AU2016213183B2

AU2016213183B2 - Coated glass sheet and insulated glazing

Info

Publication number: AU2016213183B2
Application number: AU2016213183A
Authority: AU
Inventors: Yoshihito Katayama; Kazuya Yaoita
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2015-01-28
Filing date: 2016-01-26
Publication date: 2019-07-25
Anticipated expiration: 2036-01-26
Also published as: WO2016121752A1; JP6601419B2; AU2016213183A1; CN107207331A; MY186067A; JPWO2016121752A1

Abstract

Provided is a coated glass sheet which is able to achieve high thermal insulation properties while having a good appearance from the outside when used in insulated glazing. Also provided is insulated glazing. The coated glass sheet comprises a strengthened glass sheet and a laminated coating which is provided on one main surface of the glass sheet and not provided on two or more end surfaces thereof, wherein the laminated coating will demonstrate the properties listed below in insulated glazing that has been fabricated such that a test glass sheet comprising a first transparent glass sheet with a thickness of 5 mm and having the laminated coating formed thereon is spaced apart by a spacer from a second transparent glass sheet having a thickness of 6 mm with the laminated coating surface of the test glass sheet facing the inner side, and such that there is an air layer having a thickness of 12 mm between the test glass sheet and the second transparent glass sheet. In the aforementioned insulated glazing, the solar heat gain coefficient (g value) on the side of the second transparent glass sheet with respect to solar heat from the side of the test glass sheet is 0.265 or less, b* of transmitted light in CIE 1976 L*a*b* color space is 1 or less, and the visible light reflectance on the side of the test glass sheet is 20% or less.

Description

GLASS PLATE WITH STACKED FILM AND DOUBLE GLAZING GLASS

TECHNICAL FIELD [0001] The present invention relates to a glass plate with a stacked film and a double glazing glass, in particular, to a glass plate with a stacked film and a double glazing glass suitable for strengthened glass.

BACKGROUND [0002] When considering energy-saving performance of a window glass for building, for example, a plate glass with a low-emissivity stacked film called as Low-E glass is used to attain a high heat-shielding property. Here, the high heat-shielding property can be attained by reducing a solar heat gain coefficient of glass, but it is necessary to lower visible light transmittance to reduce the solar heat gain coefficient.

[0003] In general, reflectance becomes too high if the visible light transmittance is lowered to reduce the solar heat gain coefficient in the Low-E glass. On the other hand, a reflected color tone is easy to be tinged with red and design is deteriorated especially at the plate glass side, that is, when the window glass is seen from outside of the building if the reflectance is tried to be lowered to a certain degree. Besides, in a commercial building, there is often a case when blinds are provided indoors, and when a transmitted color tone of glass is tinged with yellow, design is also deteriorated when the window glass is seen from outside of the building.

[0004] As an attempt to solve the above-stated problems, for example, there is described an art to adjust film thicknesses of metal layers containing silver as a main component and dielectric layers each constituting a low-emissivity stacked film, in Patent Reference 1.

However, it was difficult to say that the high heat-shielding property and the design when it is seen from the plate glass side are at a sufficiently satisfactory level according to the art described in Patent Reference 1.

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PRIOR ART REFERENCE

PATENT REFERENCE [0005] [Patent Reference 1] JP-A No. 2014-76918

SUMMARY OF THE INVENTION [0006] It may be desirable for an embodiment of the present invention to provide a glass plate with a stacked film capable of enabling both high heat-shielding property and good appearance from outside when used as a double glazing glass, and a double glazing glass using the glass plate with the stacked film.

[0007] A glass plate with a stacked film according to an embodiment of the present invention includes: a strengthened glass plate having rectangular principal surfaces; and a stacked film provided on one principal surface of the glass plate and not provided on two or more end faces of the glass plate, wherein the stacked film includes the following properties as a double glazing glass using the stacked film: in the double glazing glass manufactured by forming the stacked film on one principal surface of a first transparent glass plate with a thickness of 5 mm to be a glass plate with a stacked film for test, separately disposing the glass plate with the stacked film for test and a second transparent glass plate with a thickness of 6 mm through a spacer arranged at a periphery such that a stacked film surface of the glass plate with the stacked film for test opposes to one principal surface of the second transparent glass plate, to have an air cavity with a thickness of 12 mm between the glass plate with the stacked film for test and the second transparent glass plate, a solar heat gain coefficient (g value) measured at the second transparent glass plate side for solar radiation from the glass plate with the stacked film for test side based on IS09050:2003 is 0.265 or less; a value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding transmitted light obtained by irradiating visible light defined in IS09050:2003; and a visible light reflectance measured at the glass plate with the stacked film for test side based on IS09050:2003 is 20% or less.

[0008] A glass plate with a stacked film according to another embodiment of the present

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2016213183 06 Jun 2019 invention includes: a strengthened glass plate having rectangular principal surfaces; and a stacked film provided on one principal surface of the glass plate and not provided on two or more end faces of the glass plate, wherein the stacked film includes n-layers (n is an integer of two or more) of metal layers each containing silver as a main component, and n+1 5 layers of dielectric layers respectively stacked to sandwich the metal layers, and the stacked film satisfies either one of the following two configurations, a first metal layer nearest to the glass plate among the metal layers contains at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6 mass% or more relative to a total amount of silver and the metal, where when the proportion is less than 9 mass%, a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the glass plate is 100 nm or less, and the first metal layer and at least one layer among the metal layers other than the first metal layer each contain at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 1.5 mass% or more relative to a total amount of silver and the metal independently, a total of contents of the metals in the metal layers each containing the metal in the proportion of 1.5 mass% or more is 4 mass% or more, and a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the glass plate is 95 nm or less.

[0009] A double glazing glass according to an embodiment of the present invention includes: a glass plate with a stacked film which includes a strengthened first glass plate having 20 rectangular principal surfaces; and a stacked film provided on one principal surface of the first glass plate and not provided on two or more end faces of the first glass plate; and a second glass plate having rectangular principal surfaces and separately disposed from the glass plate with the stacked film through a spacer, wherein a solar heat gain coefficient (g value) measured at the second glass plate side for solar radiation from the glass plate with the stacked film side 25 based on IS09050:2003 is 0.265 or less; a value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding transmitted light obtained by irradiating visible light defined in IS09050:2003; and a visible light reflectance measured at the glass plate with the stacked film side based on IS09050:2003 is 20% or less.

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2016213183 06 Jun 2019 [0010] According to an embodiment of the present invention, it may be possible to provide a glass plate with a stacked film capable of enabling both high heat-shielding property and good external appearance from outsides when used as a double glazing glass, and a double glazing glass.

BRIEF DESCRIPTION OF THE DRAWINGS [0011] [Fig. 1A] is a front view schematically illustrating a glass plate with a stacked film.

[Fig. IB] is a sectional view taken along an X-X line of the glass plate with the stacked film illustrated in Fig. 1A.

[Fig.2] is a sectional view illustrating an example of a double glazing glass.

[Fig.3] is a sectional view of one embodiment of a glass plate with a stacked film.

[Fig.4] is a sectional view illustrating a modification example of one embodiment of a glass plate with a stacked film.

MODES FOR CARRYING OUT THE INVENTION [0012] Hereinafter, embodiments of the present invention are described with reference to the drawings. Note that the present invention is not construed by being limited to the following explanation.

[0013] [Glass plate with stacked film]

Fig. 1A and Fig. IB are respectively a front view and a sectional view taken along an X-X line of the front view schematically illustrating a glass plate with a stacked film of an embodiment of the present invention. A glass plate with a stacked film 10 according to an embodiment of the present invention illustrated in Fig. 1A and Fig. IB includes a strengthened glass plate 1 and a stacked film 2 provided on one principal surface 1 s of the glass plate 1. The principal surface 1 s of the glass plate 1 is rectangular, and there are four end faces It. The stacked film 2 is not provided at the end faces It of the glass plate 1. Note that in the glass plate with the stacked film according to an embodiment of the

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2016213183 06 Jun 2019 present invention, the stacked film may be provided at up to two end faces among the four end faces. The stacked film 2 is a low-emissivity stacked film capable of supplying properties of the following (1-a) to (3-a) to a double glazing glass when the double glazing glass having a specific constitution as described below is manufactured by using the stacked film 2.

[0014] The double glazing glass to evaluate the stacked film is manufactured such that a glass plate with a stacked film for test is made by forming the stacked film on one principal surface of a first transparent glass plate with a thickness of 5 mm, then the glass plate with the stacked film for test and a second transparent glass plate with a thickness of 10 6 mm are separately disposed so that a stacked film surface of the glass plate with the stacked film for test is opposed to one principle surface of the second transparent glass plate through a spacer arranged at a periphery thereof to have an air cavity with a thickness of 12 mm between the glass plate with the stacked film for test and the second transparent glass plate. The double glazing glass manufactured as stated above has properties of the following (1-a), (2-a) and (3-a).

[0015] (1-a) A solar heat gain coefficient (g value) measured at the second transparent glass plate side for solar radiation from the glass plate with the stacked film for test side based on IS09050:2003 is 0.265 or less.

(2-a) A value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding 20 transmitted light obtained by irradiating visible light defined in IS09050:2003.

(3-a) A visible light reflectance measured at the glass plate with the stacked film for test side based on IS09050:2003 is 20% or less.

[0016] Hereinafter, there are explained the glass plate 1 and the stacked film 2 held by the glass plate with the stacked film 10 of the embodiment.

[0017] (Glass plate)

The glass plate 1 is not particularly limited as long as it is plate-shaped glass which is strengthened and whose principal surfaces are rectangular, and for example, an inorganic and transparent glass plate such as a window glass for building, a normally used float glass,

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2016213183 06 Jun 2019 or a soda-lime glass manufactured by a roll-out method, can be used. There are air-cooling tempering, chemically strengthening, and so on as strengthening methods of a glass plate, and an air-cooled tempered glass plate is preferable as the glass plate 1. Strengthening of the glass plate 1 may be carried out before the stacked film 2 is provided on the principal surface, or a non-heat-treated product where a stacked film is formed on a principal surface of a glass plate at a manufacturing time may be heat-treated to thereby make it into the air-cooled tempered glass plate 1 as described later. The latter one is preferable in an embodiment of the present invention.

[0018] The glass plate 1 is appropriately selected in accordance with performance required for the glass plate with the stacked filmlO. When the glass plate with the stacked filmlO is used as a part of a double glazing glass, colorless glass such as clear glass and extra clear glass is preferable as the glass plate 1 when the visible light transmittance at a certain level or more is required. Besides, the colorless glass is preferable from a viewpoint of obtaining a high color rendering property.

[0019] As the glass plate 1, there can also be used various kinds of glass such as borosilicate glass, low expansion glass, zero-expansion glass, low expansion crystallized glass and zero-expansion crystallized glass. A thickness of the glass plate 1 is not necessarily limited, and is preferably a thickness capable of keeping the visible light transmittance of the glass plate 1 at a constant level or more and securing sufficient mechanical strength, and for example, 0.5 to 20 mm is suitable.

[0020] A shape of the glass plate 1 is not particularly limited as long as it is plate-shaped and has a pair of rectangular principal surfaces. The pair of principle surfaces may each have a planar shape with a flat plane, or a curved plate shape where a whole or a part of the pair of principal surfaces has a curvature. Note that the principal surfaces are rectangular means that the principal surfaces have substantially rectangle shapes, and for example, a glass plate where corners at a peripheral part are cut-off is also included in the category.

[0021] (Stacked film)

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In the glass plate with the stacked film 10, the stacked film 2 is provided over a whole surface on the principal surface 1 s of the glass plate 1, on the other hand, it is not provided at the four end faces It of the glass plate 1. In the glass plate with the stacked film of the embodiment, the stacked film may be provided at one or two end faces among the four end faces of the glass plate, but it is preferable that the stacked film is not provided at any of the four end faces.

[0022] The glass plate with the stacked film according to an embodiment of the present invention is normally used by being fitted into a window independently or being made to be a laminated glass or a double glazing glass together with other members. A sectional view of an example of a double glazing glass according to an embodiment of the present invention where the glass plate with the stacked film 10 is used as a composing member is illustrated in Fig. 2. Double glazing glass 3 has a constitution where the glass plate with the stacked film 10 having the first transparent glass plate 1 and the stacked film 2 and a second transparent glass plate 32 are separately disposed through a spacer 33 arranged at a periphery so as to have a cavity 34 therebetween. In the double glazing glass 3, a stacked film 2 surface of the glass plate with the stacked film 10 is separately disposed to oppose to one principal surface of the second transparent glass plate 32. [0023] In the glass plate with the stacked film according to an embodiment of the present invention and the double glazing glass using the glass plate with the stacked film, 20 the stacked film is not provided at two or more end faces, preferably at all of the end faces of the glass plate, and therefore, it is preferable because there are an effect to suppress deterioration of the stacked film caused by materials containing plasticizer such as a setting block and a glazing channel when it is fitted to a window of a building or the like, and an effect to suppress lowering of adhesive force with a rustproof material of a wire glass.

[0024] In the glass plate with the stacked filmlO, the stacked film 2 is a low-emissivity stacked film satisfying all of the above-stated (1 -a) to (3-a) when it is evaluated as the double glazing glass for evaluation having the above-stated specific constitution.

[0025] <Properties of stacked film>

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The stacked film 2 is, for example, the double glazing glass having the similar constitution as illustrated in Fig. 2, where the cavity 34 is an air cavity, and it can be evaluated by the double glazing glass where a thickness tl of the first transparent glass plate 1, a thickness t2 of the second transparent glass plate 32, and a thickness t3 of the cavity (air cavity) 34 are respectively 5 mm, 6 mm, and 12 mm (hereinafter, it is called as “double glazing glass

30”). Besides, in this case, the transparent glass plate 1 with the thickness of 5 mm where the stacked film 2 to be evaluated is provided is called as “a glass plate with a stacked film for test 1 Ox”.

[0026] Here, the transparent glass plate used for the evaluation or the like in this description means glass where the visible light transmittance measured based on IS09050:2003 is 80% or more, and absolute values of a* and b* in the CIE 1976 L*a*b* chromaticity coordinates of transmitted light obtained by irradiating visible light defined in IS09050:2003 are both five or less regardless of the thickness.

[0027] In this description, the visible light transmittance measured based on

IS09050:2003 is represented by “Tv”, and the visible light reflectance is represented by “Rv” according to need. Besides, the transmitted light obtained by irradiating the visible light defined in IS09050:2003 is also called just as the “transmitted light”, and similarly, reflected light obtained by irradiating the visible light defined in IS09050:2003 is also called just as the “reflected light”. Further, b* and a* in the CIE 1976 L*a*b* chromaticity coordinates are also called just as “b*”, “a*”, respectively.

[0028] Hereinafter, there are explained properties of the stacked film in the glass plate with the stacked film of the embodiment which are evaluated by using the double glazing glass for evaluation, for example, the double glazing glass 30. Note that in the following explanation, there are described as the properties of the double glazing glass 30, and they 25 are all originated in properties of the stacked film 2. Besides, in the double glazing glass using the glass plate with the stacked film of the embodiment, the glass plate with the stacked film is normally manufactured to oppose to the other glass plate with a space such that the stacked film faces inside, and is used such that the glass plate with the stacked film 8

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2016213183 06 Jun 2019 side is exposed to the outdoors and the opposing glass plate side positions at an indoor side. Evaluation using the double glazing glass 30 is evaluation assuming the use as stated above.

[0029] In the double glazing glass 30 using the stacked film 2, (1-a) the solar heat gain coefficient (g value) measured at the second transparent glass plate 32 side for solar radiation from the glass plate with the stacked film for test 1 Ox side based on IS09050:2003 is 0.265 or less. The solar heat gain coefficient (g value) is preferably 0.257 or less.

[0030] Here, the solar heat gain coefficient (g value) is a value indicating a ratio of heat quantity flowing in the second transparent glass plate 32 side (an indoor side) when solar energy incident from the glass plate with the stacked film for test 1 Ox side (an outdoor side) is set as one. It is possible to know a heat-shielding property, that is, to what degree of heat (solar heat) generated by sunlight is shielded from the solar heat gain coefficient (g value).

[0031] The solar heat gain coefficient is a ratio of total heat quantity of heat directly transmitted (hereinafter, it is also referred to as “transmitted heat”) and heat absorbed and then radiated to the second transparent glass plate 32 side (the indoor side) (hereinafter, it is also referred to as “radiant heat”), for the solar energy incident from the glass plate with the stacked film for test 1 Ox side (the outdoor side). The solar heat gain coefficient is represented by a number from 0 (zero) to 1.

[0032] Note that concretely, the solar heat gain coefficient can be calculated in a manner that spectral properties and emissivity in the double glazing glass 30 are measured and introduced into a predetermined calculation formula. The smaller the solar heat gain coefficient is, the smaller the ratio of the total heat quantity of the transmitted heat and the 25 radiant heat for the solar heat quantity incident from the glass plate with the stacked film for test lOx side in the double glazing glass 30.

[0033] In the double glazing glass 30 using the stacked film 2, (2-a) the value of b* in the CIE 1976 L*a*b* chromaticity coordinates is one or less regarding the transmitted

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2016213183 06 Jun 2019 light obtained by irradiating the visible light defined in IS09050:2003.

[0034] The transmitted light incident from the glass plate with the stacked film for test lOx side (the outdoor side) of the double glazing glass 30 and transmitted toward the second transparent glass plate 32 side (the indoor side) and the transmitted light incident from the second transparent glass plate 32 side (the indoor side) of the double glazing glass 30 and transmitted toward the glass plate with the stacked film for test lOx side (the outdoor side) are the same, and either transmitted light may be used for the measurement. [0035] The b* of the transmitted light of the double glazing glass 30 is preferably b* < 0 (zero). In the double glazing glass 30, when the sunlight incident from the glass plate with the stacked film for test lOx side (the outdoor side) shines on a blind provided at the indoor side, a color tone is not tinged with yellow as long as the b* of the transmitted light is in the above-stated range.

[0036] In the double glazing glass 30 using the stacked film 2, (3-a) the visible light reflectance measured at the glass plate with the stacked film for test lOx side based on

IS09050:2003 is 20% or less. Hereinafter, the visible light reflectance measured at the glass plate with the stacked film for test lOx side based on 1S09050:2003 is also referred to as Rvout. The Rv_out is preferably 18% or less. In the double glazing glass 30, when the glass is seen from outside, reflection is not too high, and an appearance becomes excellent in design as long as the Rv_out is in the range.

[0037] In the double glazing glass 30 using the stacked film 2, it is preferable that one or two or more properties selected from the following (4-a), (5-a), (6-a), (7-a) and (8-a) is further held in addition to have the properties of the above-stated (1-a), (2-a) and (3-a). It is more preferable to have all of the properties of (4-a) to (8-a).

[0038] (4-a) A visible light reflectance measured at the second transparent glass plate side based on IS09050:2003 is 20% or less.

(5-a) A difference between the visible light reflectance measured at the glass plate with the stacked film for test side and the visible light reflectance measured at the second transparent glass plate side based on !S09050:2003is 10% or less.

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2016213183 06 Jun 2019 (6-a) Both values of a* and b* in the CIE 1976 L*a*b* chromaticity coordinates are two or less regarding each reflected light obtained by irradiating visible light defined in IS09050:2003 at the glass plate with the stacked film for test side and the second transparent glass plate side.

(7-a) A visible light transmittance measured based on IS09050:2003 is 30% or more.

(8-a) A color rendering property of transmitted light evaluated by an average color rendering evaluation index (Ra) using a D65 light source based on JIS Z8726 (1990) is 85% or more.

[0039] The visible light reflectance measured at the second transparent glass plate 32 side based on IS09050:2003 is also referred to as Rvin similar to the Rvout. The Rvin is preferably 20% or less as described in (4-a), more preferably 18% or less, and particularly preferably 16% or less. The double glazing glass 30 has the property of (4-a), and thereby, it becomes possible to suppress reflection in the room due to reflected light into the second transparent glass plate 32 side (the indoor side).

[0040] The difference between the Rv_out and the Rvin is preferably 10% or less as described in (5-a), more preferably 9% or less, and particularly preferably 8% or less. Note that the difference between the Rv_out and the Rvin is a value obtained by subtracting a small value from a large value between the Rv_out and the Rvin. The double glazing glass 30 has the property of (5-a), and thereby, it becomes easy to adjust the color tones of both the outdoor side and the indoor side into ones excellent in design.

[0041] Both values of a* and b* in the CIE 1976 L*a*b* chromaticity coordinates are preferably two or less as described in (6-a) in the reflected light at the glass plate with the stacked film for test lOx side and the reflected light at the second transparent glass plate 32 side. The double glazing glass 30 has the property of (6-a), and thereby, it becomes possible to suppress redness and yellowness of the reflected light both at the glass plate with the stacked film for test 1 Ox side (the outdoor side) and at the second transparent glass plate 32 side (the indoor side).

[0042] The value of a* of the reflected light at the glass plate with the stacked film for

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2016213183 06 Jun 2019 test lOx side (the outdoor side) is more preferably -20 to 1, and particularly preferably -15 to 0 (zero). The value of b* of the reflected light at the glass plate with the stacked film for test lOx side (the outdoor side) is more preferably -30 to 1, and particularly preferably

-25 to 0 (zero). The value of a* of the reflected light at the second transparent glass plate

32 side (the indoor side) is more preferably -20 to 1, and particularly preferably -15 to 0 (zero). The value of b* of the reflected light at the second transparent glass plate 32 side (the indoor side) is more preferably -30 to 1, and particularly preferably -25 to 0 (zero).

[0043] The Tv of the double glazing glass 30 is preferably 30% or more as described in (7-a). The double glazing glass 30 has the property of (7-a), and thereby, it is possible to have sufficient lighting in the building. The Tv of the double glazing glass 30 is preferably 60% or less from a viewpoint of an antiglare property. The Tv of the double glazing glass 30 is particularly preferably 35 to 55%.

[0044] The color rendering property of the transmitted light evaluated by the average color rendering evaluation index (Ra) using the D65 light source based on JIS Z8726 (1990) of the double glazing glass 30 is concretely 85% or more as described in (8-a).

The color rendering property according to (8-a) is 85% or more, and thereby, the appearance when the double glazing glass 30 is seen from outside the building becomes a natural neutral color. The color rendering property is preferably 87% or more, and more preferably 90% or more.

[0045] Hereinabove, the properties of the stacked film of the glass plate with the stacked film according to an embodiment of the present invention are explained regarding a case when they are evaluated by the double glazing glass using the glass plate with the stacked film for test. The constitutions of the glass plate with the stacked film for test and the double glazing glass using the glass plate with the stacked film used in the above are both the constitutions to evaluate the stacked film of the glass plate with the stacked film of an embodiment, and the constitution of the glass plate with the stacked film of an embodiment of the present invention is not limited to the constitution of the glass plate with the stacked film for test. Besides, use of the glass plate with the stacked film of the

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2016213183 06 Jun 2019 present invention is not limited to the double glazing glass, and the constitution of the double glazing glass according to an embodiment of the present invention is not limited to the constitution of the double glazing glass for evaluation.

[0046] A haze value of the glass plate with the stacked film according to an embodiment of the present invention is preferably 2% or less so as to secure transparency. The haze value of the glass plate with the stacked film is more preferably 1% or less. In the glass plate with the stacked film, the haze value of the glass plate is normally approximately 0.0 to 0.1%, and the haze value as a whole of the glass plate with the stacked film largely depends on the haze value of the stacked film. That is, it is essential for the stacked film to have the properties satisfying (1-a), (2-a) and (3-a) in the above-stated evaluation, and it is preferable to have one or more properties selected from (4-a) to (8-a), and further, the stacked film having the haze value that the glass plate with the stacked film when it is used has the haze value of 2% or less is preferable.

[0047] The constitution and a manufacturing method of the stacked film in the glass plate with the stacked film of the embodiment are as described later. When the glass plate is an air-cooled tempered glass plate or a curved plate-shaped glass plate, there is a case when a precursor of the glass plate with the stacked film is heat-treated to, for example, 600° C or more to obtain the glass plate with the stacked film of the embodiment. That is, there is a case when the glass plate with the stacked film is obtained not by performing the heat treatment to the glass plate to, for example, 600° C or more, to thereby make it the air-cooled tempered glass plate or the curved plate-shaped glass plate, and then, forming the stacked film on one principal surface, but by forming the precursor of the stacked film on the glass plate before the heat treatment is performed, then performing the heat treatment to obtain the glass plate with the stacked film whose glass plate is the air-cooled tempered glass plate or the curved plate-shaped glass plate. The curved plate-shaped glass plate is a glass plate in a curved plate-shape which is strengthened by the heat treatment. In such a case, a composing material of the stacked film is selected as described later so that the haze value of the glass plate with the stacked film becomes 2%

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2016213183 06 Jun 2019 or less as the heat-treated stacked film.

[0048] In the glass plate with the stacked film of the embodiment, it is preferable that the number of white spots each having a diameter of 0.5 mm or more observed in a range of 100 mm x 100 mm at the stacked film surface after performing a humidity resistance test where the glass plate with the stacked film is kept under conditions of 50°C, 90% RH for two weeks is five pieces or less. If the stacked film surface after the humidity resistance test satisfies the above-stated condition, it can be said that sufficient humidity resistance is held when the glass plate with the stacked film is kept in case when, for example, double glazing glass is manufactured by using the glass plate with the stacked film of the embodiment.

[0049] Constitution of stacked film>

In the stacked film of the glass plate with the stacked film according to the embodiment, a constitution thereof is not particularly limited as long as the properties satisfying (1-a), (2-a) and (3-a) in the above-stated evaluation are held. There can be cited, for example, a stacked film (X) or a stacked film (Y) respectively having the following constitutions as the stacked film capable of satisfying (1-a), (2-a) and (3-a) in the above-stated evaluation. [0050] The stacked film (X) includes n-layers (n is an integer of two or more) of metal layers containing silver as a main component, and n+1 layers of dielectric layers stacked to sandwich the metal layers, where a first metal layer nearest to the glass plate among the metal layers contains at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6 mass% or more relative to a total amount of silver and the metal. Note that when the proportion of the metal relative to the total amount of silver and the metal is 6 mass% or more and less than 9 mass%, a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the glass plate is 100 nm or less. When the proportion of the metal relative to the total amount of silver and the metal is 9 mass% or more, the thickness of the dielectric layer between the first metal layer and the second metal layer which is the second nearest to the glass plate is not particularly limited. Note that in this description, each of thicknesses of the metal layers, the dielectric layers and other layers

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2016213183 06 Jun 2019 constituting the stacked film stands for a geometrical thickness.

[0051] The stacked film (Y) includes n-layers (n is an integer of two or more) of metal layers containing silver as a main component, and n+1 layers of dielectric layers stacked to sandwich the metal layers. In the stacked film (Y), the first metal layer nearest to the glass plate among the metal layers contains at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 1.5 mass% or more relative to the total amount of silver and the metal, and at least one layer from among the metal layers other than the first metal layer among the metal layers contains at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in the proportion of 1.5 mass% or more relative to the total amount of silver and the metal. Further, in the stacked film (Y), a total of the contents of the metal in the metal layer containing the metal in the proportion of 1.5 mass% or more is 4 mass% or more. In the stacked film (Y), a constitution of the n-layers of metal layers satisfies the above-stated condition, and the thickness of the dielectric layer between the first metal layer and the second metal layer which is the second nearest to the glass plate is 95 nm or less.

[0052] The n-layers (n is an integer of two or more) of metal layers containing silver as the main component held by the stacked film (X) and the stacked film (Y) are the metal layers responsible for supplying low-emissivity to the stacked film. Note that in this description, containing a certain component as a main component means that a proportion of the component contained as a main component relative to all constituent components exceeds 50 mass%. In the stacked film (X) and the stacked film (Y), specific metal layers among the n-layers of metal layers each containing silver as the main component contain at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel to have the above-stated content, in addition, the thickness of the dielectric layer between the first metal layer which is the nearest to the glass plate and the second metal layer which is the second nearest to the glass plate is set to be in the above-stated range as according to need in the stacked film (X) and as an essential requirement in the stacked film (Y), and thereby, all of the properties of (1 -a), (2-a) and (3-a) become attainable in the evaluation.

[0053] In the stacked film (X), the number of layers of the metal layers containing

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2016213183 06 Jun 2019 silver as the main component may be two or more, is preferably two to four, more preferably two or three, and particularly preferably two. Fig. 3 is a sectional view of one embodiment of a glass plate with a stacked film 10A having a stacked film whose number of layers of the metal layers containing silver as the main component is two as the stacked film (X). The glass plate with the stacked filmlOA has a stacked film 2A on one principle surface 1 s of the glass plate 1.

[0054] The stacked film 2A includes a first dielectric layer 21, a first metal layer 22, a second dielectric layer 23, a second metal layer 24 and a third dielectric layer 25 from the glass plate 1 side in sequence. The first metal layer 22 and the second metal layer 24 are both the metal layers each containing silver as the main component. Besides, the first metal layer 22 contains at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6 mass% or more relative to the total amount of silver and the metal. Note that in the first metal layer 22, when the proportion of the metal relative to the total amount of silver and the metal is 6 mass% or more and less than 9 mass%, a thickness of the second dielectric layer 23 between the first metal layer 22 and the second metal layer 24 is

100 nm or less. In the first metal layer 22, when the proportion of the metal relative to the total amount of silver and the metal is 9 mass% or more, the thickness of the second dielectric layer 23 is not particularly limited. In each layer, a near side to the glass plate 1 is called as a “glass plate side”, and an opposite side is called as a “surface side”. Hereinafter, each layer constituting the stacked film 2A is explained.

[0055] The first metal layer 22 contains silver as the main component, and at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in the proportion of 6 mass% or more relative to the total amount of silver and the metal in addition to silver as the main component. Hereinafter, at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel is also called as a metal M. Besides, a proportion (mass%) of the metal M relative to a total amount of silver and the metal M is called as a content of the metal M. The content of the metal M in the first metal layer 22 is more preferably 7.5 mass% or more, and particularly preferably 9 mass% or more. An upper limit of the content of the metal M in

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2016213183 06 Jun 2019 the first metal layer 22 is preferably approximately 30 mass% from a balance between an effect and economic efficiency.

[0056] As the metal M, one kind selected from palladium, gold, chromium, cobalt and nickel may be used independently, or two or more kinds may be used together. Among them, 5 palladium and gold are preferable as the metal M, and palladium is particularly preferable.

Note that the metal M is a metal which is easy to form a solid solution with silver being a main material of the first metal layer 22. The metal M is used, and thereby, it is possible to suppress that the haze value of the stacked film 2A obtained by performing the heat treatment largely increases even when the heat treatment is performed in tempering and bending of the glass plate.

[0057] The first metal layer 22 is able to contain additive elements other than silver and the metal M. As the additive elements, for example, there can be cited metallic elements such as copper and titanium. When the additive elements are contained, a total content of the additive elements is preferably 5 mass% or less in all components constituting the first metal layer 22, more preferably 3 mass% or less, and further preferably 1 mass% or less.

[0058] The second metal layer 24 is not particularly limited as long as it is a metal layer containing silver as the main component. The second metal layer 24 may contain the metal M similar to the first metal layer 22 according to need. A preferable mode of 20 the metal M is similar to a case of the first metal layer 22. Note that the content of the metal M when the second metal layer 24 contains the metal M depends on performance required for the stacked film.

[0059] Regarding thicknesses of the first metal layer 22 and the second metal layer 24, a proportion of the thickness of the second metal layer 24 relative to the thickness of the first metal layer 22 is preferably in a range of 0.8 to 1.6. A value of the proportion between these two metal layers is more preferably 0.85 to 1.5, and particularly preferably 0.9 to 1.4. Specifically, the thickness of the first metal layer 22 is preferably 8 to 25 nm, and more preferably 10 to 20 nm. The thickness of the second metal layer 24 is

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2016213183 06 Jun 2019 preferably 10 to 30 nm, and more preferably 12 to 25 nm in addition to satisfy the above-stated proportion value.

[0060] As each of the first dielectric layer 21, the second dielectric layer 23 and the third dielectric layer 25 in the stacked film 2A, there can be used dielectric layers which are generally used in a manner sandwiching metal layers in a stacked film including the metal layers each containing silver as the main component without any particular limitation. Specifically, there can be cited a dielectric layer containing an oxide, a nitride, an oxynitride, and so on of a metal or an element capable of being formed on the glass plate 1, on the first metal layer 22, and on the second metal layer 24. As the metal and the element, there can be cited zinc, tin, titanium, silicon, aluminum, chromium, nickel, niobium, an alloy of them, and so on. Besides, for example, elements selected from tin, aluminum, chromium, titanium, silicon, boron, magnesium, gallium, and so on may be doped to the oxide, the nitride, the oxynitride, and so on of the metal and the element constituting the dielectric layer in a form of the oxide, the nitride and the oxynitride in addition to the above-stated metal and element.

[0061] Note that a stress change due to the heat treatment is large in the nitride layer and the oxynitride layer, and the stress accumulated in the film due to the heat-treatment takes stability away from the metal layer, and therefore, the stacked film in the glass plate with the stacked film of the embodiment preferably has a constitution where the nitride layer or the oxynitride layer is not held between the metal layer nearest to the stacked film surface among the metal layers and the glass plate. In the stacked film 2A, at least the first dielectric layer 21 and the second dielectric layer 23 are preferably neither the nitride layer nor the oxynitride layer from a viewpoint of forming efficiency. More preferably, all of the first dielectric layer 21, the second dielectric layer 23 and the third dielectric layer 25 are the oxide layers.

[0062] Among the oxide layers, a dielectric layer capable of homogenizing and densifying these metal layers 22, 24 and improving adhesiveness with the metal layers 22, 24, for example, a dielectric layer containing an oxide of zinc is preferable as the first

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2016213183 06 Jun 2019 dielectric layer 21, the second dielectric layer 23 and the third dielectric layer 25 because they sandwich the first metal layer 22 and the second metal layer 24 each containing silver as the main component.

[0063] When the dielectric layers 21, 23, 25 are the dielectric layers each containing the oxide of zinc, an oxide constituent element other than zinc can be contained. As the oxide constituent element other than zinc, there can be cited, for example, tin, aluminum, chromium, titanium, silicon, boron, magnesium, gallium, and one kind or two or more kinds from among these can be contained. The oxide constituent element other than zinc is contained, and thereby, it is possible to improve adhesiveness with a layer which is in contact with this layer, and to improve visible light transmittance.

[0064] Tin, aluminum, chromium, titanium, silicon, boron, magnesium and gallium being the oxide constituent elements other than zinc are contained in the dielectric layers 21, 23, 25 as, for example, a tin oxide (SnCh), an aluminum oxide (AI2O3), a chromium oxide (CnCh), a titanium oxide (T1O2), a silicon oxide (S1O2), a boron oxide (B2O3), a 15 magnesium oxide (MgO), a gallium oxide (Ga2O3), or as a composite oxide thereof. As the oxide constituent element other than zinc, aluminum and tin are preferable because they are cheap. Aluminum is preferable because it is a cheap material and a film-forming rate can be made high. Tin is also preferable because it is a relatively cheap material.

[0065] When the oxide constituent element other than zinc is contained in the dielectric layer containing the zinc oxide, it is preferable that the oxide constituent element other than zinc is contained 1 to 50 mass% within a total amount (within 100 mass%) of zinc and the oxide constituent element other than zinc (except oxygen). It is possible to effectively improve the visible light transmittance by setting a proportion of the oxide constituent element other than zinc at 1 mass% or more. Besides, it is possible to secure stability of the metal layers 22, 24 formed among the dielectric layers 21, 23, 25 by setting the proportion of the oxide constituent element other than zinc at 50 mass% or less.

[0066] In the stacked film 2A, when the content of the metal M in the first metal layer is 9 mass% or more, the thicknesses of the first to third dielectric layers 21, 23, 25 are

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2016213183 06 Jun 2019 not necessarily limited. The thicknesses of the first and third dielectric layers 21,25 are preferably 10 to 50 nm independently, and more preferably 20 to 45 nm. Besides, as the thickness of the second dielectric layer 23 sandwiched between the first metal layer 22 and the second metal layer 24, it is preferably thicker than the thicknesses of the first and third dielectric layers 21, 25, to be 60 to 120 nm, and more preferably 70 to 110 nm. In the stacked film (X), the content of the metal M in the first metal layer 22 is set to be 9 mass% or more, and the thicknesses of the dielectric layers 21, 23, 25 are set to be in the above-stated range, and thereby, it is possible to further lower the visible light reflectance, and to enable a good reflected color tone.

[0067] On the other hand, in the stacked film 2 A, when the content of the metal M in the first metal layer 22 is 6 mass% or more and less than 9 mass%, the thickness of the second dielectric layer 23 sandwiched between the first metal layer 22 and the second metal layer 24 is 100 nm or less. The thickness of the second dielectric layer 23 is preferably 60 to 100 nm, and more preferably 70 to 100 nm. The thicknesses of the first dielectric layer 21 and the third dielectric layer 25 are not necessarily limited, but both are preferably thinner than the thickness of the second dielectric layer 23. Specifically, the thicknesses of the first dielectric layer 21 and the third dielectric layer 25 are set to be the same as the thicknesses of the first dielectric layer 21 and the third dielectric layer 25 when the content of the metal M in the first metal layer 22 is 9 mass% or more. In the stacked film (X), the content of the metal M in the first metal layer 22 is set to be 6 mass% or more and less than 9 mass%, and the thicknesses of the dielectric layers 21, 23, 25 are set to be in the above-stated range, and thereby, it is possible to further lower the visible light reflectance, and to enable the good reflected color tone.

[0068] In the stacked film (Y), the number of layers of the metal layers each containing silver as the main component may be two or more, is preferably two to four, more preferably two or three, and particularly preferably two as same as the stacked film (X). When the number of layers of the metal layers each containing silver as the main component is two, the content of the metal M in each metal layer is 1.5 mass% or more,

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2016213183 06 Jun 2019 and a total of the metal M contents in the respective layers is 4 mass% or more. When the number of layers of the metal layers containing silver as the main component is three or more, the metal layer nearest to the glass plate and at least one layer from among remaining metal layers each contain the metal M in the proportion of 1.5 mass% or more, and the total of the metal M contents in the respective layers is 4 mass% or more. The metal M contents may be the same or different in the respective metal layers.

[0069] A more preferable content of the metal M content in each metal layer is 4 mass% or more, and particularly preferably 7 mass% or more in the metal layer nearest to the glass plate. Further, in other metal layers containing the metal M for 1.5 mass% or more, the metal M content is more preferably 2 mass% or more, and particularly preferably

2.5 mass% or more. In the metal layer where the metal M content is not defined, the metal M may be contained, or may not be contained. When the metal M is contained, the content is preferably 1.5 mass% or more. An upper limit of the metal M content in each metal layer is preferably approximately 20 mass%.

[0070] As a stacked constitution in the stacked film (Y), for example, there can be cited a stacked constitution similar to the stacked film 2A of the glass plate with the stacked filmlOA illustrated in Fig. 3, that is, a constitution having the first dielectric layer, the first metal layer, the second dielectric layer, the second metal layer and the third dielectric layer from the glass plate side in sequence. In the stacked film as stated above, the stacked film (Y) preferably has all the same constitution as the stacked film (X) regarding the metal layers except that the contents of the metal M in the first metal layer and the second metal layer are different.

[0071] When the stacked film (Y) has the same stacked constitution as the stacked film 2A, the dielectric layers preferably have all the same constitution as the stacked film (X) except that the thickness of the second dielectric layer is different. In the stacked film (Y), the thickness of the second dielectric layer sandwiched between the first metal layer and the second metal layer is 95 nm or less. The thickness of the second dielectric layer is preferably 60 to 95 nm, and more preferably 70 to 95 nm. The thicknesses of the first 21

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2016213183 06 Jun 2019 dielectric layer and the third dielectric layer are not necessarily limited, and both are preferably thinner than the thickness of the second dielectric layer. The thicknesses of the first dielectric layer and the third dielectric layer are specifically set to be the same as the thicknesses of the first dielectric layer and the third dielectric layer in the stacked film (X).

In the stacked film (Y), the metal layers have the above-stated constitution, and the thicknesses of the dielectric layers are set to be in the above-stated range, and thereby, it is possible to further lower the visible light reflectance, and to enable the good reflected color tone.

[0072] In the stacked film, when the number of layers of the metal layers each containing silver as the main component is two, the stacked film preferably has a layer constitution where a cross section is illustrated in Fig. 4 in both the stacked film (X) where the metal M content in the first metal layer near to the glass plate is 6 mass% or more and the stacked film (Y) where the metal M contents in the first metal layer near to the glass plate and in the second metal layer far from the glass plate are both 1.5 mass% or more and the total of the metal M contents in the respective layers is 4 mass% or more.

[0073] Fig. 4 is a sectional view illustrating a modification example of one embodiment of the glass plate with the stacked film. A glass plate with a stacked film 10B includes a stacked film 2B on one principal surface 1 s of the glass plate 1. The stacked film 2B includes the first dielectric layer 21, the first metal layer 22, a first barrier 20 layer 26, the second dielectric layer 23, the second metal layer 24, a second barrier layer 27, the third dielectric layer 25 and a protective layer 28 from the glass plate 1 side in sequence.

[0074] The first metal layer 22 and the second metal layer 24 are both able to be set to be the same as the first metal layer 22 and the second metal layer 24 of the stacked film 2A in the glass plate with the stacked filmlOA.

[0075] The first dielectric layer 21 is made up of a first amorphous dielectric layer 211 and a first crystalline dielectric layer 212 from the glass plate side. The second dielectric layer 23 is made up of a second crystalline dielectric layer 231, a second amorphous

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2016213183 06 Jun 2019 dielectric layer 232 and a third crystalline dielectric layer 233 from the glass plate side.

Further, the third dielectric layer 25 is made up of a fourth crystalline dielectric layer 251 and a third amorphous dielectric layer 252 from the glass plate side.

[0076] In the stacked film 2B, it is constituted such that the first, second and third dielectric layers 21, 23, 25 each have the crystalline dielectric layer and the amorphous dielectric layer, and the first crystalline dielectric layer 212 and the second crystalline dielectric layer 231 are disposed to sandwich the first metal layer 22, and the third crystalline dielectric layer 233 and the fourth crystalline dielectric layer 251 are disposed to sandwich the second metal layer 24, respectively, further the first, second and third amorphous dielectric layers 211, 232, 252 are disposed at both sides thereof.

[0077] In the stacked film 2B, in both the stacked film (X) and the stacked film (Y), a total thickness of each layer constituting the first dielectric layer 21, that is, the thickness of the first dielectric layer 21 can be set to be the same as the thicknesses in case of the stacked film (X) and the stacked film (Y) in the stacked film 2A. The thickness of the second dielectric layer 23 and the thickness of the third dielectric layer 25 are also the same.

[0078] Besides, the stacked film 2B has a constitution where the first barrier layer 26 and the second barrier layer 27 are held at the surface side of each of the first metal layer 22 and the second metal layer 24 so as to be in contact with each metal layer, and the protective layer 28 is held at the surface side of the third dielectric layer 25 at the most surface side.

[0079] As stated above, the stacked film in the glass plate with the stacked film of the embodiment preferably has a constitution where the nitride layer or the oxynitride layer is not held between the metal layer nearest to the stacked film surface among the metal layers 25 and the glass plate. In the stacked film 2B, at least the first dielectric layer 21, the first barrier layer 26 and the second dielectric layer 23 are preferably neither the nitride layer nor the oxynitride layer from a viewpoint of forming efficiency. More preferably, it is preferable that all of the first dielectric layer 21, the first barrier layer 26, the second

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2016213183 06 Jun 2019 dielectric layer 23, the second barrier layer 27 and the third dielectric layer 25 are the oxide layers.

[0080] The first to fourth crystalline dielectric layers 212, 231, 233 and 251 are dielectric layers having high crystallinity disposed so as to sandwich the first and second metal layers 22, 24 as stated above. The crystalline dielectric layer is able to homogenize and densify the first metal layer 22 and the second metal layer 24 formed therebetween owing to crystallization thereof, or the like.

[0081] As composing materials of the crystalline dielectric layers 212, 231, 233 and 251, it is possible to use by appropriately selecting dielectric materials with high crystallinity from among the dielectric materials described above as the materials composing the dielectric layers 21, 23, 25 and so on in the stacked film 2A. Among the dielectric materials described above, specifically, there are preferably used the zinc oxide or the zinc oxide containing the oxide constituent element other than zinc such as aluminum, titanium, tin, and so on as the dielectric materials with high crystallinity.

[0082] Among them, the zinc oxide containing aluminum is particularly preferable in points of crystallinity, film-forming rate, and economic efficiency. When aluminum is contained in the zinc oxide, it is contained as an aluminum oxide (AI2O3) or as a composite oxide of zinc and aluminum as described above. A content of aluminum in the zinc oxide containing aluminum is preferably 1 to 10 mass%, and more preferably 1 to 5 mass% in a 20 total amount (in 100 mass%) of zinc and aluminum.

[0083] Thicknesses of the first to fourth crystalline dielectric layers 212, 231, 233 and 251 are preferably 3 to 15 nm independently. The thickness of each of the crystalline dielectric layers 212, 231, 233 and 251 is set to 3 nm or more, and thereby, it is possible to accelerate the crystallization, and to homogenize and densify the first and second metal layers 22, 24 formed therebetween. When the thickness of each of the crystalline dielectric layers 212, 231, 233 and 251 is 15 nm, it is enough to accelerate the crystallization, and when the thickness is set to be 15 nm or less, it is possible to suppress that properties of the first and second metal layers 22, 24 are lowered due to roughness of 24

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2016213183 06 Jun 2019 surfaces of the crystalline dielectric layers 212, 231, 233 and 251. The thickness of each of the crystalline dielectric layers 212, 231,233 and 251 is more preferably 5 to 11 nm from viewpoints of homogenizing and densifying the first and second metal layers 22, 24 and enabling good properties.

[0084] Note that the first barrier layer 26 and the second barrier layer 27 are respectively disposed at the surface sides of the first and second metal layers 22, 24 so as to be in contact with each metal layer. Accordingly, the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251 respectively disposed at the surface sides of the first and second metal layers 22, 24 from among the first to fourth crystalline dielectric layers 212, 231, 233 and 251 are respectively disposed at the surface sides of the first and second metal layers 22, 24 through the first barrier layer 26 and the second barrier layer 27. However, it is possible to sufficiently achieve functions to homogenize and densify the first and second metal layers 22, 24 by being used together with the first crystalline dielectric layer 212 and the third crystalline dielectric layer 233 respectively disposed at the glass plate sides of the first and second metal layers 22, 24.

[0085] The first, second and third amorphous dielectric layers 211, 232 and 252 are amorphous dielectric layers respectively disposed between, upward or downward of the first to fourth crystalline dielectric layers 212, 231, 233 and 251 provided to sandwich the first and second metal layers 22, 24. In the amorphous dielectric layers, crystal grains are 20 not grown, and therefore, it becomes possible to secure flatness as a whole of the stacked film 2B by providing the amorphous dielectric layers between, upward or downward of the crystalline dielectric layers.

[0086] As composing materials of the amorphous dielectric layers 211, 232 and 252, it is possible to use by appropriately selecting amorphous dielectric materials from among the dielectric materials described above as the materials composing the dielectric layers 21, 23, 25 and so on in the stacked film 2A. Among the dielectric materials described above, specifically, there are preferably used the zinc oxide containing the oxide constituent element other than zinc such as tin, aluminum and titanium for 10 mass% or more, or the

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2016213183 06 Jun 2019 like as the amorphous dielectric materials.

[0087] Among them, the zinc oxide containing tin is particularly preferable from points of amorphousness and economic efficiency. When tin is contained in the zinc oxide, it is contained as the tin oxide (SnCh) or a composite oxide of zinc and tin. A content of tin in the zinc oxide containing tin is preferably 20 to 80 mass%, and more preferably 30 to 70 mass% in a total amount (in 100 mass%) of zinc and tin so as to obtain sufficient amorphousness.

[0088] In thicknesses of the first, second and third amorphous dielectric layers 211, 232, 252, the thicknesses of the first and third amorphous dielectric layers 211, 252 are preferably 5 to 45 nm independently, and more preferably 10 to 35 nm. Besides, as the thickness of the second amorphous dielectric layer 232 sandwiched between the second crystalline dielectric layer 231 and the third crystalline dielectric layer 233, it is set such that the thickness of the second dielectric layer 23 is in each of the thickness ranges in each of the cases in consideration that the stacked film 2B belongs either to the stacked film (X) or the stacked film (Y).

[0089] When the stacked film 2B is the stacked film (X) and the metal M content in the first metal layer 22 is 9 mass% or more, the thickness of the second amorphous dielectric layer 232 is preferably 30 to 100 nm, and more preferably 40 to 80 nm. When the stacked film 2B is the stacked film (X) and the metal M content in the first metal layer

22 is 6 mass% or more and less than 9 mass%, the thickness of the second amorphous dielectric layer 232 is preferably 50 to 90 nm, and more preferably 60 to 90 nm. When the stacked film 2B is the stacked film (Y), the thickness of the second amorphous dielectric layer 232 is preferably 50 to 85 nm, and more preferably 60 to 85 nm. [0090] The thicknesses of the first, second and third amorphous dielectric layers 211,

232, 252 are respectively set to the above-stated ranges, and thereby, it is possible to increase the visible light transmittance and to appropriately reduce a film-formation time to have good productivity while securing the flatness as a whole of the stacked film 2B. [0091] The first barrier layer 26 and the second barrier layer 27 are respectively

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2016213183 06 Jun 2019 provided to suppress oxidation of the first metal layer 22 and the second metal layer 24 at the formation time of the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251.

[0092] Composing materials of the first barrier layer 26 and the second barrier layer

27 are not particularly limited as long as it is possible to suppress the oxidation. As the composing materials of the first and second barrier layers 26, 27, there can be cited, for example, titanium, a zinc-aluminum alloy, a nickel-chromium alloy, or one containing an oxide of the above and formed of a metal or an oxide where oxygen is lacked relative to a stoichiometric composition. The material is set to be formed of the metal or the oxide where oxygen is lacked relative to the stoichiometric composition, and thereby, it is possible to suppress the oxidation of the first metal layer 22 at the formation time of the second crystalline dielectric layer 231 and the oxidation of the second metal layer 24 at the formation time of the fourth crystalline dielectric layer 251, respectively.

[0093] A material containing titanium or a titanium oxide as a main component is preferable as the first and second barrier layers 26, 27. The material containing the titanium oxide as the main component is one containing titanium for 50 atom% or more in a total amount (100 atom%) of titanium and an oxide constituent element (except oxygen) other than titanium.

[0094] It is possible that constituent elements other than titanium can be contained in the first and second barrier layers 26, 27. As the constituent elements other than titanium, there can be cited, for example, niobium, tantalum, zirconium, silicon, tungsten and molybdenum, and one kind or two or more kinds among the above can be contained. In an oxidation preventing barrier layer, titanium, niobium, tantalum, tungsten and molybdenum are contained as, for example, TiOx (x < 2), hfeOx (x < 5), Ta₂O_x (x < 5),

ZrOx (x < 2), SiOx (x < 2), WOx (x < 3), MoOx (x < 3), or as a composite thereof.

[0095] When the constituent elements other than titanium are contained in the first and second barrier layers 26, 27, the constituent elements other than titanium are preferably set to 30 atom% or less, more preferably set to 20 atom% or less, and further preferably set to

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2016213183 06 Jun 2019 atom% or less in a total amount (100 atom%) of titanium and the constituent elements other than titanium from a viewpoint of reducing a material cost. The first and second barrier layers 26, 27 are each preferably formed of only titanium or the titanium oxide, and particularly preferably formed of only TiOx (1 < x < 2) being the oxide where oxygen is lacked relative to the stoichiometric composition.

[0096] Note that a part or all of the first and second barrier layers 26, 27 are respectively oxidized at the formation times of the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251. Accordingly, after the formation of the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251, they are not necessarily constituted of the oxide where oxygen is lacked relative to the stoichiometric composition, and for example, they may be each constituted of an oxide layer having the stoichiometric composition formed by oxidation and a non-oxide layer remained without being oxidized, or constituted of only the oxide layer having the stoichiometric composition formed by oxidation.

[0097] Thicknesses of the first and second barrier layers 26, 27 are preferably 1 nm or more independently. The thickness of each of the first and second barrier layers 26, 27 is set to 1 nm or more, and thereby, it is possible to effectively suppress the oxidation of the first metal layer 22 and the second metal layer 24. The thickness of each of the first and second barrier layers 26, 27 is not particularly limited as long as it is 1 nm or more, and it is enough to suppress the oxidation of the first metal layer 22 and the second metal layer if the thickness is 10 nm, and the visible light transmittance can be effectively increased by setting the thickness to be 10 nm or less.

[0098] The protective layer 28 has a function to increase durability of the stacked film 2B, particularly an abrasion resistance of a surface, and a function as a barrier for moisture, 25 and oxygen during heat treatment. As the protective layer 28, it is not particularly limited as long as the above-stated functions are improved. For example, the protective layer 28 containing the oxynitride of titanium, silicon, aluminum or the like as a main component is preferable. Further, a carbon layer containing carbon as a main component capable of

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2016213183 06 Jun 2019 improving the abrasion resistance from the film-formation to the heat treatment may be provided at an uppermost surface of the protective layer 28 though it is disappeared when the heat treatment is performed. On the other hand, in a non-heat-treated product before the heat treatment, it is preferable that the protective layer 28 is previously set to be a layer containing the titanium oxide as a main component.

[0099] A thickness of the protective layer 28 is preferably 1 nm or more. When the thickness of the protective layer 28 is 1 nm or more, the durability is effectively improved. When the thickness of the protective layer 28 is 15 nm, it is enough to secure the durability, and productivity of the protective layer 28 improves by setting the thickness to be 15 nm or 10 less. The thickness of the protective layer 28 is more preferably 10 nm or less, and further preferably 6 nm or less.

[0100] (Manufacturing of glass plate with stacked film)

Manufacturing of the glass plate with the stacked film of the embodiment includes: a forming process forming respective layers constituting a stacked film in sequence on one 15 principal surface of a glass plate whose principal surface is larger than a glass plate with a stacked film to be manufactured by a common procedure; and a cutting process cutting the glass plate with the stacked film after the forming process into a desired size with rectangular principal surfaces. Strengthening of the glass plate in the glass plate with the stacked film is normally carried out by the air-cooling tempering, specifically, carried out 20 by performing the heat treatment (heat treatment process) after stacking the respective layers. As an order of each process, it is essential to perform the cutting process after the forming process. An order of the heat treatment is no object, but it is preferable to perform the heat treatment after the cutting process.

[0101] When the stacked film is formed, the principal surface of the glass plate where 25 the stacked film is formed is clean processed, and the respective layers of the stacked film are sequentially formed on this principal surface. A forming method is not particularly limited, and there can be applied physical vapor deposition methods (a vacuum deposition method, an ion plating method, a sputtering method), chemical vapor deposition methods

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2016213183 06 Jun 2019 (a thermal CVD method, a plasma CVD method, a photo-CVD method), an ion beam sputtering method, and so on. When an area of the glass plate is large, a direct current or an alternating current dual sputtering method is preferable because uniformity of the thickness is easy to control, and it is excellent in productivity.

[0102] Hereinafter, the forming method of the respective layers are concretely explained while using the glass plate with the stacked filmlOA illustrated in Fig. 3 and the glass plate with the stacked film 10B illustrated in Fig. 4 as examples. Note that the glass plates with the stacked film 10A, 10B in Fig. 3 and Fig. 4 are each illustrated under an already cut state, but actually, the respective layers are formed on one principle surface of a glass plate whose principal surface is larger than the glass plate with the stacked film to be manufactured.

[0103] The forming method of the first, second and third dielectric layers 21, 23, 25 in the stacked film 2A of the glass plate with the stacked filmlOA is not particularly limited. For example, they can be formed by selecting a sputtering target and atmosphere gas in accordance with the composing materials, and performing the sputtering by a common procedure. When these dielectric layers are provided as, for example, metal oxide layers, they can be formed by using a metal target as the sputtering target, and performing reactive sputtering in sputtering gas where a concentration of oxidizing gas is made sufficiently high. As the metal target, for example, the metal target containing zinc is suitably used.

[0104] It is possible that the oxide constituent element other than zinc can be contained in the metal target containing zinc. As the oxide constituent element other than zinc, there can be cited, for example, tin, aluminum, chromium, titanium, silicon, boron, magnesium, gallium, and one kind or two or more kinds can be contained. When the oxide constituent element other than zinc is contained, it is preferable that the oxide constituent element other than zinc is set to 1 to 50 mass% in a total amount (100 mass%) of zinc and the oxide constituent element other than zinc.

[0105] When the first to fourth crystalline dielectric layers 212, 231, 233, 251 in the stacked film 2B of the glass plate with the stacked film 10B are each formed as, for

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2016213183 06 Jun 2019 example, the zinc oxide layer containing aluminum, it is possible to form by using a metal target containing zinc and aluminum at a desired ratio, for example, containing aluminum for 1 to 10 mass% in a total amount (100 mass%) of zinc and aluminum, and performing the reactive sputtering.

[0106] Similarly, when the first, second and third amorphous dielectric layers 211, 232,

252 in the stacked film 2B of the glass plate with the stacked film 10B are each formed as, for example, the zinc oxide layer containing tin, it is possible to form by using a metal target containing zinc and tin at a desired ratio, for example, containing tin for 30 to 70 mass% in a total amount (100 mass%) of zinc and tin, and performing the reactive sputtering.

[0107] The forming method of the first metal layer 22 and the second metal layer 24 is not also particularly limited. For example, it is possible to form the first metal layer 22 and the second metal layer 24 by using a target which contains silver as a main component and contains at least one kind of metal M selected from palladium, gold, chromium, cobalt and nickel in a predetermined proportion relative to a total amount of silver and the metal M as a sputtering target, and by performing sputtering under an atmosphere containing only inert gas such as argon.

[0108] Specifically, when the stacked film has the constitution of the stacked film (X), there is used a target containing silver as the main component and the metal M in a proportion of 6 mass% or more relative to the total amount of silver and the metal M as the sputtering target used for the formation of the first metal layer 22, and there is used a target containing silver as the main component as the sputtering target for the second metal layer 24. When the stacked film has the constitution of the stacked film (Y), there are used targets which contain silver as the main component and the metal M in the proportion of

1.5 mass% or more relative to the total amount of silver and the metal M independently as each of the sputtering target used for the forming of the first metal layer 22 and the sputtering target for the second metal layer 24, and a total of contents of the metal M content (mass%) relative to the total amount of silver and the metal M in the first metal

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2016213183 06 Jun 2019 layer 22 and the metal M content (mass%) relative to the total amount of silver and the metal M in the second metal layer 24 becomes 4 mass% or more,.

[0109] It is preferable to form the first barrier layer 26 and the second barrier layer 27 by performing sputtering while using a metal target such as titanium or a reducing oxide 5 target, and by using inert gas as the sputtering gas.

[0110] When the stacked film 2B of the glass plate with the stacked film 10B includes, for example, a titanium oxynitride layer as the protective layer 28, the titanium oxynitride layer is obtained by, for example, performing heat treatment as described later on a titanium nitride layer formed as described below. It is possible to form the titanium 10 nitride layer by performing sputtering while using a titanium target and under an atmosphere of sputtering gas composed of mixed gas of argon and nitrogen. Besides, for example, when a carbon layer containing carbon as a main component is held as the protective layer 28, the carbon layer may be formed by performing sputtering while using a carbon target and under an atmosphere containing only inert gas such as argon.

[0111] After the stacked film is formed, the glass plate with the stacked film is cut so as to be a desired production shape. The glass plate where the stacked film is formed is cut, and therefore, the stacked film is not provided at two or more end faces in the glass plate with the stacked film according to an embodiment of the present invention.

According to a method where the film-formation is performed after it is cut into the production shape, the stacked film is formed also on the glass plate end faces.

[0112] A non-heat-treated product of the glass plate with the stacked film is thereby obtained. When the glass plate with the stacked film of the embodiment is obtained by performing the heat treatment on the non-heat-treated product obtained as stated above, the non-heat treated product is treated as a precursor, and the glass plate with the stacked film 25 obtained by performing heat treatment is made to be the glass plate with the stacked film according to an embodiment of the present invention.

[0113] When the glass plate with the stacked film is obtained as a heat-treated product, the obtained precursor of the glass plate with the stacked film is heated by a heating

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2016213183 06 Jun 2019 furnace at a heating temperature according to purposes, for example, the heating temperature for tempering and the heating temperature for bending for a predetermined time. For example, when the air-cooling tempering of a glass substrate is performed as for the precursor of a glass plate with a stacked film using a float glass substrate as the glass plate, the heat treatment is preferably performed at 500 to 700° C as a surface temperature of the precursor of the glass plate with the stacked film for 1 to 30 minutes. [0114] Besides, there are known, for example, the following method as the forming method of the first metal layer 22 and the second metal layer 24. Two kinds of metal targets containing silver and the metal M are prepared such that the metal M contents are different. There is obtained a precursor of a metal layer where metal films having different metal M contents are stacked by using the obtained two kinds of targets such that a film thickness and the metal M content become desired values as a finally obtained metal layer. This precursor is burned, and thereby, there is obtained a metal layer containing silver as the main component and containing a predetermined amount of metal M as one layer having a uniform composition.

[0115] In the glass plate with the stacked film of the embodiment, when other layers constituting the stacked film are formed similar to the above, and the metal layer is formed according to the above-stated method, there is obtained a precursor of the glass plate with the stacked film where at least the metal layer is not in a final mode by cutting into a rectangle having a desired size after the film-formation. As a condition to burn the precursor of the glass plate with the stacked film such that the metal layers becomes one layer having a uniform composition, a burning condition at 500 to 700° C as a surface temperature of the precursor of the glass plate with the stacked film is preferable. [0116] It is preferable that the glass plate with the stacked film according to an embodiment of the present invention has a haze value of 2% or less also in a case when the heat treatment under a temperature condition of, for example, 600° C or more is performed during the manufacturing process.

[0117] Use of the glass plate with the stacked film according to an embodiment of the

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2016213183 06 Jun 2019 present invention is not limited. For example, it can be used as composing members of a low-emissivity laminated glass and double glazing glass. It is preferable to be used as the composing member of the double glazing glass.

[0118] As the laminated glass, there can be cited, for example, a laminated glass having a constitution where two pieces of oppositely arranged transparent substrates sandwich an intermediate film, and are adhered by the intermediate film. It is possible to use the glass plate with the stacked film of the embodiment as one of the transparent substrates of the laminated glass as stated above. In this case, the stacked film is used by being arranged at the intermediate film side. The other transparent substrate is preferably 10 a transparent glass plate. When the laminated glass is used as window glass, it is used by setting the glass plate with the stacked film side at the outdoor side. Note that the laminated glass may be one having three pieces or more of transparent substrates.

[0119] As the double glazing glass, there can be cited, for example, double glazing glass having a constitution where two pieces of oppositely arranged transparent substrates 15 are sealed through a spacer at a peripheral part, and a cavity is formed between the opposing transparent substrates. It is possible to use the glass plate with the stacked film of the embodiment as one of the transparent substrates of the double glazing glass as stated above. In this case, the stacked film is disposed at the cavity side. The other transparent substrate is preferably a transparent glass plate. Besides, the cavity is preferably the air 20 cavity or the cavity filled with inert gas such as argon. When the double glazing glass as stated above is used as window glass, it is used by setting the glass plate with the stacked film side at the outdoor side. Note that the double glazing glass may be one having three pieces or more of transparent substrates.

[0120] [Double glazing glass]

The double glazing glass according to the embodiment of an present invention is constituted by using the glass plate with the stacked film of the embodiment as one transparent substrate of the double glazing glass, and a second transparent glass plate as the other transparent substrate. Fig. 2 illustrates the sectional view of the example of the

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2016213183 06 Jun 2019 double glazing glass according to an embodiment of the present invention. The double glazing glass 3 is an example using the glass plate with the stacked film 10 as the composing member, and the stacked film 2 surface of the glass plate with the stacked filmlO is separately disposed to oppose to one principal surface of the second transparent glass plate 32. Besides, the double glazing glass 3 includes the cavity 34 between the glass plate with the stacked filmlO and the second transparent glass plate 32 by the spacer 33 arranged at the periphery of both.

[0121] The double glazing glass according to the embodiment of an present invention has properties of the following (1-b), (2-b) and (3-b).

(1-b) A solar heat gain coefficient (g value) measured at the second transparent glass plate side for solar radiation from the glass plate with the stacked film side based on IS09050:2003 is 0.265 or less.

(2-b) A value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding transmitted light obtained by irradiating visible light defined in IS09050:2003.

(3-b) A visible light reflectance measured at the glass plate with the stacked film side based on IS09050:2003 is 20% or less.

[0122] The properties of (1-b) to (3-b) are properties respectively corresponding to (1-a) to (3-a) in the evaluation of the glass plate with the stacked film according to the embodiment of an present invention. Regarding (1-b) to (3-b) in the double glazing glass 20 according to an embodiment of the present invention, preferable ranges are the same as the preferable ranges in (1-a) to (3-a). Further, the double glazing glass according to an embodiment of the present invention preferably has properties corresponding to (4-a) to (8-a) in the evaluation of the glass plate with the stacked film according to an embodiment of the present invention, and is particularly preferably in preferable ranges in these properties.

[0123] While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the embodiments described herein may be embodied in a variety of other forms;

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2016213183 06 Jun 2019 furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the inventions. For example, the glass plate with the stacked film is suitable for building, and it is not necessarily limited to the building use, and can be used for vehicles such as an automobile or the like in an applicable range.

EXAMPLES [0124] Hereinafter, the glass plate with the stacked film of an embodiment of the present invention is specifically explained with reference to examples. Note that the present invention is not limited thereto. Examples 1, 2, 8 are examples, and examples 3 to 7 are comparative examples.

[0125] (Examples 1 to 8)

Each of glass plates each with stacked film of 1 to 8 having a constitution illustrated in Table 1 was manufactured as the glass plate with the stacked film. That is, a soda-lime glass plate (manufactured by Asahi Glass Co., Ltd., (FL5, FL6), 100 mm x 180 mm x5 mmt, 100 mm χ 180 mm x 6 mmt) was used as the glass plate, a precursor of a stacked film was formed on one principal surface thereof by a DC sputtering method according to the following methods, and thereafter, it was cut and burned to thereby form each film to have a film constitution and a thickness as illustrated in Table 1, to manufacture a glass plate with a stacked film having the stacked film on one principal surface of the glass plate and not having the stacked film at four end faces.

[0126] In Table 1, the glass plate, and respective films of the stacked film are illustrated in a stack order from a left side. Each layer was represented by composing materials and thicknesses each indicated by a numeric character in parentheses (a unit of 25 each thickness is [nm]). Besides, abbreviations of the composing materials according to the examples 1 to 8 illustrated in Table 1 have the following meaning, and a thickness of a layer without any indication of thickness is also as described below. Note that the each of glass plates each with stacked film of 1 to 8 is each the glass plate with the stacked film

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2016213183 06 Jun 2019 having the same constitution as the glass plate with the stacked film 10B whose cross section is illustrated in Fig. 4.

[0127] FL5; manufactured by Asahi Glass Co., Ltd., soda line glass plate, FL5 (5 mmt)

FL6; manufactured by Asahi Glass Co., Ltd., soda line glass plate, FL6 (6 mmt)

SZO; an oxide layer of zinc and tin (SnZn oxide layer)

AZO; an oxide layer of zinc and aluminum (AlZn oxide layer), with a layer thickness of 10 nm when the thickness is not illustrated.

AgPd; a layer where palladium is doped into silver, a latter numeric character of AgPd in

Table 1 indicates a proportion (mass%) of palladium relative to a total amount of palladium and silver.

TiOx; a layer formed of a titanium oxide at a stoichiometric composition ratio or a non-stoichiometric composition ratio, with a layer thickness of 4 nm when the thickness is not illustrated.

TiOxNy; a layer formed of a titanium oxynitride at a stoichiometric composition ratio or a non-stoichiometric composition ratio, with a layer thickness of 3.5 nm when the thickness is not illustrated.

[0128] (1) Formation of stacked film precursor

In the examples 1 to 8, the precursor of the stacked film is formed on the glass plate as a thin-film stacked part by sequentially forming a first oxide layer of zinc and tin (an SnZn oxide layer), a first oxide layer of zinc and aluminum (an AlZn oxide layer), a first silver palladium 1 layer (an AgPdl layer = a layer containing Pd for 1 mass% relative to a total amount of Ag and Pd) or a first silver palladium 1 layer (the AgPdl layer) and a silver palladium 30 layer (an AgPd30 layer = a layer containing Pd for 30 mass% relative to a total amount of Ag and Pd), a first titanium layer (a Ti barrier layer), a second oxide layer of zinc and aluminum, a second oxide layer of zinc and tin, a third oxide layer of zinc and aluminum, a second silver palladium 1 layer (the AgPdl layer) or a second silver palladium 1 layer (the AgPdl layer) and the silver palladium 30 layer (the AgPd30 layer),

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2016213183 06 Jun 2019 a second titanium layer, a fourth oxide layer of zinc and aluminum, a third oxide layer of zinc and tin, and a titanium nitride layer (an TiNx layer) according to the following method.

[0129] At an inline-type sputtering apparatus used for the sputtering, there are placed a titanium target (a Ti target), a target formed of a zinc alloy containing 50 mass% of tin (an

SnZn alloy target), a target formed of a zinc alloy containing 2 mass% of aluminum (an

AlZn alloy target), a silver target containing 1 mass% of palladium (an AgPdl target), and a silver target containing 30 mass% of palladium (an AgPd30 target) on a cathode in a film-forming chamber. Then, a cleaned glass plate is introduced into a load-lock chamber, 10 and a whole of a vacuum chamber is evacuated to 2.0 x 10^-4 Pa to form each layer as described below.

[0130] <SnZn oxide layer>

SnZn oxide layer was formed by introducing argon and oxygen as discharge gas into the vacuum chamber at 30 : 70 seem, and by performing a reactive DC magnetron sputtering 15 while using the SnZn alloy target. The sputtering target was 70 x 200 mm², and 500 W was applied as a sputtering power. At this time, a pressure in the vacuum chamber was

0.4 Pa.

[0131] <AlZn oxide layer>

AlZn oxide layer was formed by introducing oxygen as the discharge gas into the vacuum 20 chamber at 100 seem, and by performing a DC magnetron sputtering while using the AlZn alloy target. The sputtering target was 70 x 200 mm², and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. All of thicknesses of the AlZn oxide layers were set to 10.0 nm.

[0132] <AgPdl layer>

AgPdl layer was formed by introducing argon as the discharge gas into the vacuum chamber at 50 seem, and by performing the DC magnetron sputtering while using the AgPdl target. The sputtering target was 70 x 200 mm², and 100 W was applied as the sputtering power.

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2016213183 06 Jun 2019 [0133] <AgPd layer>

AgPdl layer and AgPd30 layer were formed by introducing argon as the discharge gas into the vacuum chamber at 50 seem, and by performing the DC magnetron sputtering continuously using the AgPdl target and the AgPd30 target in sequence. The sputtering targets were each 70 x 200 mm², and 100 W was applied as the sputtering power. The continuously formed AgPdl layer and AgPd30 layer became one AgPd layer by the following heat treatment (burning) after the stacked film precursor was formed on the glass plate, and a total of respective film thicknesses was set as a final AgPd layer film thickness.

[0134] <Ti barrier layer>

Ti barrier layer was formed by introducing argon as the discharge gas into the vacuum chamber at 100 seem, and by performing the DC magnetron sputtering while using the Ti target. The sputtering target was 70 x 200 mm², and 50 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. All of thicknesses 15 of the Ti barrier layers were set to 4.0 nm. Note that the Ti barrier layer is a layer existing as a TiOx layer in the finally obtained stacked film of the glass plate with the stacked film.

[0135] <Ti nitride layer>

Ti nitride layer was formed by introducing argon and nitrogen as the discharge gas into the vacuum chamber at 70 : 30 seem, and by performing the DC magnetron sputtering while using the Ti target. The sputtering target was 70 x 200 mm², and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. All of thicknesses of the TiNx layers were set to 3.5 nm. Note that the TiNx layer is a layer existing as a TiOxNy layer in the finally obtained stacked film of the glass plate with the stacked film.

[0136] (2) Cutting

The obtained glass plates each with the precursor of the stacked film were each cut with a glass cutter to be a rectangle with principal surfaces size of 70 mm x 100 mm, and there were obtained precursor examples 1 to 8 of the glass plates each with the stacked film

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2016213183 06 Jun 2019 having the precursor of the stacked film on one principal surface of the glass plate and not having the precursor of the stacked film at four end faces of the glass plate.

[0137] (3) Burning (heat treatment)

The manufactured precursor examples 1 to 7 of the glass plates each with the stacked film were burned at a setting temperature of 700° C for five minutes by using a desktop electric furnace, and the precursor example 8 was burned at the setting temperature of 750°C for four minutes, to obtain the glass plates each with the stacked film of the examples 1 to 8 whose stacked constitutions were illustrated in Table 1. A maximum attained temperature at the glass plate surface at this time was 650°C. A Pd content (mass% of Pd relative to the total amount of Ag and Pd) in the AgPd layer after the burning was measured by using a fluorescent X-ray “ZSX-lOOe” manufactured by Rigaku Corporation or an ICP-OES “SPS3100” manufactured by Hitachi High-Technologies Corporation. [0138] [Table 1]

Example	Stacking configuration of glass plate with stacked film
1	FL5/SZO(22)/AZO/AgPd 10.5( 14)/TiOx/AZO/SZO(79)/AZO/AgPd9.7( 17)/TiOx/AZO/SZO( 17)/TiOxNy
2	FL5/SZO(22)/AZO/AgPd 15.5(14)/TiOx/AZO/SZO(82)/AZO/AgPd 1 (19)/TiOx/AZO/SZO(21 )/TiOxNy
3	FL5/SZO(22)/AZO/AgPd5.7(l 4)/TiOx/AZO/SZO(79)/AZO/AgPd5.3 (17)/TiOx/AZO/SZO( 17)/TiOxNy
4	FL5/SZO(22)/AZO/AgPd8.3 (14)/TiOx/AZO/SZO(82)/AZO/AgPd 1 (19)/TiOx/AZO/SZO(2 l)/TiOxNy
5	FL5/SZO(22)/AZO/AgPd 1(11 )/TiOx/AZO/SZO(89)/AZO/AgPd 10.4(22)/TiOx/AZO/SZO( 15)/TiOxNy
6	FL5/SZO(22)/AZO/AgPdl(13)/TiOx/AZO/SZO(85)/AZO/AgPdl(24)/TiOx/AZO/SZO(21)/TiOxNy
7	FL5/SZO(3 2)/AZO/AgPd 1(13 )/TiOx/AZO/SZO(8 5)/AZO/AgPd 1 (18)/TiOx/AZO/SZO(21 )/TiOxNy
8	FL6/SZO(29)/AZO/AgPd9(16)/TiOx/AZO/SZO(59)/AZO/AgPd2.5(15)/TiOx/AZO/SZO(18)/TiOxNy

[0139] (Evaluation)

The obtained glass plates each with the stacked film of 1 to 8 were evaluated as follows. Note that in double glazing glass for evaluation described below, double glazing glasses using the glass plates each with the stacked film of the examples 1, 2, 8 are the double glazing glasses according to examples of embodiments of the present invention.

[0140] Performance of the double glazing glass having the following constitution, that

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2016213183 06 Jun 2019 is, the double glazing glass 30 for evaluation having the same constitution as illustrated in Fig. 2 was found by calculation by using spectroscopic measurement results by a spectrophotometer, and emissivity measurement results regarding the glass plates with the stacked films of 1 to 8.

[0141] In the double glazing glass, a case was considered when a transparent glass plate with a thickness of 6 mm was used as a transparent opposite substrate (the second transparent glass plate 32 in the double glazing glass 30) opposed to the glass plate with the stacked film, a thickness of a cavity between the glass plate with the stacked film and the transparent opposite substrate was 12 mm, and air is filled into the cavity. The spectrophotometer measurement was performed by using “U4100” manufactured by HITACHI Corporation. The emissivity was found by using a conversion formula with a measurement result by an FT/IR “Frontier Gold” manufactured by Perkin Elmer Co., Ltd. being an infrared spectrograph found in advance and a surface resistance value (Rs). When a vertical emissivity became less than 0.03 by the conversion formula, the calculation was performed by setting the vertical emissivity as 0.03.

[0142] Note that measurement of the surface resistance value (Rs) of the stacked film surface of each of the glass plates each with the stacked film of 1 to 8 was performed by using a portable surface resistance meter “STRATOMETER” manufactured by NAGY instruments.

[0143] <Double glazing glass; optical characteristics>

There were found the solar heat gain coefficient (g value) at the transparent opposite substrate side for the solar radiation from the glass plate with the stacked film side, the visible light transmittance (Tv), the visible light reflectance (Rv_out) at the glass plate with the stacked film side, and the visible light reflectance (Rvin) at the transparent opposite substrate side regarding the double glazing glasses for evaluation using the glass plates each with the stacked film of 1 to 8. The solar heat gain coefficient (g), the visible light transmittance (Tv) and the visible light reflectance (Rv) were found based on fS09050: 2003.

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2016213183 06 Jun 2019 [0144] <Double glazing glass; optical characteristics (color tone)>

There were found the values of a* and b* in the CIE 1976 L*a*b* chromaticity coordinates obtained by irradiating the visible light defined in IS09050:2003, as for the transmitted light, the reflected light at the glass plate with the stacked film side, and the reflected light at the transparent opposite substrate side regarding each of the double glazing glasses for evaluation using the glass plates each with the stacked film of 1 to 8. [0145] <Double glazing glass; color rendering property>

There was found the color rendering property of the transmitted light evaluated by the average color rendering evaluation index (Ra) using the D65 light source based on JIS

Z8726 (1990) regarding each of the double glazing glasses for evaluation using the glass plates each with the stacked film of 1 to 8.

[0146] <Glass plate with stacked film; haze value>

There was measured a haze value (H (%)) of the glass plates each with the stacked film of to 8. The haze measurement was performed by using a haze meter “HZ-2” manufactured by Suga Test Instruments Co., Ltd..

[0147] <Glass plate with stacked film; humidity resistance>

There was visually observed the number of white spots each of whose diameter was 0.5 mm or more observed in a predetermined range at the stacked film surface after performing the humidity resistance test where the glass plates each with the stacked film of 1 to 8 were 20 kept under conditions of 50° C, 90% RH for two weeks. A case when the number of the white spots per a range of 100 mm x 100 mm was five pieces or less was evaluated as “o”.

Evaluation results obtained in the above are illustrated in Table 2.

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2016213183 06 Jun 2019 [0148] [Table 2]

Example	Double glazing glass	Glass plate with stacked film
g value	Ra (%)	Transmitted light	Reflected light (glass plate with stacked film side)	Reflected light (opposite substrate side)	H(%)	Humidity resistance test
Tv (%)	a*	b*	RVout (%)	a	b*	Rv_in(%)	a*	b*
1	0.259	93.7	38.1	-2.5	-3.1	11.8	-0.5	-21.2	14.6	-6.2	-0.7	0.15	o
2	0.250	87.4	42.9	-7.9	0.6	19.1	-12.2	-17.7	14.7	15.7	-1.5	0.13	o
3	0.294	97.8	47.1	-2.2	5.5	19.4	-7.2	-16.4	20.2	-6.6	-1.0	0.15	o
4	0.280	95.6	50.0	-4.0	10.3	24.9	-12.4	-15.5	18.2	0.3	-16.6	0.15	o
5	0.260	97.4	40.5	-1.2	5.4	14.6	-8.6	-24.6	26.5	-8.2	11.9	0.21	o
6	0.245	92.7	51.1	-1.8	16.4	26.4	-14.0	-22.9	28.3	-6.6	-10.5	0.15	o
7	0.334	95.7	62.1	-2.8	11.4	19.5	-7.7	-20.7	20.1	-5.7	-12.1	0.11	o
8	0.249	94.2	41.8	-3.7	-1.3	15.7	0.2	-13.7	12.2	-4.8	-11.9	0.09	o

EXPLANATION OF REFERENCE SIGNS [0149] 10 ... glass plate with stacked film, 1 ... glass plate (first transparent glass plate),

2 ... stacked film, 3 ... double glazing glass, 32 ... second transparent glass plate, 33 ...

spacer, 34 ... cavity, 10A, 10B ... glass plate with stacked film, 2A, 2B ... stacked film, 21 ... first dielectric layer, 22 ... first metal layer, 23 ... second dielectric layer, 24 ... second metal layer, 25 ... third dielectric layer, 26 ... first barrier layer, 27 ... second barrier layer, 28 ... protective layer.

[0150] It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

[0151] In the claims which follow and in the preceding description, except where the context requires otherwise due to express language or necessary implication, the word “comprise” and 15 “contain” or variations such as “comprises”, “comprising”, “contains” or “containing” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments.

Claims

1. A glass plate with a stacked film comprising:

a strengthened glass plate having rectangular principal surfaces; and

5 a stacked film provided on one principal surface of the glass plate and not provided on two or more end faces of the glass plate, wherein the stacked film includes the following properties as a double glazing glass using the stacked film:

in the double glazing glass manufactured by forming the stacked film on one principal

10 surface of a first transparent glass plate with a thickness of 5 mm to be a glass plate with a stacked film for test, separately disposing the glass plate with the stacked film for test and a second transparent glass plate with a thickness of 6 mm through a spacer arranged at a periphery such that a stacked film surface of the glass plate with the stacked film for test opposes to one principal surface of the second transparent glass plate, to have an air cavity with a thickness of

15 12 mm between the glass plate with the stacked film for test and the second transparent glass plate, a solar heat gain coefficient (g value) measured at the second transparent glass plate side for solar radiation from the glass plate with the stacked film for test side based on IS09050:2003 is 0.265 or less;

20 a value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding transmitted light obtained by irradiating visible light defined in IS09050:2003; and a visible light reflectance measured at the glass plate with the stacked film for test side based on IS09050:2003 is 20% or less.

25

2. The glass plate with the stacked film according to claim 1, wherein the stacked film includes n-layers (n is an integer of two or more) of metal layers each including silver as a main component, and n+1 layers of dielectric layers respectively stacked to sandwich the metal layers, and

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2016213183 06 Jun 2019 the stacked film satisfies either one of the following two configurations, a first metal layer nearest to the glass plate among the metal layers including at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6 mass% or more relative to a total amount of silver and the metal, where when the proportion

5 is less than 9 mass%, a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the glass plate is 100 nm or less, and the first metal layer and at least one layer among the metal layers other than the first metal layer each including at least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 1.5 mass% or more relative to a total amount of silver and

10 the metal, a total content of the metals in the metal layers each including the metal in the proportion of 1.5 mass% or more is 4 mass% or more, and a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the glass plate is 95 nm or less.

3. The glass plate with the stacked film according to claim 1 or claim 2,

15 wherein the stacked film does not include a nitride layer or an oxynitride layer between the metal layer nearest to the stacked film surface and the glass plate.

4. A double glazing glass, comprising:

a glass plate with a stacked film which includes a strengthened first glass plate having rectangular principal surfaces; and a stacked film provided on one principal surface of the first

20 glass plate and not provided on two or more end faces of the first glass plate; and a second glass plate having rectangular principal surfaces and separately disposed from the glass plate with the stacked film through a spacer, wherein a solar heat gain coefficient (g value) measured at the second glass plate side for solar radiation from the glass plate with the stacked film side based on

25 IS09050:2003 is 0.265 or less;

a value of b* in a CIE 1976 L*a*b* chromaticity coordinates is one or less regarding transmitted light obtained by irradiating visible light defined in IS09050:2003; and

11399142_1 (GHMatters) P106128AU

2016213183 06 Jun 2019 a visible light reflectance measured at the glass plate with the stacked film side based on IS09050:2003 is 20% or less.

5. The double glazing glass according to claim 4, wherein a visible light reflectance measured at the second glass plate side based

5 on IS09050:2003 is 20% or less.

6. The double glazing glass according to claim 4 or claim 5, wherein a color rendering property of transmitted light evaluated by an average color rendering evaluation index (Ra) using a D65 light source based on JIS Z8726 (1990) is 85% or more.

10

7. The double glazing glass according to any one of claims 4 to 6, wherein both values of a* and b* in the CIE 1976 L*a*b* chromaticity coordinates are two or less regarding each reflected light obtained by irradiating visible light defined in IS09050:2003 at the glass plate with the stacked film side and the second glass plate side.

15

8. The double glazing glass according to any one of claims 4 to 7, wherein a visible light transmittance measured based on IS09050:2003 is 30% or more.

9. The double glazing glass according to any one of claims 4 to 8, wherein a difference between the visible light reflectance measured at the glass

20 plate with the stacked film side and the visible light reflectance measured at the second glass plate side based on IS09050:2003 is 10% or less.

10. The glass plate according to any one of claims 1 to 3, wherein:

the stacked film includes n-layers (n is an integer of two or more) of metal layers that include silver as a main component, and n+ 1 layers of dielectric layers stacked to

25 sandwich the metal layers, each of the first metal layer nearest to the glass plate among the metal layers and at least one layer from among the metal layers other than the first metal layer, independently, includes at least one kind of metal selected from palladium, gold,

11399142_1 (GHMatters) P106128AU

2016213183 06 Jun 2019 chromium, cobalt and nickel in a proportion of 1.5 mass% or more relative to the total amount of silver and the metal, a total of the contents of the metal in the metal layer including the metal in the proportion of 1.5 mass% or more is 4 mass% or more, and

5 a thickness of the dielectric layer between the first metal layer and the second metal layer which is the second nearest to the glass plate is 95 nm or less;

each of the dielectric layers has a crystalline dielectric layer and an amorphous dielectric layer;

the crystalline dielectric layers are disposed so as to sandwich the metal layers;

10 the amorphous dielectric layers are disposed between the crystalline dielectric layers, or upward and downward of the crystalline dielectric layers;

the amorphous dielectric layer includes zinc oxide and at least one kind of element selected from tin, aluminum and titanium in a proportion of 10 mass% or more relative to the total amount of zinc and the element.

11. The glass plate according to 15 claim 10, wherein the crystalline dielectric layer that includes zinc oxide also includes aluminum, and a content of aluminum in the zinc oxide that includes aluminum is 1 to 10 mass% relative to the total amount of zinc and aluminum.

12. The glass plate according to claim 10 or 11, wherein the amorphous dielectric layer that includes zinc oxide also includes tin in a proportion of 20 to 80 mass%

20 relative to the total amount of zinc and tin.

13. The glass plate according to any one of claims 10 to 12, wherein a nitride layer is not included between the metal layer nearest to the stacked film surface and the glass plate.

14. The glass plate according to any one of claims 1 to 3, wherein:

25 the stacked film includes n layers (n is an integer of two or more) of metal layers including silver as a main component, and n+ 1 layers of dielectric layers stacked to sandwich the metal layers, a first metal layer nearest to the glass plate among the metal layers includes at

11399142_1 (GHMatters) P106128AU

2016213183 06 Jun 2019 least one kind of metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6 mass% or more relative to a total amount of silver and the metal, when the proportion is less than 9 mass%, a thickness of the dielectric layer between the first metal layer and a second metal layer which is the second nearest to the

5 glass plate is 100 nm or less; and a nitride layer is not included between the metal layer nearest to the stacked film surface and the glass plate.

15. The glass plate according to claim 14, wherein the dielectric layers are oxide layers.