JPH1134216A - Laminate and glass laminate for window - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate near to a hue-free state and reduced in the change of an incident hue even if an incident angle is changed by successively providing first, second, third, fourth and fifth layers on a substrate and constituting the first, third and fifth layers of oxide and forming the second and fourth layers of a metal based on Ag and setting the thickness of the first layer to a specific value with respect to that of the fifth layer. SOLUTION: A laminate is constituted by successively providing first, second, third, fourth and fifth layers 1-5 on a substrate 11 from a substrate side and the first, third and fifth layers 1, 3, 5 are composed of oxide of at least one metal selected from a group consisting of Sn, Zn and Ti. The second and fourth layers 2, 4 are composed of a metal based on Ag. In this laminate, the thickness of the first layer is set to 60-90% of that of the fifth layer. When the thickness of the first layer is below 60% of that of the fifth layer, a laminate showing a gentle reflecting hue near to a hue-free state is not obtained and, when the thickness of the first layer exceeds 90 of that of the fifth layer, the film thicknesses of the oxide of the first and fifth layers 1, 5 becomes almost the same and the laminate reduced in the change of a reflecting hue even if an incident angle is changed can not be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more particularly, to a laminate having low heat radiation and high heat insulation.
The present invention relates to a laminate having a mild external color tone and having a small external color tone even when the incident angle is changed. In particular, Lo
wE glass (Low Emissivity Gla)
ss).

[0002]

2. Description of the Related Art In cold regions such as Hokkaido, a double glazing having a structure in which two glasses are laminated via an insulating air layer is used as a window glass. The double glazing is effective in taking in sunlight from the outside and blocking heat radiation from the room to the outside, thereby improving the indoor heat retention and reducing the heating load.

In recent years, two glass substrates 31a and 31b shown in FIG.
In a double-layer glass laminated so as to form a heat-insulating air layer 33 between a and 31b, a low-radiation coating 34 is disposed on the heat-insulating air layer 33 side of the indoor glass substrate 31b. A laminate using glass having high heat insulation called E glass has been used. This glass laminate transmits light having a wavelength of about 0.3 to 2.0 μm contained in sunlight and takes in sunlight into the room, while blocking heat conduction from the indoor side to the outdoor side by the heat insulating air layer. In this operation, the low radiation performance of the low radiation coating 34 can improve the heat retention and the heat insulation performance.

[0004] By the way, in a window glass used in a region that does not require heating of a room as in a cold region, for example, a window glass used in a warm region west of the Kanto region, rather than blocking radiation of heat from the room to the outside, it is more preferable. There is a demand for improving the cooling efficiency by blocking the flow of heat from the outside to the room, suppressing the heating of the room atmosphere by sunlight from the outside, and improving the cooling efficiency. Furthermore, not only window glasses for buildings and houses, but also window glasses for vehicles such as automobiles and trains, the area has been increased for the purpose of improving appearance, livability in a vehicle compartment, external visibility, and the like. Therefore, similarly, it is required to suppress the heating of the indoor atmosphere.

Therefore, as shown in FIG. 4, similar to the laminate shown in FIG. 3, two glass substrates 41a and 41a are provided.
b is sealed with the peripheral part 42, and the glass substrates 41a and 41
b, a laminated body using Low-E glass having a low-radiation coating 44 on the side of the heat-insulating air layer 43 of the outdoor glass substrate 41a in the double-layer glass laminated so as to form the heat-insulating air layer 43 therebetween. It is being used.

As a Low-E glass used for these laminates, a layer having high infrared reflection characteristics and a transparent dielectric layer having high visible light transmittance are sequentially laminated on a glass substrate. Various forms have been proposed. In these low-E glasses having a multilayer structure,
A film containing Ag as a main component is used as a film having infrared reflection characteristics, and ZnO, SnO
₂ , an oxide film such as TiO ₂ or a nitride film such as SiN _x is used.

However, a glass laminate using the above-described low-E glass having a multilayer structure as a glass substrate is a low-E glass.
Since the color tone is expressed by the light interference effect of the E film, the color tone of the reflected light viewed from the glass substrate side largely changes depending on the incident angle. Therefore, for example, there is an inconvenience that the appearance of a building with a window glass made of this glass laminate is different from that of a building viewed from the front and a case where the building is viewed obliquely at a different angle. Was.

Several proposals have been made to improve such disadvantages. For example, JP-A-7-165
No. 442 discloses a first dielectric material layer, a first layer based on a metal having infrared reflective properties, a second dielectric material layer, a second layer based on a metal having infrared reflective properties, and a third dielectric material. A transparent substrate having a continuous layer of material deposited thereon, wherein the thickness of the first metal-based layer is about 50-80% of the thickness of the second metal-based layer. Base materials have been proposed.

Japanese Patent Publication No. Hei 8-500061 discloses (a) a base coat made of an anti-reflective metal oxide applied to the surface of a substrate with a thickness not exceeding about 275 °;
(b) a first reflective metal layer applied on the base coat, (c) an intermediate layer made of an anti-reflective metal oxide applied on the first reflective metal layer, (d) A) a second reflective metal layer applied over said intermediate anti-reflective layer; and (e) an outer anti-reflective layer comprising a metal oxide retained over said second reflective metal layer. There has been proposed a coated substrate composed of a substrate having a coating film on the surface, comprising a reflective characteristic layer.

Japanese Patent Application Laid-Open No. 8-304601 discloses that a first layer of a transparent dielectric non-absorbent material having an optical thickness of 60 to 75 nm, a substrate adjacent to a substrate, and a geometric thickness of 9 to 11 nm. A second layer of transparent dielectric non-absorbent material having an optical thickness of 135-170 nm; a second layer of silver or silver alloy having a geometric thickness of 12-15 nm. A layer carrying a third layer of a transparent dielectric non-absorbent material having an optical thickness of 45 to 65 nm, wherein the coated substrate has a luminous transmittance TLC of greater than 70%, a solar of less than 47% Factor F
A coated substrate characterized by exhibiting a color purity at s, and a reflection normal to the opposing surface of 12% or less has been proposed.

Further, Japanese Patent Application Laid-Open No. 4-500184 discloses a first layer made of a dielectric material, a second layer made of a partially reflective material, a third layer made of a dielectric material, and a third layer made of a dielectric material. A fourth layer made of a dielectric material and a fifth layer made of a dielectric material, wherein each of the first, third, and fifth dielectric material layers has a refractive index of 1.7 to 2.7. Wherein the first and fifth layers have an optical thickness that is approximately 33% to 45% of the optical thickness of the third layer. Almost colorless solar control layered coatings have been proposed.

In Japanese Patent Application Laid-Open No. Hei 8-104547, a metal oxide film as a first layer, a film mainly composed of Ag as a second layer, and a third layer are formed on a glass plate in this order from the glass plate side. A heat-insulating glass in which a metal oxide film is formed as a fourth layer, a film containing Ag as a main component as a fourth layer, a metal oxide film as a fifth layer, and a protective film as a sixth layer if necessary. The material film is composed of one or more layers containing one or both of tin oxide and zinc oxide as a main component as a whole of the first layer, the third layer or the fifth layer, and the thickness of the third layer is Insulated glass having a thickness of 65 nm to 80 nm, a thickness of the second layer of 7 nm to less than 11 nm, and a thickness of the fourth layer of more than 11 nm to 14 nm is proposed.

Further, Japanese Patent Application Laid-Open No. 8-239245 discloses that, in a sputter-coated glass product in which a multilayer system is sputter-coated on a glass substrate, a) a thickness of about 300 to 550 ° from the glass substrate outward. Si ₃ N _{4 with}
B) a layer of nickel or nichrome having a thickness of about 7 mm or less; c) a layer of silver having a thickness of about 70-130 mm; and d) a layer of about 7 mm or less. a layer of nickel or nichrome having, e) a layer the Si ₃ N ₄ having a thickness of about 700~1100Å, f) a layer of nickel or nichrome having about 7Å or less than this thickness, g) about 70 A) a layer of silver having a thickness of about 190 °; h) a layer of nickel or nichrome having a thickness of about 7 ° or less; and i) a layer of Si ₃ N ₄ having a thickness of about 350-700 °. Sputter-coated glass articles having a multilayer system have been proposed.

However, these conventional laminates or materials having a multilayer structure are still insufficient in the property that the reflection color tone seen from the outside changes according to the incident angle, that is, the improvement of the incident angle dependence of the reflection color tone. Was not.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminate having a gentle external color tone and having a small change in the color tone of reflected light viewed from the substrate side even when the incident angle is changed. Is to do. Another object of the present invention is to provide a glass laminate for windows having high heat insulating properties, having a gentle appearance color tone, and having a small change in the color tone of reflected light viewed from the substrate side even when the incident angle is changed. Is to provide the body.

[0016]

In order to solve the above-mentioned problems, the present invention provides a substrate, a first layer made of an oxide, and a metal containing Ag as a main component on the substrate in this order from the substrate side. A third layer made of an oxide, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of an oxide, wherein the thickness of the first layer is a fifth layer. 60-90% of the thickness of
Is provided.

Adjusting the ratio of the thickness of the second layer to the thickness of the fourth layer in order to reduce the change in the reflection color tone due to the incident angle has already been proposed in Japanese Patent Application Laid-Open No. 7-165442. As described above, a sufficient effect has not yet been obtained. Therefore, the inventor of the present invention focused on not only the thickness ratio of the second layer and the fourth layer but also the thickness ratio of the oxide layer of the first layer and the fifth layer, and made intensive studies. . Therefore, as shown in FIG. 2, when viewed from the front (near the incident angle of 0 degree)
Indicate substantially the same reflection color tone (in the figure, the value of x on the CIE chromaticity coordinates is about 0.305 and the value of y is about 0.343), and the thickness of the oxide of the first layer is about 5th. A laminate having a thickness smaller than that of the oxide of the layer,
The change in the reflection color tone depending on the incident angle was compared between a laminate having a thickness smaller than the thickness of the oxide of the layer. As is clear from FIG. 2, it has been found that when the thickness of the first layer is smaller than the thickness of the fifth layer (curve A in the figure), the change in the reflection color tone due to the incident angle is smaller. . Based on this finding, it has been found that when the thickness of the first oxide layer is smaller than the thickness of the fifth layer, a laminate in which the change in the reflection color tone due to the incident angle is small can be obtained. It came to come to mind.

Hereinafter, the laminate of the present invention will be described in detail. The laminate of the present invention, as shown in FIG.
Basically, a first layer 1, a second layer 2, a third layer 3, a fourth layer 4, and a fifth layer 5 are sequentially provided on the base 11 from the base side.

In the laminate of the present invention, the substrate is not particularly limited, and examples thereof include a glass substrate. When the laminate of the present invention is used for window glass for buildings or vehicles, soda lime glass is generally used as the glass substrate.

In the laminate of the present invention, the first layer disposed on the substrate, the third layer disposed on the second layer, and the fifth layer disposed on the fourth layer Is not particularly limited, and may be made of any oxide material commonly used for this type of laminate. As a specific example of the first layer, the third layer and the fifth layer, at least one selected from the group consisting of Sn, Zn and Ti, which is a material frequently used as a coating material for window glasses for construction and vehicles. One example is a layer containing an oxide of one kind of metal. In particular, as the first layer, the third layer, and the fifth layer, a second layer or a fourth layer made of a metal containing Ag as a main component and formed on the upper layer of each layer is stably formed; A layer containing a Zn oxide is preferable because the second layer or the fourth layer is formed while having high crystallinity.

Further, the layer containing the oxide of Zn contains ZnO as a main component, since the internal stress in the layer is reduced and a layer having good adhesion to the substrate is obtained.
A layer containing at least one metal element selected from l, Cr, Ti, Si, B, Mg and Ga is particularly preferred. A layer containing ZnO as a main component, in particular, a layer containing ZnO and Al or a layer containing ZnO and Sn is compatible with a second layer or a fourth layer made of a metal containing Ag as a main component and formed on each layer. Is good. Further, a layer containing ZnO and Al is useful because Al is an inexpensive material and the film formation speed of the layer is high. Further, Sn is preferable because it is a relatively inexpensive material.

In the present invention, when the layer made of Zn oxide is a layer containing ZnO and the above-mentioned metal elements, the content ratio of these metal elements is preferably 1 to 10 at%, particularly 2 to 6 at%. It is preferred that If the content ratio of these metal elements is too large, the crystallinity of the oxide of Zn necessary for stabilization of the second layer or the fourth layer composed of a metal containing Ag as a main component and formed on the upper layer of each layer is reduced. Tend to.

In the laminate of the present invention, the first layer, the third layer and the fifth layer may be layers having the same component or composition or layers having different components and compositions. Further, each of the first, third, and fifth layers may have a structure in which a plurality of oxide layers are stacked. For example, the first layer may be a layer having a multilayer structure composed of ZnO and SnO ₂ . Forming all oxide layers with the same material is advantageous in that the number of targets can be reduced when forming each layer by a multi-pass method using an in-line sputtering apparatus.

In the laminate of the present invention, the second layer provided on the first layer and the fourth layer provided on the third layer are made of a metal containing Ag as a main component. A layer composed of only Ag, or a layer mainly composed of Ag,
This is a layer containing another metal element, for example, another metal element such as Pd, Au, or Cu. When the second layer or the fourth layer contains Ag and another metal element, the content ratio of the other metal element is A
0.3 to 10 at with respect to the total amount of g and other metal elements.
%. 0.3at% of other metal elements
If less than 10%, the effect of stabilizing Ag is reduced, and 10 at%
Even if it is excessive, the effect of stabilization decreases again. In particular, in the present invention, the second layer or the fourth layer is composed of P as another metal element.
A layer containing d is preferable because a layer having excellent chemical durability can be formed. When Pd is contained, A
Immobilization of g atoms, that is, reduction of Ag migration can be achieved. In the layer composed of Ag and Pd, when the amount of Pd added increases, the film formation rate decreases,
Visible light transmittance also decreases, and emissivity increases, Lo
This is not preferable as a wE film. for that reason,
The addition amount of Pd is suitably 5.0 at% or less. Further, when the amount of Pd added increases, the material cost when forming the second layer or the fourth layer significantly increases.
A range of about t% is appropriate.

In the laminate of the present invention, the second layer and the fourth layer may be layers composed of the same components or compositions, or layers composed of different components and compositions.
In addition, each of the second layer and the fourth layer may be a layer having a structure in which a plurality of metal layers are stacked. For example, the second layer may be a layer having a multilayer structure including Ag and Pd.

Further, in the laminate of the present invention, an interface between a layer composed of a metal containing Ag as a main component and a layer composed of an oxide, for example, an interface between a first layer and a second layer, and an interface between the second layer and the second layer. At the interface between the third layer, the interface between the third layer and the fourth layer, and the interface between the fourth layer and the fifth layer, a metal thin film or A barrier layer made of a nitride film (a layer that prevents oxidation of a layer made of a metal containing Ag as a main component) may be provided. In particular, a barrier is provided at the interface between the second and third layers and / or at the interface between the fourth and fifth layers.
The laminated body of the present invention in which the layers are provided includes a layer (third layer or fifth layer) made of an oxide on a layer (second layer or fourth layer) made of a metal containing Ag as a main component. When the layers are stacked in an atmosphere containing oxygen, it is effective in that a layer made of a metal containing Ag as a main component can be prevented from being oxidized by oxygen in the atmosphere.

As the metal thin film or nitride film forming the barrier layer, Ti, Zn, Ta, NiCr, SiN _x
Is preferable. Its film thickness is 1-5n
m is preferred. When the thickness is less than 1 nm, the function as a barrier layer is not sufficiently exhibited. On the other hand, when the thickness is more than 5 nm, problems such as a decrease in visible light transmittance of the laminate and an influence on the color tone occur. Here, if the SiN _x film is a perfect transparent nitride film, its thickness may exceed 5 nm.

In the laminate of the present invention, an overcoat layer may be further laminated on the fifth layer. It is preferable that a SnO ₂ layer containing Si is formed as the overcoat layer. The SnO ₂ layer containing Si has good compatibility with the layer containing ZnO as a main component, and is effective since a strong adhesion is obtained at the interface. The content ratio of Si to the total amount of Sn and Si in the SnO ₂ layer containing Si is preferably 5 to 95 at%. In particular, the content is preferably 30 to 90 at%, more preferably 40 to 90 at%.

The overcoat layer improves the function of preventing water from entering (water resistance). S to SnO ₂
When i is added, the formed film becomes a dense film from a crystalline structure to an amorphous structure. If the proportion of Si is too small,
The moisture resistance of the film decreases. In addition, the film approaches the crystalline state from the amorphous state and loses the smoothness of the film surface. On the other hand, if the proportion of Si is too large, arcing is likely to occur when the film is formed by the DC sputtering method, and the productivity is reduced. The thickness of the Sn-containing SnO ₂ layer is not particularly limited, but is required to be about 5 nm or more in order to improve the water resistance and the scratch resistance. The performance is improved. There is no particular upper limit on the thickness of the layer, but sufficient performance can be obtained with a thickness of 20 nm.

In the laminate of the present invention, the thickness of the first layer is 60 to 90% of the thickness of the fifth layer. If the thickness of the first layer is less than 60% of the thickness of the fifth layer, the difference between the two thicknesses becomes too large, so that a laminate having a gentle reflection color close to achromatic cannot be obtained. Further, when the thickness of the first layer exceeds 90% of the thickness of the fifth layer, the thickness of the oxide of the first layer and the thickness of the oxide of the fifth layer become substantially the same, and the incident angle However, it is not possible to obtain a laminate in which the change in the reflection color tone is small even if the value is changed.

In the laminate of the present invention, the thickness of the first layer is set to 60 to 90% of the thickness of the fifth layer, and
By setting the thickness of the second layer to 50 to 90% of the thickness of the fourth layer, the effect of reducing the change in the reflection color tone due to the incident angle can be further remarkable, which is preferable. In the laminate of the present invention, when the sum of the optical thicknesses of the first layer, the third layer, and the fifth layer is relatively thin, that is, 300 nm or less, the thickness of the first layer is changed to the thickness of the fifth layer. 6 of thickness
By setting the thickness of the third layer to 300% or more of the thickness of the first layer while setting the thickness to 0 to 90%, the effect of reducing the change in the reflection color tone due to the incident angle is made more remarkable. It is preferable because it can be performed.

In a first preferred embodiment of the laminate according to the present invention, the first to fifth layers have a thickness of 32 nm to 41 nm, respectively, and the geometrical shape of the second layer. The optical thickness of the third layer is 113 nm.
１４145 nm, geometric thickness of the fourth layer is 8 nm８12 n
m, and the optical thickness of the fifth layer is 45 nm to 60 nm. The laminate having the thickness of each layer in these ranges has a gentle reflection color tone close to achromatic color, and shows a characteristic that the reflection color tone from the substrate side is small even when the incident angle is changed. In addition, the low-E glass originally has high heat insulation properties, and has appropriate visible light transmittance and visible light reflectivity that does not hinder practical use as window glass for buildings and vehicles. Are better.

According to a second preferred embodiment of the laminate of the present invention, the first to fifth layers have a thickness of 41 nm to 50 nm, respectively, Target thickness is 6 nm to 9 nm, and the optical thickness of the third layer is 150 nm to
177 nm, the geometric thickness of the fourth layer is 11 nm to 15 n
m, and a configuration in which the optical thickness of the fifth layer is 62 nm to 74 nm. In this configuration, the first layer, the third layer,
Since the thickness of the fourth layer and the fifth layer is thicker than that of the above-described configuration, the change in the color tone when the thickness of the first layer, the third layer, and the fifth layer fluctuates is smaller than that of the above-described configuration. Therefore, it is preferable in that it can be manufactured stably.

According to a third preferred embodiment of the laminate of the present invention, the first layer to the fifth layer have thicknesses of 63 nm to 71 nm, respectively, and the geometrical shape of the second layer. The optical thickness of the third layer is from 165 nm to 9 nm, and the optical thickness of the third layer is from 165 nm to 9 nm.
187 nm, geometric thickness of the fourth layer is 10 nm to 14 n
m, and the optical thickness of the fifth layer is 72 nm to 82 nm. In this configuration, the thicknesses of the first layer, the third layer, and the fifth layer are further thicker than in the second preferred embodiment, and the thickness of the first layer, the third layer, and the fifth layer is changed. Since the change in color tone is even smaller than that of the above-described configuration, stable production can be achieved. Further, even if the thickness of the third layer is not more than 300% of the thickness of the first layer, the third layer has a gentle reflection color tone close to achromatic color, and the reflection color tone from the substrate side changes the incident angle. It shows the characteristic that the change is relatively small.

In the production of the laminate of the present invention, the first to fifth layers are formed by a conventional method for forming a layer composed of a metal, an alloy, a compound, etc. on a substrate whose surface has been cleaned. It can be performed by forming sequentially. The method for forming these layers is not particularly limited, and includes a vapor deposition method, CV
A method D, a sputtering method, or the like can be used. In particular, for a substrate having a large area such as a window glass, the DC sputtering method is effective in that the uniformity of the film thickness can be easily controlled and the productivity is excellent.

Further, according to the present invention, a plurality of glass substrates
The present invention provides a window glass laminate in which at least one glass substrate is a laminate according to the present invention, which is a glass laminate for windows formed by laminating through a heat insulating air layer. The laminate of the present invention is arranged on the outdoor side of the window glass laminate, and is arranged such that the surface having the first to fifth layers is on the side of the heat-insulating air layer. The window glass laminate of the present invention,
As it has high heat insulation, it has a mild color tone close to achromatic, and the color tone of the reflected light seen from the outdoor side changes little even when the incident angle is changed, so it is used as a window glass for buildings, vehicles, etc. It is suitable. For example, in the glass laminate having the configuration of FIG. 4, the one using the laminate of the present invention as the substrate 41 a has high heat insulation, has a mild outdoor reflection color tone close to achromatic, and The reflection color tone changes little even when the incident angle is changed.

[0037]

The present invention will be described more specifically with reference to the following examples and comparative examples.

(Example 1) Mechanical polishing using a brush
Polishing, washing with surfactant, rinsing with pure water
Next, 3 mm thick sodalas whose surface was cleaned
Set the glass plate in the sputtering device,
The glass laminate is manufactured by sequentially forming five layers of the above thickness.
Was. First layer 18.5 nm (optical thickness 37 nm) Second layer 7.5 nm Third layer 66 nm (optical thickness 132 nm) Fourth layer 9.5 nm Fifth layer 27 nm (optical thickness 54 nm) First layer, third layer As a layer and a fifth layer, 5 at%
Oxygen gas and argon gas using a Zn target
In a mixed gas atmosphere (oxygen / argon ratio is 10 /
In 1), the pressure is 2.2 mtorr, the input power is 2.0 W / c.
m^TwoSputtering under the condition of
And a layer containing Al was formed. In addition, the second layer and
And an Ag target containing 1 at% of Pd as a fourth layer
And pressure of 2.0 mtorr in an argon gas atmosphere.
r, input power 0.86 W / cm ^TwoUnder the condition of
To form a layer containing Ag as a main component and containing Pd
did.

Further, before forming the third and fifth layers, in order to prevent oxidation of the metal films of the second and fourth layers,
Using a Zn target containing 5 at% of Al and performing sputtering in an argon gas atmosphere under the conditions of a pressure of 2.0 mtorr and an input power of 0.2 W / cm ² ,
Zn and A at the interface between the layer and the third layer, and at the interface between the fourth layer and the fifth layer.
A barrier layer (thickness of about 3 nm) made of 1 metal was formed. This barrier layer will eventually be the third and fifth layers.
It became the same oxide layer as the layer.

The reflection color tone from the glass surface side of the obtained glass laminate was measured using ART-25G manufactured by JASCO Corporation.
Measurements were made using T at wavelengths of 380 nm to 780 nm at incident angles of 0 °, 20 °, 40 ° and 60 °. In this measurement, the reflection color tone at the incident angles of 0 ° and 60 ° (coordinate values in the CIE chromaticity coordinate diagram)
Was as follows. In the case of an incident angle of 0 ° (0.2986, 0.3455) In the case of an incident angle of 60 ° (0.3025, 0.3278) The color value represented by the coordinate value of the incident angle of 0 ° is not completely colorless, The color is slightly green. However, the greenish color tone gives a good impression to human eyes, and the external color tone is felt to be mild. In addition, the incident angle is 0 °
Comparing the case with the case of 60 °, the change in the value of x was +0.0039 and the change in the value of y was −0.0177.

Example 2 Five layers having the following thicknesses were sequentially formed in the same manner as in Example 1 except that the film thickness was changed, to produce a glass laminate. First layer 24 nm (optical thickness 48 nm) Second layer 7.5 nm Third layer 81.5 nm (optical thickness 163 nm) Fourth layer 13 nm Fifth layer 32 nm (optical thickness 64 nm) Glass of the obtained glass laminate The reflection color tone from the surface side,
The measurement was performed in the same manner as in Example 1. In this measurement result, the reflection color tone (CI
The coordinate values in the E chromaticity coordinate diagram were as follows. When the incident angle is 0 ° (0.3001, 0.3492) When the incident angle is 60 ° (0.3029, 0.3377) The reflection color tone at the incident angle 0 ° is the same as in the first embodiment.
It had a mild color tone. Also, comparing the case where the incident angle is 0 ° and the case where the incident angle is 60 °, the amount of change in the value of x is +
0.0028, the amount of change in the value of y was -0.0115.

(Example 3) Five layers having the following thicknesses were sequentially formed in the same manner as in Example 1 except that the film thickness was changed, to produce a glass laminate. First layer 34 nm (optical thickness 68 nm) Second layer 7.5 nm Third layer 88 nm (optical thickness 176 nm) Fourth layer 11.5 nm Fifth layer 38 nm (optical thickness 76 nm) Glass of the obtained glass laminate The reflection color tone from the surface side,
The measurement was performed in the same manner as in Example 1.

In the measurement results, the reflection color tones (coordinate values in the CIE chromaticity coordinate diagram) at the incident angles of 0 ° and 60 ° were as follows. In the case of an incident angle of 0 ° (0.2980, 0.3435) In the case of an incident angle of 60 ° (0.3020, 0.3280) The reflection color tone in the case of an incident angle of 0 ° is the same as in the first embodiment.
It had a mild color tone. Also, comparing the case where the incident angle is 0 ° and the case where the incident angle is 60 °, the amount of change in the value of x is +
The amount of change in the value of 0.0040, y, was -0.0155.

(Comparative Example 1) Five layers having the following thicknesses were sequentially formed in the same manner as in Example 1 except that the film thickness was changed, to produce a glass laminate. First layer 27.5 nm (optical thickness 55 nm) Second layer 7.5 nm Third layer 56 nm (optical thickness 112 nm) Fourth layer 9.5 nm Fifth layer 23 nm (optical thickness 46 nm)

The reflection color tone from the glass surface side of the obtained glass laminate was measured in the same manner as in Example 1. In the measurement results, the reflection color tones (coordinate values in the CIE chromaticity coordinate diagram) at the incident angles of 0 ° and 60 ° were as follows. When the incident angle is 0 ° (0.3005, 0.3427) When the incident angle is 60 ° (0.3137, 0.3268) When the incident angle is 0 ° and when it is 60 °,
The change in the value of x is +0.0132, and the change in the value of y is-
It was 0.0159.

The thickness of each layer in the examples and comparative examples of the present invention was measured by X-ray photoelectron spectroscopy (XPS) using sputter etching using an Ar ion beam.
The analysis was performed by performing an analysis in the depth direction from the surface. In this measurement, the sputter etching time by the Ar ion beam corresponds to the depth from the surface, that is, the film thickness. The sputter etching time of each layer was defined as the difference between the sputter etching times at which the maximum intensity at the rise and fall of the XPS peak intensity in the depth direction profile was 50% of the maximum intensity. The conversion from the sputter etching time to the film thickness was determined by a calibration curve prepared using a standard sample having a known film thickness and the same film configuration. The XPS spectrometer used was a Quantum 2000 manufactured by PHI, and a 15 kV, 20 W AlKα ray monochromatized by an X-ray monochromator was used as an X-ray source. The X-ray beam is perpendicularly incident on the sample surface,
A micro area of 100 μm on the sample surface was measured under the condition that the beam diameter was 100 μm. The detection angle of X-ray photoelectrons is 45
° and an electronic shower and A
The charge correction was performed using an r ion shower in combination. An Ar ion beam for sputter etching has an acceleration voltage of 1.
0 keV, current density 37 nA / mm ² , refracted by 5 ° for uniform energy distribution and removal of neutral particles,
The sample surface was irradiated at an incident angle of 45 °.

In both the embodiment and the comparative example, the value of x increases and the value of y decreases at an incident angle of 60 ° as compared with the case of 0 °. On the CIE chromaticity coordinates, this change is in a reddish direction. When the incident angle is 0 °, the color tone is greenish and gentle, and if the color tone is reddish, the change in the reflection color tone is particularly strongly felt. For this reason, the smaller the amount of increase in the value of x and the amount of decrease in the value of y, the better. In the example of the present invention, the amount of change in the value of x is smaller than that of the comparative example, that is, redness is suppressed. As a result, it is possible to give an impression that the change in the reflection color tone is small even when the incident angle is changed. Regarding the reflection color tone from the substrate side in the glass laminate of the present invention, the absolute value of the difference between the value of x at an incident angle of 0 ° (x coordinate in the CIE chromaticity coordinate diagram) and the value of x at 60 ° is , 0.01 or less, and particularly preferably 0.005 or less.

(Example 4) Using the glass laminate of Example 1, a 3 mm soda lime glass and another 3 mm soda lime glass were formed into a multi-layer glass through a 6 mm heat insulating air layer.
A laminate A) was produced. On the other hand, a window glass laminate (hereinafter, referred to as laminate B) was produced in the same manner as described above except that the 6 mm heat insulating air layer was changed to 12 mm. When the heat transmission coefficient of the glass laminate of Example 1 was calculated from the measured emissivity, it was 2.5 for the laminate A and 1.7 for the laminate B. From this, it was confirmed that these window glass laminates had high heat insulating properties. Further, the reflection color tone (the reflection color tone from the 31a side in FIG. 3)
With regard to, whiteness was enhanced by vitrification with multiple layers, but greenness, which is a mild color tone, was sufficiently recognized.
Furthermore, the change in the reflection color tone when viewed obliquely had no effect even if the glass was formed into a multilayer glass, and the same good results as those of the single plate of Example 1 were obtained. The same applies to the reflection color tone from the opposite side (the reflection color tone from the 41a side in FIG. 4).

[0049]

The laminate of the present invention has a gentle reflection color tone close to an achromatic color, and the color tone of the reflected light seen from the substrate side is little changed even when the incident angle is changed. In addition, the glass laminate for windows of the present invention has high heat insulating properties, has a gentle reflection color tone close to achromatic, and the color tone of the reflected light viewed from the substrate side changes even when the incident angle is changed. Is less. Therefore, the laminate and the window glass laminate of the present invention can be suitably used as a glass substrate for window glass of buildings, vehicles, and the like, utilizing their features.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a laminate of the present invention.

FIG. 2 is a view showing a result of measuring a reflection color tone from a glass surface side with changing an incident angle for a glass laminate.

FIG. 3 is a schematic cross-sectional view showing an example of a glass laminate using Low-E glass.

FIG. 4 is a schematic cross-sectional view showing another example of a glass laminate using Low-E glass.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 First layer made of oxide 2 Second layer made of metal containing Ag as main component 3 Third layer made of oxide 4 Fourth layer made of metal containing Ag as main component 5 Fifth layer made of oxide DESCRIPTION OF SYMBOLS 11 Base 31a Glass substrate 31b Glass substrate 32 Perimeter 33 Insulated air layer 34 Low reflective coating 41a Glass substrate 41b Glass substrate 42 Perimeter 43 Insulated air layer 44 Low radioactive coating

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C03C 27/06 101 C03C 27/06 101H E06B 3/66 E06B 3/66

Claims (11)

[Claims] 1. A substrate, and on the substrate, sequentially from the substrate side.
A first layer made of an oxide, a second layer made of a metal containing Ag as a main component, a third layer made of an oxide, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of an oxide And a thickness of the first layer is 60 to 90% of a thickness of the fifth layer. 2. The method according to claim 1, wherein the thickness of the second layer is 50 times the thickness of the fourth layer.
The laminate according to claim 1, wherein the laminate has a thickness of about 90%. 3. The optical system according to claim 1, wherein the sum of the optical thicknesses of the first, third and fifth layers is not more than 300 nm, and the thickness of the third layer is not less than 300% of the thickness of the first layer. Item 3. The laminate according to any one of Items 1 to 2. 4. An optical system according to claim 1, wherein said first layer has an optical thickness of 32 nm to 41 nm.
nm, the second layer has a geometric thickness of 6 nm to 9 nm, the third layer has an optical thickness of 113 nm to 145 nm, the fourth layer has a geometric thickness of 8 nm to 12 nm, and the fifth layer has an optical thickness of 8 nm to 12 nm. The laminate according to any one of claims 1 to 3, which has a thickness of 45 nm to 60 nm. 5. The method according to claim 1, wherein the first layer has an optical thickness of 41 nm to 50 nm.
nm, the geometric thickness of the second layer is 6 nm to 9 nm, the optical thickness of the third layer is 150 nm to 177 nm, the geometric thickness of the fourth layer is 11 nm to 15 nm, and the optical thickness of the fifth layer is 5 nm. The laminate according to any one of claims 1 to 3, having a thickness of 62 nm to 74 nm. 6. An optical layer according to claim 1, wherein said first layer has an optical thickness of 63 nm to 71 nm.
nm, the second layer has a geometric thickness of 6 nm to 9 nm, the third layer has an optical thickness of 165 nm to 187 nm, the fourth layer has a geometric thickness of 10 nm to 14 nm, and the fifth layer has an optical thickness of The laminate according to claim 1, having a thickness of 72 nm to 82 nm. 7. The oxide layer of the first, third and fifth layers is an oxide of at least one metal selected from the group consisting of Sn, Zn and Ti. 7. The laminate according to any one of items 6 to 6. 8. The laminate according to claim 7, wherein the first, third, and fifth layers made of an oxide are layers containing an oxide of Zn. 9. The first, third, and fifth oxide layers each include ZnO as a main component, and
The laminate according to claim 8, wherein the laminate includes at least one metal element selected from n, Al, Cr, Ti, Si, B, Mg, and Ga. 10. The substrate according to claim 1, wherein said substrate is a glass substrate.
The laminate according to any one of claims 9 to 9. 11. A window glass laminate in which a plurality of glass substrates are laminated via a heat-insulating air layer, wherein at least one glass substrate is defined by any one of claims 1 to 10. A glass laminate for windows, which is a laminate.