the position (peak position) at which the ratio of the titanium (Ti) atom content rate takes the maximum value was out of the range of 0.25 L to 0.75 L was also rejected in the scratch resistance test.
FIG. 2 shows the atomic content of Ti, Si, and O in the barrier layer of each sample of Example 1 and FIG. 3 of Comparative Example 1. In FIGS. 2 and 3, the etching time corresponds to the layer thickness of the barrier layer, and when compared with the standard sample of the SiO ₂ thin film, the etching time 1 min corresponds to the layer thickness 1 nm from the surface of the barrier layer.
As is clear from the results of ESCA in FIG. 2, the position where the ratio of the titanium (Ti) atom content rate in Example 1 takes the maximum value is 0.36 L, and titanium (Ti) atom content is present in the middle portion of the barrier layer. A titanium (Ti) rich layer having a maximum rate ratio of 80.0% or more is provided. Moreover, the atomic content rate of silicon (Si) is high on the surface side of the barrier layer and the functional thin film side. From the ESCA result of Comparative Example 1 shown in FIG. 3, it can be seen that the maximum value of the titanium (Ti) atom content ratio of the titanium (Ti) rich layer is less than 80.0%.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2013-220812 filed on Oct. 24, 2013, the contents of which are incorporated herein by reference.
The contents of JIS R 3221: 2002, JIS Z 8901: 2006 and JIS Z 8722: 2009 are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Raw material supply means 12 Conveyor belt 12a Roller 14 Main raw material supply nozzle 16 Sub raw material supply nozzle 18 Exhaust nozzle Z Glass substrate

Claims

A glass plate with a thin film having a glass substrate, a functional thin film, and a barrier layer in this order,
The barrier layer is substantially composed of a mixed oxide of silicon (Si) and titanium (Ti);
The barrier layer is titanium (Atom%) of titanium (Ti) in the mixed oxide measured by X-ray photoelectron analysis (ESCA) higher than the atomic content (Atom%) of silicon (Si) ( Ti) with a rich layer,
The maximum value of the atomic content ratio of titanium (Ti) to the total atomic content ratio of silicon (Si) and titanium (Ti) in the titanium (Ti) rich layer (Ti / (Si + Ti) (%)) is 80%. This is the glass plate with a thin film.
2. The thin film according to claim 1, wherein the silicon (Si) atomic content ratio (Si / (Ti + Si) (%)) measured by X-ray photoelectron analysis (ESCA) of the surface of the barrier layer is 35% or more. Glass plate with.
The thin film according to claim 1, wherein a ratio (Si / (Ti + Si) (%)) of silicon (Si) atomic content measured by X-ray photoelectron analysis (ESCA) of the surface of the barrier layer is 60% or more. Glass plate with.
When the thickness of the barrier layer is L (nm), the ratio of the atomic content of titanium (Ti) to the total atomic content of silicon (Si) and titanium (Ti) in the mixed oxide (Ti / ( The thin film according to any one of claims 1 to 3, wherein a portion where (Si + Ti) (%)) takes a maximum value is at a position satisfying 0.05 L to 0.95 L in the layer thickness direction of the barrier layer. Glass plate with.
When the thickness of the barrier layer is L (nm), the ratio of the atomic content of titanium (Ti) to the total atomic content of silicon (Si) and titanium (Ti) in the mixed oxide (Ti / ( The portion where Si + Ti) (%)) takes the maximum value is at a position satisfying 0.25L to 0.75L in the thickness direction of the barrier layer, and the atomic content of silicon (Si) and titanium (Ti) The portion where the ratio of the atomic content of titanium (Ti) to the total (Ti / (Si + Ti) (%)) takes the minimum value is at least one of the both ends in the layer thickness direction of the barrier layer. Item 4. The glass plate with a thin film according to any one of Items 1 to 3.
The glass plate with a thin film according to any one of claims 1 to 5, wherein the barrier layer has a thickness of 25 nm or less.
The glass plate with a thin film according to any one of claims 1 to 6, wherein the barrier layer is formed by using a transfer type atmospheric pressure CVD apparatus.
The functional thin film is an antireflection film obtained by alternately laminating a silicon oxide (SiO 2 ) film as a low refractive index film and a titanium oxide (TiO 2 ) film as a high refractive index film, 8. The antireflection film according to claim 1, wherein a total of 2 to 16 layers of SiO 2 films having a thickness of 15 nm to 100 nm and TiO 2 films having a thickness of 5 nm to 120 nm are alternately laminated. A glass plate with a thin film according to claim 1.
The glass plate with a thin film according to claim 8, wherein the antireflection film is alternately laminated in the order of a SiO 2 film and a TiO 2 film from the glass substrate side.
The glass plate with a thin film according to claim 8, wherein the antireflection film is alternately laminated in the order of a TiO 2 film and an SiO 2 film from the glass substrate side.
The glass plate with a thin film according to any one of claims 1 to 7, wherein the functional thin film is a low emission (Low-E) film.
The glass plate with a thin film according to any one of claims 1 to 7, wherein the functional thin film is a multilayer film having an IR cut function.
The thin film-attached glass plate according to any one of claims 1 to 7, wherein the functional thin film is a multilayer film having a UV cut function.
A glass substrate, a functional thin film, and a manufacturing method of a glass plate with a thin film having a barrier layer in this order, wherein the barrier layer is formed using a transport type atmospheric pressure CVD apparatus,
Monosilane (SiH 4 ) and tetraisopropoxy titanium (TTIP) as main raw materials, oxygen (O 2 ) as a secondary raw material, a main raw material supply nozzle, an upstream side in the conveyance direction of the glass substrate with respect to the main raw material supply nozzle, and From the auxiliary material supply nozzle provided on the downstream side, comprising a step of supplying onto the glass substrate conveyed in the conveyance type atmospheric pressure CVD apparatus,
The barrier layer is substantially composed of a mixed oxide of silicon (Si) and titanium (Ti);
Titanium in which the barrier layer has an atomic content (Atom%) of titanium (Ti) in the mixed oxide measured by X-ray photoelectron analysis (ESCA) higher than an atomic content (Atom%) of silicon (Si) ( Ti) with a rich layer,
The maximum ratio of the atomic content of titanium (Ti) to the total atomic content of silicon (Si) and titanium (Ti) in the titanium (Ti) rich layer (Ti / (Ti + Si) (%)) is 80% The manufacturing method of the glass plate with a thin film which is the above.