JP6611192B2 - Glass plate with low reflection coating and laminated glass using the same - Google Patents

Description

  The present invention relates to a glass plate with a low reflection coating and a laminated glass using the same.

  Conventionally, a thin film is formed by dry coating such as vapor deposition or sputtering on an inorganic oxide such as titanium oxide or silicon oxide on a substrate such as glass or plastic, and an optical multilayer film is formed by light interference such as antireflection coating. The optical design is a two-layer structure in which a high refractive index layer / low refractive index layer (optical thickness is λ / 4-λ / 4) are sequentially laminated from the surface of the substrate, and a low refractive index layer. A four-layer structure in which a high refractive index layer and a high refractive index layer are alternately repeated is known (for example, Patent Document 1). The antireflection coating disposed on the transparent substrate has a function of reducing light reflection, that is, a function of increasing light transmission. Thus, a substrate coated in this way tends to have a large ratio of transmitted light to reflected light, which improves the visibility of the object behind it. Such anti-reflective (AR) coatings are widely used in applications such as electronic equipment, lighting, appliances, architecture and displays.

  In order to further impart physical strength to a substrate having such an antireflection coating, a hard coat layer is laminated on the substrate, and a high refractive index layer and a low refractive index layer are formed on the hard coat layer. A laminated body in which layers are stacked has also been proposed (Patent Document 2).

  In addition, in the base material having an antireflection coating, when tempered glass or double tempered glass is used as the glass of the base material, the quality changes due to heat treatment at the time of manufacture, so that the quality change is prevented. A method of applying an antireflection coating to glass of a substrate and then simultaneously heat-treating the glass and the antireflection coating (Patent Document 3), and a coated article including the antireflection coating obtained by the method have been proposed (patent) Reference 4).

Japanese Patent Laid-Open No. 08-337441 JP 2001-059902 A Special table 2013-54441 gazette Special table 2013-542457 gazette

  However, the conventional glass plate with a low reflection coating has a large change due to the angle of the reflection color tone, which is particularly problematic when used in an exhibition room or a showcase of a museum or an art museum.

  An object of the present invention is to provide a glass plate with a low reflection coating having a high visible light transmittance, a low visible light reflectance, and a small angle dependency of the reflection color tone.

The glass plate with a low reflection coating of the present invention comprises a glass plate and a low reflection coating,
Low reflection coating
A medium refractive index layer composed of a p-layer disposed on a glass plate;
A high refractive index layer disposed on the middle refractive index layer;
Having a low refractive index layer disposed on the high refractive index layer,
Regarding the refractive index at a wavelength of 550 nm, the following formulas (I), (II), (III) and (IV)
n _s <n _{m (p)} (I)
n _{m (1)} <n _h (II)
n _h > n _l (III)
n _{m (p)} −n _s ≦ 0.40 (IV)
(In the formula, n _s represents a refractive index of the glass plate, n m _(p) represents the refractive index of the medium refractive index layer closest to the glass plate (M _{p layer),} n m ₍₁₎ high refractive The refractive index of the middle refractive index layer (M ₁ layer) closest to the refractive index layer is represented, n _h represents the refractive index of the high refractive index layer, n _l represents the refractive index of the low refractive index layer, and p is 2 or more. Represents the natural number of
The filling,
The refractive index of each medium refractive index layer is larger than the refractive index of the medium refractive index layer on the side close to the glass plate among the adjacent medium refractive index layers,
The difference in refractive index between the layers from the middle refractive index layer to the high refractive index layer closest to the glass plate is 0.45 or less.

  The laminated glass with a low-reflection coating of the present invention includes two glass plates with the low-reflection coating of the present invention, and two glass plates with a low-reflection coating are disposed so that the low-reflection coating is exposed to the outside. Is.

  The glass plate with a low reflection coating of the present invention has a high visible light transmittance, a low visible light reflectance, and can suppress a change in reflected color tone even when the incident angle changes. In addition, the laminated glass with a low reflection coating of the present invention including a glass plate with a low reflection coating has a high visible light transmittance, a low visible light reflectance, and can suppress a change in reflection color tone even when the incident angle changes. it can.

It is sectional drawing which shows typically one embodiment of the glass plate with a low reflection coating of this invention. It is sectional drawing which shows typically other one embodiment of the glass plate with a low reflection coating of this invention. It is sectional drawing which shows typically one embodiment of the laminated glass of this invention.

  The glass plate with a low reflection coating of the present invention comprises a glass plate and a low reflection coating. As an example of the glass plate with a low reflection coating of the present invention, FIG. 1 shows the configuration of a glass plate with a low reflection coating when the middle refractive index layer is two layers (p = 2). As shown in FIG. 1, the low reflection coating 3 includes, for example, a medium refractive index layer 4 composed of two layers disposed on a glass plate 2 and a high refractive index disposed on the medium refractive index layer 4. It has a layer 5 and a low refractive index layer 6 disposed on the high refractive index layer 5.

The glass plate 1 with a low reflection coating of the present invention has the following formulas (I), (II), (III) with respect to the refractive index at a wavelength of 550 nm (hereinafter, the refractive index in the present invention represents the refractive index at a wavelength of 550 nm). ) And (IV).
n _s <n _{m (p)} (I)
n _{m (1)} <n _h (II)
n _h > n _l (III)
n _{m (p)} −n _s ≦ 0.40 (IV)
(In the formula, n _s represents a refractive index of the glass plate, n m _(p) represents the refractive index of the medium refractive index layer closest to the glass plate (M _{p layer),} n m ₍₁₎ high refractive The refractive index of the middle refractive index layer (M ₁ layer) closest to the refractive index layer is represented, n _h represents the refractive index of the high refractive index layer, n _l represents the refractive index of the low refractive index layer, and p is 2 or more. Is a natural number.)

Refractive index n _s of the glass plate 2 used in the present invention is not particularly limited as long as it satisfies the above formula (I) and (IV), for example, a 1.35 to 1.65, preferably 1.40 to 1 .60, more preferably 1.45 to 1.55.

The refractive index n _h of the high refractive index layer 5 used in the present invention is not particularly limited as long as the above formulas (II) and (III) are satisfied, but is preferably 2.0 or more, more preferably 2.20 or more, and 2. 30 or more is more preferable. The refractive index n _h of the high refractive index layer 5 is not particularly limited, but is preferably 2.80 or less in order to suppress the angle dependency of the reflected color tone. The refractive index can be adjusted, for example, by changing the component ratio of materials described later.

The refractive index n ₁ of the low refractive index layer 6 used in the present invention is not particularly limited as long as the above formula (III) is satisfied, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.55, More preferably, 1.44 to 1.50. The refractive index can be adjusted, for example, by changing the component ratio of materials described later.

The refractive index of the medium refractive index layer 4 used in the present invention is not particularly limited as long as the above formulas (I), (II) and (IV) are satisfied, but the medium refractive index layer (M ₁ layer) closest to the high refractive index layer. ) refractive index n _{m (1 in)} is preferably from 1.80 to 2.20, 1.80 to 2.15 is more preferable. Refractive index layer adjacent to the M ₁ layer refractive index of (M _{2 layers)} n _{m (2)} is preferably from 1.60 to 1.90, 1.60 to 1.85 is more preferable. The refractive index can be adjusted, for example, by changing the component ratio of materials described later.

The relationship between the refractive index _ns of the glass plate 2 and the refractive index _{nm (p)} between the medium refractive index layer closest to the glass plate 2 satisfies the above formula (IV). n _{m (p)} -n _s is preferably 0.35 or less, more preferably 0.30 or less.

  The number of layers (p) of the medium refractive index layer is particularly limited as long as it is a natural number of 2 or more from the viewpoint that high visible light transmittance and low visible light reflectance can be obtained and the angle dependency of the reflection color tone can be reduced. Although not, 2-10 are preferable, 2-5 are more preferable, and 2-3 are more preferable.

In the glass plate with a low reflection coating of the present invention, the refractive index of each medium refractive index layer is larger than the refractive index of the medium refractive index layer on the side close to the glass plate among the adjacent medium refractive index layers. For example, in a glass plate with a low reflection coating including three (p = 3) medium refractive index layers, the refractive index of each medium refractive index layer is _{nm (3)} < _{nm (2)} < _{nm (1 ). )} Is satisfied. In a glass plate with a low-reflective coating including four (p = 4) medium refractive index layers, the refractive index of each medium refractive index layer is _{nm (4)} < _{nm (3)} < _{nm (2)} <n _Satisfies the relationship of _{m (1)} . That is, the refractive index of the middle refractive index layer of the kth (k is an arbitrary natural number from p to 2), where the middle refractive index layer closest to the high refractive index layer is first, is mn _(k) < _{nm ( Satisfy} the relationship of _k-1) .

In the glass plate with a low reflection coating of the present invention, the refractive index difference between the layers from the medium refractive index layer closest to the glass plate to the high refractive index layer (H layer) is 0.45 or less, both More preferably, it is 0.43 or less. Each interlayer means, for example, when there are two middle refractive index layers, the M ₂ layer and the M ₁ layer, and the M ₁ layer and the H layer.

  In the case where the middle refractive index layer is two layers (p = 2), the refractive index difference between the layers from the glass plate to the high refractive index layer is preferably 0.14 or more, preferably 0.15 or more. It is more preferable that

The glass plate 2 used in the present invention may be a mass-produced general-purpose composition glass plate, typically a glass plate (float glass) made of soda lime silica glass manufactured by the float process, etc. Although it is not particularly limited as long as it has the effect of the invention, it is possible to increase the visible light transmittance when a low-reflection coating is laminated. From the point of mass% converted to Fe ₂ O ₃ , the content of iron oxide is 0.00. The glass plate which is 020% or less is preferable. A commercially available product may be used as the glass plate having an iron oxide content of 0.020% by mass or less. Examples of commercially available products include Optiwhite (refractive index: 1.52, manufactured by Nippon Sheet Glass). In the present invention, visible light means light in the wavelength range of 380 to 780 nm.

  The thickness of the glass plate 2 is not particularly limited and can be appropriately changed according to the required size, durability, etc., but is preferably about 3.0 to 12 mm.

  The thickness of the low refractive index layer 6 varies depending on the type of material constituting the low refractive index layer, the configuration of the layer, and the like, and is not particularly limited, but is preferably 70 to 150 nm, more preferably 75 to 130 nm, and 78 to 110 nm. More preferably, 80-100 nm is especially preferable. In the present invention, the “thickness” of each layer means the geometric layer thickness. The geometric layer thickness means a value measured by TEM (transmission electron microscope) observation of the layer cross section.

As the material of the low refractive index layer 6 is not particularly limited, SiO _2, aluminum-doped SiO ₂ (SiO _2: Al) and the like. These may be used alone or in combination of two or more. The low refractive index layer 6 preferably contains SiO ₂ as a main component, and more preferably one or more selected from the group consisting of SiO ₂ and aluminum-doped SiO ₂ . In the aluminum-doped SiO ₂ , the aluminum content is preferably 15% by mass or less in terms of aluminum converted to Al ₂ O ₃ . When the low refractive index layer 6 includes SiO ₂ as a main component, components other than SiO ₂ are not particularly limited. The “main component” means a component that is contained most by weight.

  The thickness of the high refractive index layer 5 varies depending on the type of material constituting the high refractive index layer, the structure of the layer, and the like, and is not particularly limited, but is preferably 1 to 50 nm, more preferably 2 to 40 nm, and more preferably 5 to 35 nm. More preferably, 10-30 nm is especially preferable.

  The material for the high refractive index layer 5 is not particularly limited, and examples thereof include oxides such as indium, zirconium, cerium, titanium, tantalum, niobium, and tin. The high refractive index layer 5 preferably contains titanium oxide or niobium oxide as a main component, and more preferably consists of titanium oxide or niobium oxide. When the high refractive index layer 5 includes titanium oxide or niobium oxide as a main component, components other than titanium oxide or niobium oxide are not particularly limited.

The total thickness of the medium refractive index layer can be appropriately changed according to the type of material constituting the layer, the configuration of the layer (number of p), and the like, and is not particularly limited, but is preferably 70 to 250 nm, more preferably 90 to 200 nm. Preferably, it is 110-160 nm.
The thickness of the M ₁ layer 7 is not particularly limited, but is preferably 50 to 150 nm, more preferably 60 to 120 nm, and still more preferably 70 to 100 nm. The thickness of the M ₂ layer is not particularly limited, but is preferably 20 to 100 nm, more preferably 30 to 80 nm, and further preferably 40 to 60 nm.

The material of the M ₁ layer is not particularly limited, but is an oxide of zinc-tin alloy (ZnSnOx); zinc oxide (zinc oxide (ZnO), or zinc oxide doped with tin, aluminum, silicon, etc. (ZnO) : Sn, ZnO: Al, ZnO: Si, etc.); Tin oxide (tin oxide (SnO ₂ ), or tin oxide doped with zinc, aluminum, silicon, etc. (SnO ₂ : Zn, SnO ₂ : Al, SnO) ₂ : Si and the like)); titanium oxide doped with silicon and the like (TiO ₂ : Si and the like), silicon nitride (SiNx) and the like. These may be used alone or in combination of two or more. The M ₁ layer preferably contains one or more selected from the group consisting of the aforementioned oxides of zinc and tin, zinc oxide, tin oxide, and silicon nitride as the main component, Zinc and tin alloy oxide (ZnSnOx); zinc oxide (ZnO); tin oxide or aluminum doped zinc oxide (ZnO: Sn, ZnO: Al); tin oxide (SnO ₂ ); zinc doped More preferably, it is made of either tin oxide (SnO ₂ : Zn); silicon-doped titanium oxide (TiO ₂ : Si) or silicon nitride (SiNx). When the M ₁ layer contains, as a main component, one or more selected from the group consisting of the aforementioned zinc oxide, tin oxide, titanium oxide doped with silicon, etc., and silicon nitride, other than the above components These components are not particularly limited as long as the effects of the present invention are not impaired.
In the low reflection coating of the present invention, “consisting essentially of components” means other than that which does not affect the properties of the product of the present invention (glass plate with low reflection coating and laminated glass using the same). In other words, the content of the other atoms and impurities is preferably less than 1.0% by mass, and more preferably 0.50% by mass or less. Preferably, it is more preferable to set it as 0.10 mass% or less.

The material of the M ₂ layer is not particularly limited, but is a mixed oxide of titanium and silicon (TiSiOx), a mixed oxide of zinc and silicon (ZnSiOx), a mixed oxide of tin and silicon (SnSiOx), zinc and aluminum. Examples thereof include an oxide of an alloy (ZnAlOx), an oxide of an alloy of tin and aluminum (SnAlOx), and an oxynitride of silicon (SiOxNy). These may be used alone or in combination of two or more. The M ₂ layer is preferably one containing at least one selected from the group consisting of the aforementioned mixed oxides and alloy oxides as a main component, and is substantially a mixed oxide of titanium and silicon (TiSiOx), zinc More preferably, it is made of any one of a mixed oxide of Zn and silicon (ZnSiOx), a mixed oxide of tin and silicon (SnSiOx), and an oxynitride of silicon (SiOxNy). Components other than the above components of the M ₂ layer are not particularly limited as long as the effects of the present invention are not impaired.

As another embodiment of the present invention, FIG. 2 shows a glass plate with a low reflection coating having three medium refractive index layers. Refractive index layer adjacent to M ₂ layer 8 refractive index n _{m (3)} of (M ₃ layer 9) is preferably from 1.50 to 1.70, 1.52 to 1.68 is more preferable. Other than the M ₃ layer (glass plate, M ₁ layer, M ₂ layer, high refractive index layer, low refractive index layer, and conditions between each layer), the same ones as in the embodiment of FIG. 1 can be used.

The thickness of the M ₃ layer can be appropriately changed according to the type of material constituting the layer, the structure of the layer (number of p), and the like, and is not particularly limited, but is preferably 5 to 60 nm, more preferably 10 to 50 nm, More preferably, it is 15-40 nm.

  When the middle refractive index layer is three layers, it is not particularly limited, but since the fluctuation due to the angle of the reflection color tone can be suppressed, the refractive index difference between each layer from the glass plate to the high refractive index layer is 0.09 or more. It is preferable that it is 0.10 or more, and it is more preferable that it is 0.10 or more.

The material of the M ₃ layer is not particularly limited, but aluminum oxide (aluminum oxide (Al ₂ O ₃ ); or aluminum oxide doped with zinc, tin, silicon, or the like (Al ₂ O ₃ : Zn, Al ₂ O) ₃ : Sn, Al ₂ O ₃ : Si, etc.); silicon-rich mixed oxide (titanium, zinc, tin, etc. and silicon mixed oxide (SiTiOx, SiZnOx, SiSnOx, etc.)); silicon oxynitride (SiOxNy) and the like. These may be used alone or in combination of two or more.
The M ₃ layer is preferably one containing at least one selected from the group consisting of the above-mentioned mixed oxides and alloy oxides as a main component, and is substantially aluminum oxide (Al ₂ O ₃ ); zinc or tin. More preferably, it is made of any one of silicon-doped aluminum oxide (Al ₂ O ₃ : Zn, Al ₂ O ₃ : Sn, Al ₂ O ₃ : Si); silicon oxynitride (SiOxNy). Components other than the above components of the M ₃ layer are not particularly limited as long as the effects of the present invention are not impaired.

  In the glass plate with a low reflection coating of the invention, the low reflection coating may be laminated on the glass plate, and the low reflection coating may be formed on one side or may be formed on both sides.

  The method for producing a glass plate with a low reflection coating according to the present invention is not particularly limited, and is formed on a glass plate as a base material by a physical vapor deposition method such as a well-known sputtering method or a chemical vapor deposition method such as a vapor deposition (CVD) method. It can be produced by forming a low reflection coating.

  The glass plate with a low reflection coating of the present invention preferably has a visible light reflectance of 5.0% or less as defined in JIS R 3106: 1998 at both incident angles of 5 ° and 30 °. The method for measuring the visible light reflectance is as described in Examples described later. In the present invention, the angle indicates an angle when the vertical incident light on the low reflection coating surface side is 0 °.

  The glass plate with a low reflection coating of the present invention preferably has a visible light transmittance of 93.5% or more as defined in JIS R 3106: 1998 at both incident angles of 5 ° and 30 °. The method for measuring the visible light transmittance is as described in Examples described later.

  In the glass plate with a low reflection coating of the present invention, the reflection color tone (Rcolor) a * is usually in the range of −3.0 to 0.3 at both incident angles of 5 ° and 30 °, preferably −2. It is the range of 0-0.2, More preferably, it is the range of -1.0-0. In the glass plate with a low reflection coating of the present invention, b * of reflection color tone (Rcolor) is usually in the range of −3.0 to 3.0 at both incident angles of 5 ° and 30 °, preferably − The range is from 2.0 to 2.0, and more preferably from -1.0 to 1.0. a * and b * are chromaticities in the CIE1976 color system (L * a * b * color space; hereinafter referred to as “L * a * b * color system”) measured with a spectrocolorimeter. L *, a *, b *). a * and b * mean the value of the coating surface reflection when the glass plate with a low reflection coating is formed on one side.

In the glass plate with a low reflection coating of the present invention, the difference (Δa *) between the reflection color tone a * at an incident angle of 5 ° and the reflection color tone a * at an incident angle of 30 ° is preferably −0.5 to 0.8. More preferably, it is in the range of -0.3 to 0.5. In a glass plate with a low reflection coating, the difference (Δb *) between the b * of the reflected color tone at an incident angle of 5 ° and the b * of the reflected color tone at an incident angle of 30 ° is preferably in the range of −0.5 to 1.0. Yes, more preferably in the range of -0.1 to 0.6. In the glass plate with a low reflection coating of the present invention, the following formula (V)
Δc * = {(Δa *) ² + (Δb *) ² } ^1/2 (V)
(In the formula, Δa * and Δb * represent the color difference of the reflection color tone between the incident angles of 5 ° and 30 ° measured with a spectrocolorimeter.)
Δc * represented by is preferably in the range of 0 to 1.3, more preferably in the range of 0 to 1.0.

  As another aspect of the present invention, for example, a laminated glass with a low reflection coating as shown in FIG. The laminated glass 11 shown in FIG. 3 is a laminated glass in which both film surfaces are used externally (embodiment in which the low reflection coating is disposed on the outside). The laminated glass of the present invention includes two glass plates with the low reflection coating of the present invention described above. In the laminated glass of the present invention, two glass plates with a low reflection coating are disposed so that the low reflection coating 3 is exposed to the outside. The laminated glass of the present invention has an intermediate film 10.

  The interlayer film used for the laminated glass of the present invention is not particularly limited, and a known film can be used. As an intermediate film, the intermediate film containing a polyvinyl acetal resin, a plasticizer, etc. is mentioned, for example. It does not specifically limit as a polyvinyl acetal resin, For example, a polyvinyl butyral (PVB) resin etc. are mentioned. The plasticizer is not particularly limited, and examples thereof include triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), and tetraethylene glycol di-2-ethyl. Examples include butyrate (4GH) and tetraethylene glycol-di-2-ethylhexanoate (4GO).

  The laminated glass of the present invention may be manufactured by laminating the above-described glass plate with a low reflection coating (single plate) of the present invention by a known method, and a low reflection coating is formed on both surfaces of a commercially available laminated glass. You may manufacture by doing. The low reflection coating in the laminated glass may be formed on one side of the glass plate or may be formed on both sides.

  The laminated glass with a low reflection coating of the present invention has a JIS R at both incident angles of 5 ° and 30 ° in the case where the low reflection coating is disposed on the outside as shown in FIG. 3106: The visible light reflectance specified in 1998 is preferably 2.0% or less, and more preferably 1.4% or less. The method for measuring the visible light reflectance is as described in Examples described later.

  The laminated glass with a low reflection coating of the present invention has a visible light transmittance defined in JIS R 3106: 1998 at both incident angles of 5 ° and 30 ° when a glass plate having a thickness of 5.0 mm is used as a substrate. What is 95.5% or more is preferable. The method for measuring the visible light transmittance is as described in Examples described later.

  The laminated glass with a low reflection coating of the present invention has a reflection color tone (Rcolor) a * in the range of −10 to 10 at both incident angles of 5 ° and 30 °, preferably −5.0 to 5. It is the range of 0, More preferably, it is the range of -5.0-0. In the laminated glass of the present invention, the b * of the reflected color tone (Rcolor) is usually in the range of −10 to 10 at both incident angles of 5 ° and 30 °, preferably −5.0 to 5.0. It is a range, More preferably, it is the range of 0-5.0.

  In the laminated glass of the present invention, the color difference (Δa *) between the reflection color tone a * at an incident angle of 5 ° and the reflection color tone a * at an incident angle of 30 ° is usually in the range of 0 to 10, preferably 0 to 6. .5. In the laminated glass of the present invention, the color difference (Δb *) between the reflection color tone b * at an incident angle of 5 ° and the reflection color tone b * at an incident angle of 30 ° is usually in the range of −5.0 to 5.0, Preferably it is the range of -3.0-3.0.

In the laminated glass of the present invention, the following formula (V)
Δc * = {(Δa *) ² + (Δb *) ² } ^1/2 (V)
(In the formula, Δa * and Δb * represent the color difference of the reflection color tone between the incident angles of 5 ° and 30 ° measured with a spectrocolorimeter.)
Is usually in the range of 0 to 10.0, and is preferably in the range of 0 to 5.0 from the viewpoint that the angle dependency of the reflected color tone is low.

  The present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention are exhibited.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge.

  In the following examples and comparative examples, as the glass plate of the base material, highly transmissive glass (trade name: Optiwhite, iron oxide content: 0.020% by mass or less, refractive index: 1.52, 5.0 mm Thick, manufactured by Nippon Sheet Glass).

Example 1
Two layers of a medium refractive index layer, a high refractive index layer, and a low refractive index layer were formed on a high transmission glass plate having a thickness of 5 mm by a reactive sputtering method. Specifically, a glass plate with a low reflection coating was produced as follows.

A highly transmissive glass plate is set in an in-line magnetron sputtering apparatus (hereinafter simply referred to as “sputtering apparatus”) having a plurality of chambers through a holder. Next, the pressure in the chamber was reduced to 10 ⁻⁶ Torr. Although a rotary pump and a cryopump are used for decompression, a turbo molecular pump or an oil diffusion pump may be used instead of the cryopump. Subsequently, a Ti—Si alloy target having a Ti: Si atomic ratio of 1: 2 was used, O ₂ gas was introduced into the chamber, and the gas pressure was 5 mTorr (5 × 10 ⁻³ Torr) by reactive sputtering. They were formed TiSiOx layer (M ₂ layers).

Next, the M ₁ layer is formed. The glass plate formed of M ₂ layers, with a different chamber of a sputtering apparatus, using a Zn-Sn alloy target Zn52 wt% Sn48 wt%, the O ₂ gas at a gas pressure of the introduced 5 mTorr in the chamber, It was formed ZnSnOx layer (M ₁ layer) by reactive sputtering.

Next, a high refractive index layer (H layer) is formed. The glass plate formed of M ₁ layer, in a further chamber of the sputtering apparatus, using a Ti metal target, the O ₂ gas at a gas pressure of the introduced 5 mTorr in the chamber, the TiO ₂ layer by reactive sputtering Formed.

Next, a low refractive index layer (L layer) is formed. Using a Si-Al alloy target containing 10% by mass of Al in a further chamber of the sputtering apparatus, a glass plate with a high refractive index layer formed was introduced with O ₂ gas into the chamber and a gas pressure of 5 mTorr. Then, a SiO ₂ : Al layer was formed by reactive sputtering.

In this way, a low reflection glass plate having a low reflection coating in which an M ₂ layer, an M ₁ layer, a high refractive index layer, and a low refractive index layer were sequentially laminated on one main surface of the glass plate was produced ( (See FIG. 1). It shows in Table 1 about the structure of each layer of the obtained glass plate with a low reflection coating, and thickness.

(Examples 2 to 11)
Examples 2 to 8 are examples in which the thickness of each layer is changed with the same layer configuration as in Example 1. Examples 9 and 10 are reactive co-reactions using a Zn metal target and the Si—Al alloy target used in the L layer of Example 1 instead of the Ti—Si alloy target as the middle refractive index layer M ₂ layer. ZnSiOx sputtering layer (M ₂ layer) was formed, the configuration of the other layers is an example of the same structure as in example 1. Co-sputtering is a method in which two or more targets are placed in one chamber and different power is applied to each target to perform sputtering. The ZnSiOx layer of Example 9 contains 70 atom% of ZnO, and the ZnSiOx layer of Example 10 contains 80 atom% of ZnO. Here, the atom% of ZnO refers to the 100 fraction of the atomic ratio of zinc atoms to metal atoms. Examples 9 and 10 are examples in which the refractive index of the M ₂ layer of Examples 1 to 8 was changed greatly. In Example 11, the middle refractive index layer is made into three layers, the M ₃ layer is formed by reactive sputtering using an Al metal target, and the other layers have the same structure as in Example 1, and the M ₂ layer has the same structure. This is an example in which the thickness is changed. It shows in Table 1 about the structure of each layer of the glass plate with a low reflection coating of Examples 2-11 obtained, and thickness. In forming each layer of Examples 1 to 11, sputtering was performed in a gas atmosphere necessary for the reaction. However, Ar gas can be mixed as necessary.

(Comparative Examples 1-6)
In Comparative Example 1, a highly transmissive glass was used as it was as a glass plate having no low reflection coating. Comparative Example 2 is an example in which the thickness of each layer is changed with the same configuration as in Example 1 except that the M ₂ layer is not provided. Comparative Example 3, instead of providing the M ₂ layer, as M ₁ layer, instead of the Zn-Sn alloy target, a reactive sputtering using a Zn-Al alloy target containing 12 atom% of Al to form a M ₁ layer, The other layer configurations are the same as those in the first embodiment, and the thickness of each layer is changed. Comparative Example 4 is as M ₂ layer, in place of the Ti-Si alloy target, Zn-Al alloy M ₂ layers were formed target in a reactive sputtering using a other layer configuration similar to that of Example 1 In this configuration, the thickness of each layer is changed. Comparative Example 5, instead of providing the M ₂ layer, as M ₁ layer, instead of the Zn-Sn alloy target, to form a M ₁ layer by reactive sputtering using Ti-Si alloy target, the configuration of the other layers This is an example in which the thickness of each layer is changed with the same layer configuration as in Example 1. Comparative Example 6 is not provided with the M ₂ layer, as M ₁ layer, Zn-Sn alloy in place of the target using the Si metal target, reactive with a mixed gas of O ₂ and N ₂ in place of the O ₂ gas The M ₁ layer is formed by sputtering, and the other layers have the same layer structure as that of Example 1, and the thickness of each layer is changed. The comparative example 6 has a coating which corresponds to Example 1 of JP-T-2013-542457. It shows in Table 1 about the structure and thickness of each layer of the glass plate of Comparative Examples 1-6.

[Evaluation of optical properties]
About the glass plate of an Example and a comparative example, based on JISR3106: 1998, visible light transmittance | permeability (Tvis (%)) and visible light reflectance (Rvis (%)) were measured. Specifically, the transmission spectrum or the reflection spectrum was measured using a visible range spectrophotometer with an integrating sphere, and the visible light transmittance and the visible light reflectance were calculated based on the calculation method of JIS R 3106: 1998. The results are shown in Table 2. The visible light reflectance is a value on the low-reflection coating surface side, and the visible light reflectance is a value including both the front surface reflected light and the back surface reflected light of the coating layer. In Table 2, “T: 0 °” means that the perpendicular incident light on the low reflection coating surface side was measured for the visible light transmittance, and “30 °” was the low reflection coating for the visible light transmittance and the visible light reflectance. It means that 30 ° incident light on the surface side (angle when the vertical is 0 °) was measured, and “R: 5 °” means 5 ° incident light (perpendicular to the low reflection coating surface side for visible light reflectance). This means that the angle when measured at 0 ° was measured. In Table 2, a * and b * represent values measured by a spectrocolorimeter, Δc * represents a value represented by the following formula (V), and Δa * and Δb * represent 5 ° incident light. And the color difference of reflection color tone between 30 ° and incident light.
Δc * = {(Δa *) ² + (Δb *) ² } ^1/2 (V)

  The glass plate with a low-reflection coating of the example had a visible light reflectance of 5.0% or less and a visible light transmittance of 93.9% or more at both incident angles of 5 ° and 30 °. In addition, the glass plate with a low reflection coating of the example has −1.0 ≦ a * when the reflection color tone (reflection on the coating surface) expressed in the L * a * b * color system is both 5 ° and 30 °. ≦ 0.1 and −0.3 ≦ b * ≦ 0.4. Further, in the glass plate with a low reflection coating of the example, the color difference in reflection color tone between 5 ° and 30 ° was −0.1 ≦ Δa * ≦ 0.8 and 0 ≦ Δb * ≦ 0.5. . Furthermore, the glass plate with a low reflection coating of the examples had a transmission color tone (coating surface reflection) of −0.4 ≦ a * ≦ −0.3 and 0 ≦ b * ≦ 0.1.

On the other hand, Comparative Example 1 having only a glass plate having no low reflection coating also had a visible light transmittance of 91.1% and a high visible light reflectance of 8.0%. In Comparative Examples 2 and 3 having only one medium refractive index layer, Δa * was larger than that of the example, and the color difference of reflection color tone depending on the angle was large with respect to a *. While the medium refractive index layer has a two-layer, the difference refractive index n _m and ₍₂₎ of the refractive index layers (M ₂ layer) in the most close to the refractive index n _s and the glass plate of the glass plate is 0.41 Comparative In Example 4, Δa * was larger than that of the example, and the color difference of reflection color tone depending on the angle was large with respect to a *. In Comparative Example 5 having only one medium refractive index layer, the visible light reflectance was as high as 5.5% compared to the Example. In Comparative Example 6 having only one medium refractive index layer, the color difference of the reflection color tone depending on the angle was larger with respect to a * and b * than in the example.

(Application examples)
Next, as an application mode of the present invention, a laminated glass will be described below.

(Examples 1B to 11B and Comparative Examples 1B to 6B)
Laminated glasses (Examples 1B to 11B and Comparative Examples 1B to 6B) including two glass plates (single plates) of Examples 1 to 11 and Comparative Examples 1 to 6 were produced. Specifically, a laminated glass was produced as follows.

First, two highly transmissive glass plates cut to a desired size and polished on the end surfaces were prepared. By the sputtering method described above, a low-reflective coating in which a medium refractive index layer, a high refractive index layer, a low refractive index layer, and a medium refractive index layer are sequentially laminated as in Examples 1 to 11 and Comparative Examples 1 to 6 is formed. did. The two low-reflection coating glass plates are sandwiched with a polyvinyl butyral (PVB) film as a thermoplastic intermediate film with the low-reflection coating on the outside, and bonded with an autoclave to obtain a laminated glass plate. . As a result, a laminated glass with low reflection coating (both film surfaces were used externally) in which two glass plates with low reflection coating were arranged so that the low reflection coating was exposed to the outside. About each obtained laminated glass (Examples 1B-11B and Comparative Examples 1B-6B), the characteristic was evaluated similarly to the glass plate of Examples 1-11 and Comparative Examples 1-6. The results are shown in Table 3. In Table 3, “5 °” means that 5 ° incident light (angle when the vertical is 0 °) was measured for visible light transmittance and visible light reflectance, and “30 °” was visible light. It means that 30 ° incident light (angle when vertical is 0 °) was measured for transmittance and visible light reflectance. In Table 3, a * and b * represent values measured with a spectrocolorimeter, Δc * represents a value represented by the following formula (V), and Δa * and Δb * are 5 °. It represents the color difference in reflection color tone between incident light and 30 ° incident light.
Δc * = {(Δa *) ² + (Δb *) ² } ^1/2 (V)

  The laminated glass of the example had a visible light reflectance of 1.7% or less and a visible light transmittance of 95.7% or more at both incident angles of 5 ° and 30 °. Moreover, the laminated glass of an Example WHEREIN: -9.2 <= a * <= 2.0 and 1.9 in the reflection color tone represented by L * a * b * color system in both 5 degrees and 30 degrees. ≦ b * ≦ 5.6. Further, in the laminated glass of the example, the color difference in reflection color tone between 5 ° and 30 ° was 1.1 ≦ Δa * ≦ 8.1 and −2.9 ≦ Δb * ≦ 2.9. Furthermore, the color difference of the reflection color tone represented by the said Formula (V) of the laminated glass of an Example was 1.17 <= c * <= 8.12.

  On the other hand, the laminated glass of Comparative Example 1B had a visible light reflectance of 7.6% or more. The laminated glasses of Comparative Examples 2B to 4B had a large change in reflection color tone, Δc * was 10.8 or more, and the angle dependency of the reflection color tone was high. The comparative example 5B had a visible light reflectance of 2.6% or more. In Comparative Example 6B, the change in the reflection color tone was large, Δc * was 11.4, and the angle dependency of the reflection color tone was high.

  From the above results, it was confirmed that the glass plate with a low reflection coating of the present invention and the laminated glass using the same have high visible light transmittance, low visible light reflectance, and small angle dependency of reflected color tone. .

  Since the glass plate with a low reflection coating of the present invention and the laminated glass using the same have high visible light transmittance, low visible light reflectance, and small angle dependency of reflection color tone, Useful when used in showcases.

Claims (12)

It has a glass plate and a low reflection coating,
Low reflection coating
A medium refractive index layer composed of a p-layer disposed on a glass plate;
A high refractive index layer disposed on the middle refractive index layer;
Having a low refractive index layer disposed on the high refractive index layer,
Regarding the refractive index at a wavelength of 550 nm, the following formulas (I), (II), (III) and (IV)
n _s <n _{m (p)} (I)
n _{m (1)} <n _h (II)
n _h > n _l (III)
n _{m (p)} −n _s ≦ 0.40 (IV)
(In the formula, n _s represents a refractive index of the glass plate, n m _(p) represents the refractive index of the medium refractive index layer closest to the glass plate (M _{p layer),} n m ₍₁₎ high refractive The refractive index of the middle refractive index layer (M ₁ layer) closest to the refractive index layer is represented, n _h represents the refractive index of the high refractive index layer, n _l represents the refractive index of the low refractive index layer, and p is 2 or more. Is a natural number.)
The filling,
The refractive index of each medium refractive index layer is larger than the refractive index of the medium refractive index layer on the side close to the glass plate among the adjacent medium refractive index layers,
The refractive index difference between the layers from the refractive index layer closest to the glass plate to the high refractive index layer is either Ri der 0.45 or less,
The refractive index of the M ₁ layer at a wavelength of 550 nm is 1.80 to 2.20,
The refractive index of the M ₂ layer at a wavelength of 550 nm is 1.60 to 1.90.
Glass plate with low reflection coating. It has a glass plate and a low reflection coating,
Low reflection coating
A medium refractive index layer composed of a p-layer disposed on a glass plate;
A high refractive index layer disposed on the middle refractive index layer;
Having a low refractive index layer disposed on the high refractive index layer,
Regarding the refractive index at a wavelength of 550 nm, the following formulas (I), (II), (III) and (IV)
n _s <N _{m (p)}               (I)
n _{m (1)} <N _h               (II)
n _h > N _l                   (III)
n _{m (p)} -N _s ≦ 0.40 (IV)
(In the above formula, n _s Represents the refractive index of the glass plate, n _{m (p)} Is the medium refractive index layer (M _p Layer) and n _{m (1)} Is the medium refractive index layer (M ₁ Layer) and n _h Represents the refractive index of the high refractive index layer, n _l Represents the refractive index of the low refractive index layer. p is a natural number of 2 or more. )
The filling,
The refractive index of each medium refractive index layer is larger than the refractive index of the medium refractive index layer on the side close to the glass plate among the adjacent medium refractive index layers,
The refractive index difference between each layer from the middle refractive index layer closest to the glass plate to the high refractive index layer is 0.45 or less,
A glass plate with a low reflection coating, wherein p is 3, and the difference in refractive index between each layer from the glass plate to the high refractive index layer is 0.09 or more. The refractive index of the low refractive index layer at a wavelength of 550 nm is 1.40 to 1.60,
The glass plate with a low reflection coating according to claim 1 or 2 , wherein the high refractive index layer has a refractive index of 2.0 or more at a wavelength of 550 nm. p is 2, a glass plate with low-reflective coating according to claim 1 or 3 refractive index difference between the layers from the glass plate to the high refractive index layer is either 0.14 or more. The refractive index of the M ₁ layer at a wavelength of 550 nm is 1.80 to 2.20,
The refractive index of the M ₂ layer at a wavelength of 550 nm is 1.60 to 1.90,
The glass plate with a low reflection coating according to claim 2 , wherein the M ₃ layer has a refractive index of 1.50 to 1.70 at a wavelength of 550 nm. In Fe ₂ O ₃ wt% in terms of the content of iron oxide contained in the glass plate, a glass with a low-reflection coating according to any one of claims 1 to 5, at 0.020% or less Board. The low refractive index layer contains SiO ₂ as a main component,
The glass plate with a low reflection coating according to any one of claims 1 to 6 , wherein the high refractive index layer contains titanium oxide or niobium oxide as a main component. The low refractive index layer is at least one selected from the group consisting of SiO ₂ and aluminum-doped SiO _{2. The} glass plate with a low reflection coating according to any one of claims 1 to 7 . In the medium refractive index layer,
M ₁ layer as the main component,
An oxide of an alloy of zinc and tin (ZnSnOx),
Zinc oxide (ZnO),
Zinc oxide doped with tin or aluminum (ZnO: Sn, ZnO: Al),
Tin oxide (SnO ₂ ),
Zinc-doped tin oxide (SnO ₂ : Zn),
Including at least one selected from the group consisting of silicon-doped titanium oxide (TiO ₂ : Si) and silicon nitride (SiNx),
M ₂ layer as the main component,
Mixed oxide of titanium and silicon (TiSiOx),
Mixed oxide of zinc and silicon (ZnSiOx),
The glass plate with a low reflection coating according to claim 1 or 4 , comprising at least one selected from the group consisting of a mixed oxide of tin and silicon (SnSiOx) and silicon oxynitride (SiOxNy). In the medium refractive index layer,
M ₁ layer as the main component,
An oxide of an alloy of zinc and tin (ZnSnOx),
Zinc oxide (ZnO),
Zinc oxide doped with tin or aluminum (ZnO: Sn, ZnO: Al),
Tin oxide (SnO ₂ ),
Zinc-doped tin oxide (SnO ₂ : Zn),
Including at least one selected from the group consisting of silicon-doped titanium oxide (TiO ₂ : Si) and silicon nitride (SiNx),
M ₂ layer as the main component,
Mixed oxide of titanium and silicon (TiSiOx),
Mixed oxide of zinc and silicon (ZnSiOx),
Mixed oxide of tin and silicon (SnSiOx),
Including one or more selected from the group consisting of silicon oxynitride (SiOxNy) and zinc-aluminum alloy oxide (ZnAlOx),
M ₃ layer as the main component,
Aluminum oxide (Al ₂ O ₃ ),
Aluminum oxide doped with zinc or silicon (Al ₂ O ₃ : Zn, Al ₂ O ₃ : Si)) or silicon oxynitride (SiOxNy)
The glass plate with a low-reflection coating according to claim 2 or 5 . Low reflection which contains two glass plates with a low reflection coating of any one of Claims 1-10 , and the two glass plates with a low reflection coating are arrange | positioned so that a low reflection coating may be exposed outside Laminated glass with coating. A glass plate with a low reflection coating according to any one of claims 1 to 10 ,
A glass plate with a low reflection coating, wherein the low reflection coating is provided on both major surfaces of the glass plate.

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