JPH07108642A - Functional article - Google Patents

Abstract

PURPOSE:To improve resistance to marring properties on the film surface and to automate blanking by forming an oxide film which incorporates oxide containing Sn and Si as a main component on the uppermost layer in a functional article in which transparent oxide and an Ag layer are successively laminated on a transparent base body and total (2n+1) layers (n>=1) are formed. CONSTITUTION:A transparent oxide layer 2 and an Ag layer 3 are successively lamianted on a transparent base body 1 and total (2n+1) layers (n>=1) are formed. Furthermore an oxide film (STO film) 5 which incorporates oxide containing Sn and Si as a main component is formed on the uppermost layer. The refractive index of visible light of the STO film 5 is regulated to 1.5-2.0. The refractive index depends on the composition of Sn and Si of a target and sputtering conditions but is mainly controlled by the composition of the target. Further the rate of Sn and Si in the STO film 5 is regulated to 5-95% Sn for total amount of Sn and Si in atomic ratio. Thickness of the STO film 5 is regulated to 1-50nm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a functional article having excellent mechanical durability.

[0002]

2. Description of the Related Art Conventionally, a low-layer structure in which a multilayer film is formed on a large-area glass substrate by using a magnetron sputtering method.
-E glass and heat ray shielding glass are used. These glasses used for buildings and automobiles have excellent energy-saving effects and excellent design properties, and have been widely used in recent years.

In the Low-E glass using Ag, Zn is
Three-layer structure of O / Ag / ZnO, or ZnO / Ag / Z
It is common to have a multi-layer film having a five-layer structure of nO / Ag / ZnO. Since this type of Low-E glass has poor durability, it cannot be used as a single plate glass, and as a double-layer glass,
Alternatively, it is used in the form of laminated glass. A three-layer film of ZnO / Ag / ZnO is also coated on the windshield glass and rear glass of an automobile on the adhesive surface side of the laminated glass, and is put into practical use as a heat ray shielding glass.

Production of heat-ray shielding glass is carried out in a line consistent with substrate cleaning, sputtering film formation, and post-cleaning. In recent years, the process of placing a blank on the line and removing the plate from the line has been automated and automated. Tend to

[0005]

However, the low-E glass using Ag has a weak scratch resistance of the film, and thus it must be handled with extreme care before being made into a double-glazing or laminated glass. The production could not be automated.

Specifically, when trying to automate the production,
In order to prevent the glass from sticking to each other during plate cutting, resin powder is sprinkled between the glass, but Lo using Ag is used.
Since w-E glass has a weak scratch resistance of the film, this powder causes flaws on the film surface. Therefore, Low
-It is not possible to automate board removal with E-glass, and it is done manually, and paper or the like is sandwiched between the glasses instead of powder. Therefore, the production time could not be shortened and the cost was also increased.

The present invention has been made to solve the above-mentioned problems, and provides a Low-E glass using Ag, which has improved scratch resistance of the film surface and can be automatically machined. To aim.

[0008]

The present invention provides a functional article in which a transparent oxide layer and an Ag layer are sequentially laminated on a transparent substrate to form a total of (2n + 1) layers (n ≧ 1). 2. In the functional article, there is further provided an oxide film containing an oxide containing Sn and Si as a main component on the outermost layer.

The present invention also provides the above functional article in which a metal film barrier layer is formed between the Ag layer and the transparent oxide layer formed thereon.

In the present invention, the low-E film using Ag is further overcoated with an oxide film mainly containing an oxide containing Sn and Si as a protective film to improve the scratch resistance of the low-E film. The main purpose is to let you.

FIG. 1 is a functional article of Examples 1 and 5 of the present invention, FIG. 2 is a functional article of Example 2 of the present invention, FIG. 3 is of Example 3 of the present invention, and FIG. It is each sectional drawing of the functional article of Example 4 of invention, but this invention is not limited only to this.

In the figure, 1 is a transparent substrate such as glass or plastic, 2 is a transparent oxide layer, 3 is an Ag layer, and 4 is A.
A metal barrier layer 5 formed between the g layer 3 and the transparent oxide layer 2 formed thereon is an oxide film containing an oxide containing Sn and Si as a main component (hereinafter referred to as an STO film). Indicates.

In the present invention, n is not particularly limited, and n
Is larger, the Low-E performance is improved. However, the cost also increases accordingly, so that the practically sufficient Low-E
A system with a performance of about n = 1 or n = 2 is preferably adopted.

The Ag layer 3 is made of Pd, Al, C in addition to Ag.
It may contain an element such as u. The film thickness of the Ag layer is not particularly limited, but is 5 to 25 nm, particularly 8 to 15 nm,
Is preferred. If it is less than 5 nm, the Low-E performance is insufficient, and if it exceeds 25 nm, the durability of the functional article of the present invention is reduced.

The metal barrier layer 4 is provided to prevent Ag oxidation. The material forming the metal barrier layer 4 is not particularly limited, but Zn, Ti, Cr, Sn, Ni, stainless steel, Ni—Cr, SiN _x , AlN _x , BN and the like are preferably mentioned, and Zn is particularly preferable. The film thickness of the metal barrier layer 4 is preferably 1 to 5 nm. If it is less than 1 nm, the antioxidant function is insufficient, and if it exceeds 5 nm, the transmittance of the functional article of the present invention is lowered.

The STO film 5 includes Zr,
Other elements such as Ti, Ta and Bi may be contained.
The STO film preferably has a refractive index of 1.5 to 2.0. This refractive index depends on the composition of Sn and Si of the target and the sputtering conditions, but can be controlled mainly by the target composition.

The ratio of Sn to Si in the STO film 5 is not particularly limited, but in atomic ratio, Sn is 5 to 95%, preferably 20 to 90%, and particularly preferably 40 to 90% with respect to the total amount of Sn and Si. %, And If the proportion of Sn is too small, arcing is likely to occur when the film is formed by the direct current sputtering method, the applied voltage is limited, the film forming speed is significantly limited, and the productivity is reduced. If the amount of Sn is too large, the refractive index is unlikely to fall within the preferred range described above, and when overcoated, the color tone changes significantly due to optical interference.

The thickness of the STO film 5 is not particularly limited,
The range of 1 to 50 nm is preferable. To impart sufficient scratch resistance, it is necessary to have a thickness of about 10 nm or more. The scratch resistance improves as the film thickness increases, and if it is 40 to 50 nm, more sufficient scratch resistance can be obtained. If it is made too thick, the change in color tone due to optical interference becomes significant. Therefore, the overcoat film thickness is particularly preferably 10 to 30 nm.

As described above, the low-E glass multilayer film using Ag generally has a three-layer structure of ZnO / Ag / ZnO or a five-layer structure of ZnO / Ag / ZnO / Ag / ZnO. . In this case, since the uppermost layer is ZnO (refractive index of about 2.0), by adjusting the film thickness of the uppermost ZnO film and the refractive index and film thickness of the STO film 5 when overcoating the STO film 5. , It is possible to minimize the change in color tone due to overcoating.

The uppermost layer of the Low-E glass using Ag is generally an oxide (ZnO etc.), and the STO film 5 is also an oxide, which can be formed by reactive sputtering in the same atmosphere. And Sn—Si based targets can be placed in the same chamber to form, for example, a ZnO film and an STO film 5 in succession.

The STO film 5 is obtained by a reactive sputtering method in an oxygen atmosphere from a target obtained by hardening Sn and Si by a CIP method (cold isotropic press). The target is not limited to this, and a film may be formed from a mixed oxide target of SnO ₂ and SiO ₂ . In addition, a vacuum deposition method, an ion plating method, a CVD method or the like may be used.

As a transparent oxide film for improving the scratch resistance, for example, an oxide film containing an oxide containing Zr and Si or B as a main component is known (for example, Japanese Patent Application Laid-Open No. HEI-2).
-289339 gazette). When a film is formed from a metal target by reactive sputtering, Sn and S in the present invention are used.
The oxide film whose main component is an oxide containing i is Zr and Si.
The film forming speed is higher than that of an oxide film containing an oxide containing as a main component.

When the power density applied to the target is the same, as compared with the case where an oxide film is formed using a Zr-Si (atomic ratio 1: 2) target, a Sn-Si (atomic ratio 1: 1) target is used. When an oxide film is formed by using, the film forming speed is about 2.5 times, and when an Sn-Si (atomic ratio 4: 1) target is used, the film forming speed is about 2.
6 times. In reality, a large power density cannot be applied to the Zr-Si target due to arcing or the like, but a power density about 1.6 times that of the Zr-Si target can be applied to the Sn-Si target.

Therefore, when a power as large as possible is applied to the target, the film forming speed in the case of forming the film from the Sn-Si target is about four times that in the case of forming the film from the Zr-Si target. It is extremely effective in terms of production efficiency.

[0025]

In the present invention, the low-E film using Ag has improved scratch resistance of the film due to overcoating. Although various films are conceivable as the overcoat film, the oxide film containing Sn and Si as the main component in the present invention is 1) capable of stably producing reactive DC sputtering from a metal target. It has features such as high film speed, 2) variable refractive index in the range of 1.5 to 2.0 depending on target composition, and 3) harder than SnO ₂ .

[0026]

【Example】

[Example 1] A washed float glass plate having a thickness of 2 mm was set in a sputtering apparatus and exhausted to a level of 10 ^-6 Torr. Next, O ₂ gas was introduced into the chamber, the pressure was set to 2 × 10 ⁻³ Torr, and a Zn target was sputtered at a target power density of 5.2 W / cm ² ,
A 40 nm film of ZnO (first layer) was formed on the substrate.

Next, Ar is used as a gas and the pressure is set to 2 × 10.
^-3 Torr, Ag target 0.8W / power density
Sputtering with cm ² and Ag (second layer) of 15 nm
The film was formed.

Next, the gas was changed to O ₂ gas again, and ZnO (third layer) was formed to a thickness of 20 nm under the same conditions as the first layer.

Finally, the gas is a mixed gas of Ar and O ₂ (flow ratio 1: 1), the pressure is 2 × 10 ^-3 Torr, and Sn is used.
And an alloy target of Si (atomic ratio 1: 1) were sputtered at a power density of 7.8 W / cm ² to form a 10 nm oxide film (fourth layer) containing Sn and Si and having a refractive index of about 1.7. . Hereinafter, this film is referred to as STO-1.

[Example 2] ZnO / Ag / Z was formed on a float glass substrate having a thickness of 2 mm under the same method and conditions as in Example 1.
A three-layer film of nO was formed. The film thickness is 40 nm,
It was set to 10 nm and 80 nm. Subsequently, in the same manner, Ag (4th layer) and ZnO (5th layer) were each added to 10n.
m, 10 nm was formed into a film. Further, subsequently, STO-1 (sixth layer) was formed under the same method and conditions as in the case of the fourth layer of Example 1.
To a film thickness of 10 nm.

[Embodiment 3] In the same manner as in Embodiment 1, the first
The layer and the second layer were formed into a film. Next, the gas was kept as Ar, the pressure was set to 2 × 10 ⁻³ Torr, and the Zn target was sputtered at a power density of 3.0 W / cm ² to form a Zn film (barrier layer) with a thickness of 5 nm.

Next, the gas is changed to O ₂ gas and the pressure is set to 2 × 10.
^-3 Torr, Zn target with power density of 5.2 W /
The ZnO film (third layer) is sputtered at a density of 20 cm ²
nm film was formed.

Finally, the gas is a mixed gas of Ar and O ₂ (flow ratio 1: 1), an alloy target of Sn and Si (atomic ratio 1: 1) is sputtered at a power density of 7.8 W / cm ² , and STO is used. -1 (4th layer) was formed into a film of 10 nm.

[Example 4] A three-layer film of ZnO / Ag / Zn (barrier layer) / ZnO was formed on a float glass substrate under the same method and conditions as in Example 3. The film thickness is 4
It was set to 0 nm, 10 nm, 5 nm, and 80 nm. Subsequently, in the same manner, Ag (fourth layer), Zn (barrier layer), and ZnO (fifth layer) of 10 nm and 5 n, respectively.
m, 10 nm was formed into a film. Further subsequently, STO-1 (sixth layer) was prepared by the same method and condition as the fifth layer of the third embodiment.
Layer) was formed into a film having a thickness of 10 nm.

[Example 5] ZnO / Ag / Z was formed on a float glass substrate having a thickness of 2 mm under the same method and conditions as in Example 1.
A three-layer film of nO was formed. Next, a mixed gas of Ar and O ₂ (flow rate ratio of 1: 1) is used, the pressure is set to 2 × 10 ⁻³ Torr, and an alloy target having an atomic ratio of Sn and Si of 2: 8 is set to a power density of 7.8 W / cm. Sputter with ² , Sn and S
An oxide film (fourth layer) having a refractive index of about 1.6 and an atomic ratio of i to 2: 8 was formed to a thickness of 10 nm. This film is called STO-2.

Comparative Example 1 ZnO / Ag / on a float glass substrate having a thickness of 2 mm under the same method and conditions as in Example 1.
A ZnO three-layer film was formed to the same thickness as in Example 1.

[Comparative Example 2] ZnO / Ag / on a 2 mm thick float glass substrate under the same method and conditions as in Example 1.
A ZnO three-layer film was formed to the same thickness as in Example 1. Subsequently, a mixed gas of Ar and O ₂ (flow ratio 1: 1) was introduced into the chamber, the pressure was adjusted to 2 × 10 ⁻³ Torr, and S was added.
An n target was sputtered at a power density of 7 W / cm ² to form a SnO ₂ film (fourth layer) with a thickness of 10 nm.

[Comparative Example 3] ZnO / Ag / Z was formed on a float glass substrate having a thickness of 2 mm under the same method and conditions as in Example 1.
A three-layer film of nO was formed. The film thickness is 40 nm,
It was set to 10 nm and 80 nm. Subsequently, in the same manner, Ag (4th layer) and ZnO (5th layer) were respectively added to 10
nm, 10 nm was formed into a film.

[Comparative Example 4] A three-layer film of ZnO / Ag / Zn (barrier layer) / ZnO was formed on a float glass substrate under the same method and conditions as in Example 3. The film thickness of each film was the same as in Example 3.

[Comparative Example 5] A three-layer film of ZnO / Ag / Zn (barrier layer) / ZnO was formed on a float glass substrate under the same method and conditions as in Example 3. The film thickness is 4
It was set to 0 nm, 10 nm, 5 nm, and 80 nm. Subsequently, in the same manner, Ag (fourth layer), Zn (barrier layer), and ZnO (fifth layer) of 10 nm and 5 n, respectively.
m, 10 nm was formed into a film.

The wear resistance of the film surface of the various Low-E glasses thus obtained was examined by a Taber wear test and a wear test using powder. The results are shown in Table 1. Table 1
The column A indicates the change in visible light transmittance after the Taber test (unit:
%) Is shown. Column B of Table 1 shows the presence or absence of film surface flaws after the abrasion test.

The Taber test was performed under a load of 500 g and a rotation speed of 100 rotations. The change in visible light transmittance before and after the Taber test was measured by a 304 type simple transmittance meter manufactured by Asahi Bunko Co., Ltd.

A wear test using powder was conducted as follows. That is, the prepared Low-E glass was fixed with the film surface facing upward. Sprinkle the powder from above,
Another normal float glass plate was stacked. A load (150 g / cm ² ) was applied to the upper glass plate, and the glass plate was reciprocated with a constant stroke.

[0044]

[Table 1]

[0045]

Industrial Applicability The Ag-based Low-E glass of the present invention enables unmanned and automated production. In particular, it is possible to place a bare plate on the production line and remove the plate from the production line without any operator, and the production tact and the cost can be reduced.

Further, S used as a protective coat in the present invention
Since an oxide film containing an oxide containing n and Si as the main component does not have a risk of arcing during sputtering and has a high film formation rate, the target for this oxide film should be placed at the end of the production line for sputtering. This enables continuous production in the 1-pass mode.

Since the oxide film containing an oxide containing Sn and Si as a main component has a variable refractive index in the range of 1.5 to 2.0, a film having a low refractive index is used as the protective coat. Therefore, the optical characteristics such as color tone and L
The ow-E performance can be minimized.

[Brief description of drawings]

FIG. 1 is a sectional view of a functional article according to Examples 1 and 5 of the present invention.

FIG. 2 is a sectional view of a functional article of Example 2 of the present invention.

FIG. 3 is a sectional view of a functional article according to Example 3 of the present invention.

FIG. 4 is a sectional view of a functional article according to Example 4 of the present invention.

[Explanation of symbols]

 1: Transparent substrate 2: Transparent oxide layer 3: Ag layer 4: Metal barrier layer 5: Oxide film containing an oxide containing Sn and Si as a main component

Claims (5)

[Claims] 1. A functional article in which a transparent oxide layer and an Ag layer are sequentially laminated on a transparent substrate to form a total of (2n + 1) layers (n ≧ 1). S
A functional article, wherein an oxide film containing an oxide containing n and Si as a main component is formed. 2. The functional article according to claim 1, wherein a metal film barrier layer is formed between the Ag layer and the transparent oxide layer formed thereon. 3. The functionality according to claim 1 or 2, wherein the oxide film containing an oxide containing Sn and Si as a main component has a refractive index of visible light of 1.5 to 2.0. Goods. 4. The proportion of Sn in the oxide film containing the oxide containing Sn and Si as a main component is 5 to 95% in atomic ratio.
The functional article according to any one of claims 1 to 3, wherein 5. The functional article according to claim 1, wherein the oxide film containing an oxide containing Sn and Si as a main component has a thickness of 1 to 50 nm.